JP2001154317A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method for a silver halide photographic sensitive material having high sensitivity and an improved silver tone. SOLUTION: In the processing method, the silver halide photographic sensitive material with a hydrophilic colloidal layer containing flat platy silver halide grains which satisfy conditions described in this specification is developed with a developing solution containing a polyhydric alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material (hereinafter, also simply referred to as "photosensitive material"), and more particularly to a method for rapidly processing a silver halide photographic light-sensitive material having excellent sensitivity and silver tone.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for shortening the processing time of silver halide photographic materials. For example, in the medical field, regular medical examinations, the spread of medical checkups, etc., and the number of examinations including diagnosis in general medical treatment have increased sharply, which has led to an increase in the number of X-rays taken. Further speeding up of processing is desired.

However, in order to speed up processing, development,
It is necessary to reduce the processing time of each processing step such as fixing, washing, and drying, and the load on each step is increased. For example, if the development time is simply shortened, the conventional light-sensitive material is accompanied by a reduction in image density, that is, a reduction in sensitivity. For this reason, it is necessary to improve the activity of the developing solution or to set the sensitivity of the photosensitive material to a high value in advance.

In recent years, high sensitivity techniques using tabular silver halide grains containing epitaxially deposited silver halide projections having a face-centered cubic lattice structure forming an epitaxy junction have been developed by Journal of Imaging Science (JO).
URNAL OF IMAGINGNG SCIENC
E) Vol. 32, No. 4, No. 7 (1988, No. 8), JP-A No. 8-
No. 171164.

According to this technique, high sensitivity can be achieved by forming silver halide projections which are epitaxially attached to the periphery of the main plane of tabular silver halide grains.
However, this technique has the disadvantage that the deterioration of the image silver tone after the development processing is remarkable, and in particular, is remarkable in rapid processing, and the rapid processing method without the deterioration of the image silver tone after the development processing is considered. Development was urgent.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material having high sensitivity, excellent image and silver tone in rapid processing.

[0007]

The above object of the present invention is attained by the following constitutions.

[0008] 1. Processing of a silver halide photographic material having a hydrophilic colloid layer containing tabular silver halide grains satisfying the following conditions with a developer containing a polyhydric alcohol. Method.

Conditions of Tabular Silver Halide Grains The (1,1,1) plane is the main plane, and the average equivalent circle diameter is 0.1 mm.
5 to 3.0 μm, average thickness of 0.07 to 0.7 μm, including epitaxially deposited silver halide projections of a face-centered cubic lattice structure forming an epitaxy junction, wherein the silver halide projections are Located at the periphery of the grains, between the start of growth and the end of the growth, under the condition that the average intergranular distance shown below has a minimum value, the silver halide protrusions are in the vicinity of the minimum value. Form. The average interparticle distance is (volume of reaction solution / number of growing particles in reaction solution) ^1/3 .

[0010] 2. A silver halide photographic material having a hydrophilic colloid layer containing tabular silver halide grains satisfying the above conditions is treated with a developer containing a compound represented by the following general formula (1). A method for processing a silver halide photographic material. General formula (1) RSO ₃ MR represents a linear or branched alkyl group having 4 to 12 carbon atoms,
M represents a monovalent metal atom.

3. A method for processing a silver halide photographic light-sensitive material, comprising processing with a developer containing the polyhydric alcohol and the compound represented by the general formula (1).

4. Any one of the above items 1 to 3, wherein a silver halide photographic material having a hydrophilic colloid layer containing tabular silver halide grains which has been ultrafiltered from the start of the growth to the end of the growth is processed. 3. The method for processing a silver halide photographic material according to claim 1.

5. 5. The method for processing a silver halide photographic material as described in any one of the above items 1 to 4, wherein the processing is performed with a developer prepared from a solid processing agent.

6. 6. The method for processing a silver halide photographic light-sensitive material as described in any one of the above items 1 to 5, wherein the processing is performed for 90 seconds or less.

Hereinafter, the present invention will be described in more detail. The tabular silver halide grains of the present invention have two opposing parallel main planes, and the main planes are (1,1,1) planes. The average equivalent circle diameter is 0.5 to 3.0 μm, preferably 0.5 to 3.0 μm.
2.0 μm. Average thickness is 0.07 to 0.7 μm
And preferably 0.1 to 0.7 μm. The method for producing these tabular silver halide grains is a known technique, and is disclosed in U.S. Patent Nos. 4,434,226 and 4,43.
9,520, 4,414,310, 5,31
4,793, 5,334,495, 5,35
Nos. 8,840 and 5,372,927.

In the present invention, the term "tabular grains" refers to such tabular silver halide grains prepared by a known technique.

The silver halide grain of the present invention comprises, after preparing a tabular host grain, an epitaxially deposited silver halide projection having a face-centered cubic lattice structure forming the epitaxy junction, The portion is obtained by preparing the portion so as to be located at the peripheral portion of the tabular host particle.

The halogen composition of the tabular host grains of the present invention is preferably any of silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide.

When silver iodide is contained, the silver iodide content is 0.2
It is preferably from 5 to 10 mol%, more preferably from 0.25 to 6 mol%, particularly preferably from 0.4 to 2 mol%.

It is possible to include a small amount of silver chloride in tabular silver halide grains, for example, US Pat.
No. 72,927 describes silver chlorobromide tabular grains having a silver chloride content of 0.4 to 20 mol%.

In the present invention, the average equivalent circle diameter is an average projected area diameter (hereinafter referred to as a particle diameter), and is the average equivalent circle diameter of the projected area of the tabular silver halide grains (the same as that of the silver halide grains). (The diameter of a circle having a projected area), and the average thickness is an average value of the distance between two parallel main planes forming tabular silver halide grains.

The tabular silver halide grains of the present invention are crystallographically classified as twins. Twins are silver halide crystals having one or more twin planes in one grain, and the twins are classified according to a report by Klein and Moiser in Photograph Corspondents (Photograh).
phisher Korespondenz) 99 vol.9
The details are described on page 9, page 100, page 57.

The tabular silver halide grains of the present invention are prepared by forming silver halide projections on the periphery of the tabular host grains.

Here, in the present invention, the peripheral portion of the tabular grain is defined as a line defined by an outer periphery of the main plane of the tabular grain and a set of points whose distance from the outer periphery is 10% of the equivalent circle diameter of the tabular grain. Indicates the range enclosed by.

In the tabular silver halide grains of the present invention, the average distance between grains represented by the following formula during the growth process of the silver halide grains contained in the silver halide emulsion is determined from the start of the growth of the silver halide grains. The silver halide projections are formed at a time near the minimum value until the end of the growth.

In general, the production process of a silver halide emulsion is roughly divided into a nucleation step (consisting of a nucleation step and a ripening step) and a subsequent step of growing the nucleus. It is also possible to separately grow a previously prepared nuclear emulsion (or seed emulsion). The growth process may include several stages such as a first growth process and a second growth process.

In the present invention, the start of growth refers to the start of the growth process, and the end of growth refers to the end of the growth process.

The average distance between grains in the present invention is the average value of the spatial distance between the centers of gravity of silver halide grains by growth in a reaction product (silver halide emulsion) solution at the time of preparing a silver halide emulsion. In other words, in other words, assuming that all the growing particles have the same space in the reactant solution, the term refers to one side length of a cube having a volume equal to the space of one particle. Specifically, it is defined by the following equation.

Average distance between grains = (volume of reaction solution / number of grains grown in reaction solution) ^{1/3 In} the growth process of silver halide grains, addition of an aqueous silver salt solution or an aqueous halide salt solution mainly used for grain growth. By
The amount of the reactant solution in the reaction vessel increases as the particles grow,
At the same time, the average interparticle distance increases. The average intergranular distance in the course of silver halide grain growth is directly reflected in the volume of the reactant solution during silver halide grain growth.

In the present invention, the minimum value of the average intergranular distance of the silver halide grains is defined as the average intergranular distance (μm) of the silver halide grains on the vertical axis and the growth start of the silver halide grains on the horizontal axis. It takes the time until the end of growth and means at least one of the minimum value and the minimum value in the obtained graph. That is, the point at which the average distance between silver halide grains decreases and starts to increase, or the point at which the average distance is reduced and the process ends, is the final point.

There may be a plurality of the minimum values, and it is preferable to prepare by adding iodide ions at a time near at least one of them including the minimum value.

In the present invention, the near time refers to the time at which the minimum value is shown or the time at which the minimum value is shown.
The range is preferably 30 minutes, more preferably ± 15 minutes, and particularly preferably ± 5 minutes. It is important to add iodide ions at a time within this range.

The halogen composition of the silver halide projections of the present invention is preferably any of silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide.

When silver iodide is contained, the silver iodide content is 0.1
Is preferably from 13 to 13 mol%, more preferably from 0.1 to 10 mol%.

When depositing the silver halide projections on the tabular host grains, halogen ions are introduced. When a plurality of halide ions are introduced, it is preferable to add them from the one having high solubility of silver salt. .

Since the solubility of silver iodide is lower than the solubility of silver bromide, and the solubility of silver bromide is lower than the solubility of silver chloride, when halide ions are added in a preferred order, chloride ions adhere near the junction. The chance to do it is higher.

In the present invention, the silver halide projections are located closest to the periphery of the tabular host grains and less than 50% of the (1,1,1) plane of the tabular grains, preferably the tabular grains. A much smaller percentage of the (1,1,1) plane of the
%, More preferably less than 10%, and most preferably less than 5%, a better effect is obtained.

When the tabular grains have a central region having a low silver iodide concentration and a side region having a high silver iodide concentration, the silver halide projections are typically located on the periphery of the tabular grains. It is preferable to limit.

In the present invention, the silver halide projections are
0.3 to 25 mol% of the total silver content of the grains is preferable,
~ 15 mol% is more preferred.

The temperature of the emulsion containing the tabular host grains when introducing the halogen ions is introduced at an arbitrary temperature of 35 to 70 ° C. Further, pAg is 6 to 8.5 and pH is 4
The range of ~ 9 is preferred.

When the silver halide projections are deposited on the tabular host grains, a spectral sensitizing dye is usually added as a site director when the silver halide projections are epitaxially attached before the introduction of the halogen ions. It is not added in the present invention.

When the silver halide projections are epitaxially deposited, it is preferable to use a production facility capable of controlling the average distance between silver halide grains.

For example, when the silver halide projections are epitaxially deposited, it is preferable to control the average intergranular distance of the silver halide to 0.60 to 1.00 times the growth start time, preferably 0.60 times. More preferably, it is controlled to 0.80 times.

Specifically, when the silver halide projections are epitaxially deposited, the value of the average intergranular distance is set to 0.4.
It is preferably controlled to 0 μm or less, more preferably to 0.30 μm or less, and particularly preferably to 0.20 μm or less. In the present invention, it is preferable to perform ultrafiltration on part or all of the tabular silver halide grains from the start to the end of the growth.

In the present invention, ultrafiltration is preferably performed between the start of the growth of the silver halide grains and the end of the growth. An example of a preferable manufacturing apparatus applicable to this 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 (halide), preferably bromine, iodine or chlorine. It has a halide addition line 5 for adding an aqueous solution of an alkali metal salt, an aqueous solution of an ammonium salt or a mixture thereof. In addition, it has a stirring mechanism 2 for stirring the dispersion medium and the reactant solution (mixture of the dispersion medium and the silver halide grains) during the preparation of the silver halide emulsion. The stirring mechanism can be in any conventional manner.

The silver chloride aqueous solution is added to the reaction vessel from the silver addition line 4 at a flow rate controlled by the silver addition valve 20. The aqueous halide salt 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 at the liquid level, 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 halogen 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 underlying silver halide nucleus grains is formed. Subsequently, the nucleation step is completed through an aging step as required.

Thereafter, when the addition of the aqueous silver salt solution and the aqueous halide salt solution is continued, the second stage of silver halide formation, ie, the growth process stage, is performed, and additional silver halide produced as a reaction product in that process is removed. Deposits on the initially formed 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 passed through the liquid take-out line 8 by the circulation pump 13 to form an ultrafiltration unit. 12 and returned to the reaction vessel through the liquid return line 9. At this time, the pressure applied to the ultrafiltration unit is adjusted by a pressure adjusting valve 18 provided in the middle of the liquid return line 9 so that a part of the solution of the water-soluble salt contained in the reactant solution is removed. And discharged out of the system through the permeated liquid discharge line 10.

In the present invention, it is preferable to arbitrarily control the amount of permeate (ultrafiltration flux) of the solution of the water-soluble salt separated by the ultrafiltration membrane. For example, the flow control valve 1 provided in the middle of the permeate discharge line 10
9 can be used to control the ultrafiltration flux. At that time, in order to minimize the pressure fluctuation of the ultrafiltration unit 12, the valve 25 provided in the middle of the permeated liquid return line 11 may be opened to use the permeated liquid return line 11. Further, the valve 25 is closed and the permeated liquid return line 11 is closed.
Need not be used, and they can be arbitrarily selected according to operating conditions. For detection of the ultrafiltration flux, a flow meter 14 provided in the middle of the permeated liquid discharge line 10 may be used, or the ultrafiltration flux may be detected by a mass change using the permeated liquid receiving container 27 and the scale 28. Good.

The circulation flow rate through the ultrafiltration step is preferably sufficiently high. Specifically, the residence 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, more preferably within 15 seconds, and particularly preferably within 10 seconds. .

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

As described above, 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 preferably used. However, materials and structures which act on the silver halide emulsion and adversely affect the photographic performance, etc., should be avoided. Is preferred. In addition, the molecular weight of the ultrafiltration membrane used in the ultrafiltration module can be arbitrarily selected.

The tabular silver halide grains of the present invention are preferably monodisperse emulsions having a narrow grain size distribution. Specifically, (standard deviation of grain size / average grain size) × 100 = width of grain size distribution ( %), The distribution is defined as 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

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

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

In the preparation of the tabular silver halide grains of the present invention, during the growth, a silver salt solution and a halide solution are added by a double jet method. Particles having a desired particle size and distribution can be obtained by a method in which the size distribution is not spread due to Ostwald ripening, that is, a method in which the size is gradually changed within the range of 30 to 100% of the rate at which new nuclei are generated. As another condition for further growth, a method of growing by adding silver halide fine particles, dissolving and recrystallizing as described in the 88th Annual Meeting of the 1983 Annual Meeting of the Photographic Society of Japan is also preferably used. Especially silver iodide fine grains,
Silver bromide fine grains, silver iodobromide fine grains, and silver chloride fine grains are preferably used.

The tabular silver halide grains of the present invention may be so-called halogen conversion type (conversion type) grains. The amount of halogen conversion is 0.2 to
It is preferably 0.5 mol%, and the conversion may be performed during physical ripening or after completion of physical ripening. As a method of halogen conversion, an aqueous halogen solution or fine silver halide particles having a smaller solubility product with silver than the halogen composition of the grain surface before the halogen conversion is usually added. The particle size at this time is preferably 0.2 μm or less, more preferably 0.02 μm or less.
０．１0.1 μm.

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

In producing the tabular silver halide grains of the present invention, stirring conditions during production are extremely important. As the stirrer, an apparatus described in JP-A-62-160128, in which an additive liquid nozzle is installed in the liquid near the mother liquor suction port of the stirrer, is particularly preferably used. At this time,
The rotation speed of the stirring is preferably set to 100 to 1200 rpm.

The silver halide grains of the present invention may have dislocation lines. The dislocation line is described in, for example, 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. That is, silver halide grains taken out carefully so as not to apply enough pressure to generate dislocation lines from the emulsion are placed on a mesh for electron microscope observation,
Observation is performed by a transmission method in a state where the sample is cooled so as to prevent damage (eg, printout) due to an electron beam. At this time, since the electron beam is more difficult to penetrate as the thickness of the particles is larger, a high-pressure type (200 μm for particles having a thickness of 0.25 μm) is used.
(kV or more) can be observed more clearly using an electron microscope.

The tabular silver halide grains of the present invention can be used in one or both of the step of forming grains and the step of growing the grains, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), Adding a metal ion using at least one selected from a rhodium salt (including a complex salt) and an iron salt (including a complex salt), and causing the metal element to be contained inside the particle or on the surface of the particle or both. Can be.

The tabular silver halide grains used in the present invention are spectrally sensitized by methine dyes and the like.

Sensitizing dyes preferably used in the light-sensitive material of the present invention include cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar, hemicyanine, styryl, and hemioxonol dyes.
The site director described above may be used. Particularly useful dyes are those belonging to cyanines, merocyanines and complex merocyanines.

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

The merocyanine or complex merocyanine includes a pyrazolin-5-one nucleus, a thiohydantoin nucleus and a 2-thiooxazolidin-nucleus as nuclei having a ketomethine structure.
A 5- to 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a thiazoline-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. In addition, the emulsion layer may contain, in addition to the sensitizing dye, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect. For example, it may contain an aminostilbene compound substituted with a nitrogen-containing heterocyclic nucleus group, an aromatic organic acid formaldehyde condensate, a cadmium salt, an azaindene compound, or the like.

It is preferable to add the spectral sensitizing dye as a dispersion of solid fine particles rather than as a solution of an organic solvent. In particular, it is preferable to disperse in a water system substantially free of an organic solvent and / or a surfactant, and to add in a state of a solid fine particle dispersion substantially insoluble in water. The particle size after dispersion is preferably 1 μm or less.

At the time of addition, spectral sensitization may be carried out by using a site director added at the time of forming silver halide projections, or when spectral sensitization is carried out with another sensitizing dye, emulsion may be added after formation of silver halide projections. It can be added at any time before the preparation of the coating solution.

In the present invention, the preferable conditions of the chemical ripening step, for example, pH, pAg, temperature, time and the like are not particularly limited, and can be carried out under conditions generally used in the art.

For chemical sensitization, a sulfur sensitizing method using a compound containing sulfur capable of reacting with silver ions or active gelatin,
A selenium sensitization method using a selenium compound, a tellurium sensitization method using a tellurium compound, a reduction sensitization method using a reducing substance, gold or the like, a noble metal sensitization method using a noble metal, or the like can be used alone or in combination. Among them, sulfur sensitization method,
Selenium sensitization, tellurium sensitization, reduction sensitization, and the like are preferably used.

In the case of selenium sensitization, the selenium sensitizer used includes a wide variety of selenium compounds. Examples of useful selenium sensitizers include colloidal selenium metal, isoselenocyanate (such as allyl isoselenocyanate). ), Selenoureas (N, N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoropropylselenourea, N, N, N'- Trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, selenoketones (selenoacetone, selenoacetophenone, etc.), selenoamides (selenoacetamide) , N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (2-sele Propionate, methyl 3-selenobutylate), selenophosphates (tri -p-
Triselenophosphate, etc.), and selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, selenoketones, selenides.

The amount of the selenium sensitizer used depends on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally from 10 ^-8 to 10 ^-4 per mol of silver halide.
Use about moles. Depending on the nature of the selenium compound to be used, the method of addition may be a method of adding a single or mixed solvent of water or an organic solvent such as methanol, ethanol or the like, or a method of preliminarily mixing with a gelatin solution and adding. The method may also be the method disclosed in JP-A-4-140739, that is, a method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

The temperature of chemical ripening using a selenium sensitizer is as follows:
It is preferably in the range of 40 to 90 ° C, more preferably 45 to 90 ° C.
80 ° C. The pH is 4 to 9, and the pAg is 6 to 9.5.
Is preferable.

With respect to tellurium sensitizers and sensitization methods, a wide variety of tellurium sensitizers are used, and examples of useful tellurium sensitizers include telluroureas (N, N-dimethyltellurourea,
Tetramethyltellurourea, N-carboxyethyl-N,
N'-dimethyltellurourea, N, N'-dimethyl-N '
Phenyltellurourea), phosphine tellurides (tributylphosphine telluride, tricyclohexylphosphine telluride, tri-i-propylphosphine telluride, butyl-di-i-propylphosphine telluride, dibutylphenylphosphine telluride, etc.), Examples include telluramides (telluroacetamide, N, N-dimethyltellurobenzamide, etc.), telluroketones, telluroesters, isotellocyanates, and the like. The technology for using the tellurium sensitizer is based on the technology for using the selenium sensitizer.

As the hydrophilic colloid used in the light-sensitive material of the present invention, gelatin is preferably used, but other hydrophilic colloids can be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, protein hydroxyethylcellulose such as albumin and casein, carboxymethylcellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, dextran, sugar derivatives such as starch derivatives, polyvinyl alcohol Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. it can. Especially with gelatin, average molecular weight 50
It is preferable to use 00 to 10,000 dextran or polyacrylamide in combination. These examples are described in, for example, JP-A-1-307778, JP-A-2-62532, and JP-A-2-2-232.
No. 4748, No. 2-44445, No. 1-66031
No. JP-A-64-65540 and JP-A-63-101841.
And No. 63-153538.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull. Soc. Sci. Photo. Japan
an, No. In addition to enzyme-treated gelatin as described on page 1630 (1966), gelatin derivatives (e.g., acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkane sultones, vinylsulfonamides, maleimide compounds) , Polyalkylene oxides, epoxy compounds, etc.).

The silver halide emulsion used in the method for processing a silver halide photographic light-sensitive material of the present invention can use various photographic additives before and after physical ripening or chemical ripening.

Compounds used in such a step include, for example, Research Disclosure (RD) N
o. 17643 (December 1978), (RD) No.
18716 (November 1979) and (RD) No. Three
Various compounds described in 08119 (December 1989) can be used. The types and locations of the compounds described in these three RDs are described below.

[0084]

[Table 1]

The support for the silver halide photographic light-sensitive material used in the method for processing a silver halide photographic light-sensitive material of the present invention includes those described in the above RD.
A suitable support is a polyethylene terephthalate film or the like, and the support surface may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or may be subjected to corona discharge or ultraviolet irradiation.

In the processing method of the present invention, processing is carried out with a developer containing a polyhydric alcohol. The polyhydric alcohol of the present invention has 5 to 20 hydroxyl groups and 5 to 20 carbon atoms,
It refers to a solid at room temperature. The saccharides may be used alone or in combination of two or more.

Preferred specific examples of the saccharide are shown below.
The present invention is not limited to these. A-1: D-trait A-2: L-trait A-3: meso-trait A-4: adunit A-5: D-arabit A-6: L-arabit A-7: adunit A-8: xylit A-9: D-Sorbit A-10: L-Sorbit A-11: D-Mannit A-12: D-Edit A-13: D-Tallit A-14: Dulcit A-15: Alit A-16: Persett A-17: Borremit A-18: β-sedoheptite A-19: meso-inosit Next, the compound of the general formula (1) of the present invention will be described. In the general formula (1) RSO ₃ M general formula (1), R represents a linear or branched alkyl group having 4 to 12 carbon atoms, M represents a monovalent metal atom. Preferred alkali metal atoms include, for example, Na, K and the like.

Hereinafter, specific examples of the compound represented by the formula (1) will be shown, but the present invention is not limited thereto. _{B-1: CH 3 - (} CH 2) 3 SO 3 Na B-2: CH 3 - (CH 2) 4 SO 3 Na B-3: CH 3 - (CH 2) 5 SO 3 Na 3 B-4: _{CH 3 -CH (CH 3) -} (CH 2) 3 SO 3 Na B-5: CH 3 - (CH 2) 6 SO 3 K B-6: CH 3 - (CH 2) 7 SO 3 Na B-7 : CH ₃ —CH (CH ₃ ) — (CH ₂ ) ₅ SO ₃ Na B-8: CH ₃ — (CH ₂ ) ₃ —CH (CH ₃ ) — (C
_{H 2) 2 SO 3 Na B} -9: C 2 H 5 -CH (C 2 H 5) - (CH 2) 4 SO 3 K B-10: CH 3 - (CH 2) 9 SO 3 Na B-11 : CH ₃ —CH ₂ —CH ₂ —CH (CH ₂ —CH _{2
-CH 3) - (CH 2)} 4 SO 3 Na B-12: CH 3 - (CH 2) 3 -CH (CH 3) SO 3 N
a In the method for developing a silver halide photographic light-sensitive material of the present invention, processing is performed using an automatic developing machine.
Completed within 0 seconds. That is, the time from when the tip of the photosensitive material starts to be immersed in the developing solution to when the tip comes out of the drying zone through a processing step (so-called Dry to
Dry time) is 90 seconds or less, and more preferably 15 seconds to 90 seconds.

The development time is 3 to 40 seconds, preferably 6 to 40 seconds.
20 seconds. The development temperature is 25 to 50C, preferably 30 to 40C. Fixing temperature is about 20-40 ° C and 29
The fixing time is preferably 3 to 30 seconds, and more preferably 4 to 20 seconds.

In the drying step, it is preferable that the automatic developing machine is provided with a drying zone in which hot air of usually 35 to 100 ° C., preferably 40 to 80 ° C. is blown or heating means by far infrared rays is provided.

The automatic developing machine is provided with a mechanism for applying water or a rinsing solution of an acidic solution having no fixing ability to the photosensitive material during each of the developing, fixing and washing steps (Japanese Patent Laid-Open No.
-264953), and it is preferable that a device capable of adjusting a developing solution and a fixing solution is further incorporated.

In the processing method of the present invention, the replenishment rates of the developing solution and the fixing solution are each preferably 180 ml / m ² or less, more preferably 8 to 160 ml / m ² .
It is particularly preferred that the treatment is performed at 10 to 100 ml / m ² .

The developing agent used in the processing method of the present invention may be any of reductones, phenidone, hydroquinone, and any other commonly used photographic processing agents. preferable. Examples of the reductone include an enediol type, an enaminol type, an enediamine type, a thiol enol type and an enamine thiol type, and are preferably compounds represented by the general formula (2).

[0094]

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In the general formula (2), R ₁ and R ₂ each represent a hydroxy group, a substituted or unsubstituted amino group (each of a substituent such as ethyl, butyl or hydroxyethyl) or an acylamino group (acetylamino, Benzoylamino, etc.), alkylsulfonylamino group (methanesulfonylamino, butanesulfonylamino, etc.), arylsulfonylamino group (benzenesulfonylamino, p-toluenesulfonylamino, etc.), alkoxycarbonylamino group (methoxycarbonylamino, etc.), mercapto group Or an alkylthio group (e.g., methylthio, ethylthio), and preferably R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q are each a hydroxy group, a carboxyl group, an alkoxy group (methoxy, ethoxy, butoxy, etc.), a hydroxyalkyl group (hydroxymethyl, hydroxyethyl, etc.), a carboxyalkyl group (carboxymethyl, carboxyethyl, etc.), Sulfo group (including salt), sulfoalkyl group (sulfoethyl, sulfopropyl, etc.), amino group (including alkyl substitution), aminoalkyl group (aminoethyl, aminopropyl, etc.), alkyl group (methyl, ethyl, propyl, butyl) , Pentyl, etc.)
Or an aryl group (phenyl, p-tolyl, naphthyl, etc.)
Or a non-metallic atomic group bonded to each other to form a 5- to 8-membered ring together with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y. These 5-8
The membered rings may form a saturated or unsaturated fused ring.

Examples of the 5- to 8-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring,
Examples thereof include an azacyclohexenone ring, a uracil ring, a cycloheptenone ring, a cyclohexanone ring, an azepine ring, and a cyclooctenone ring, and a 5- to 6-membered ring is preferable. Among them, preferred examples of the 5- to 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexanone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.

When Y represents ＮＲNR ₃ , R ₃ is a hydrogen atom,
It represents a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group, and specific examples of each substituent are the same groups as those described above for R ₁ , R ₂ , P and Q. Can be mentioned.

Hereinafter, specific examples of the compound represented by the formula (2) will be shown, but the present invention is not limited thereto.

[0100]

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[0101]

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[0102]

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[0103]

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The salts of the reductones include, for example, lithium, sodium, potassium, ammonium and the like.

Of these, ascorbic acid or erythorbic acid (stereoisomer) is preferred, and the above-mentioned exemplified compound (2-1) is preferred.

The amount of these reductones to be added to the developing solution is not particularly limited, but is practically 0.1 to 100 g, preferably 0.5 to 60 g, more preferably 1 to 30 g per liter of the processing solution. Is desirable in order to obtain the effect of suppressing the formation of a white precipitate.

The reductones may contain only one kind or two or more kinds. Further, in addition to sulfite, an organic reducing agent can be used as a preservative. In addition, bisulfite adducts of chelating agents and hardeners can be used. It is also preferable to add a silver sludge inhibitor. Addition of a cyclodextrin compound is also preferable, and compounds described in JP-A-1-124852 are particularly preferable. An amine compound can be added to the developer, and for example, a compound described in US Pat. No. 4,269,929 is particularly preferable.

When developing the silver halide photographic light-sensitive material of the present invention, a buffer may be used as a developer, and the buffer may be sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate. Trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), o -Potassium hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-
Potassium sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned.

Examples of development accelerators include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, and other 1-phenyl- compounds.
If necessary, 3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added.

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, 2
Representative examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine, and 1-phenyl-5-mercaptotetrazole as an example.

Further, in the developer composition, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, cyclodextrin compound and the like can be used as an organic solvent for increasing the solubility of the developing agent. Further, various additives such as a stain inhibitor, an anti-sludge agent and a layering effect promoter can be used.

The fixing agent used in the method for processing a silver halide photographic light-sensitive material of the present invention may contain a compound known as a fixing agent. Fixing agents, chelating agents, pH buffers, hardeners, preservatives, and the like can be added.
Nos. 242246 (page 4) and JP-A-5-113632 (pages 2 to 4) can be used. Other known fixing accelerators can also be used.

Prior to the treatment, it is preferable to add a starter, and it is also preferable to add the solidified starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkali metal atom such as KBr, an organic inhibitor, and a development accelerator are used.

[0114]

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

Example 1 (Preparation of Seed Emulsion-1) Seed Emulsion-1 was prepared as follows. A ₁ ossein gelatin 24.2g Water 9657ml polypropylene oxy - polyethyleneoxy - disuccinate sodium salt (10% aqueous ethanol solution) 6.78 mL of potassium bromide 10.8 g 10% nitric acid 114 ml B ₁ 2.5 N aqueous silver nitrate solution 2825ml C ₁ the solution to the solution a ₁ with a mixing and stirring machine shown in Japanese Patent Publication No. 58-58288 in 2825ml D ₁ 1.75N potassium bromide aqueous solution following silver potential control amount 42 ° C. with potassium bromide 841g water B ₁ and solution C ₁ Each of 46
4.3 ml was added by the simultaneous mixing method over 1.5 minutes to perform nucleation.

After stopping the addition of the solution B ₁ and the solution C ₁ ,
By taking 60 minutes to raise the temperature of the solution A ₁ to 60 ° C., the pH was adjusted to 5.0 with 3% KOH, the simultaneous mixing method solution B ₁ and solution C ₁ again, each 55 0.4 ml /
Min was added at a flow rate of 42 minutes. From this 42 ° C to 60
The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise to 0 ° C. and the re-mixing with the solutions B ₁ and C ₁ was +8 mv and +16 mv, respectively, using the solution D _1. It controlled so that it might become. 3% KO after completion of addition
The pH was adjusted to 6 with H, and desalting and washing were immediately performed.

In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed 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 is 0.06.
It was confirmed by an electron microscope that the average particle diameter was 4 μm and the average particle diameter (in terms of circular diameter) was 0.595 μm. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

(Preparation of Emulsion Em-1) Em-1 was prepared using Seed Emulsion-1 and the following four kinds of solutions. A ₂ ossein gelatin 34.03g polypropylene oxy - polyethyleneoxy - finish 3150ml with disuccinate sodium salt (10% aqueous ethanol solution) 2.25 ml Seed emulsion -1 1.722 mole equivalent water. B ₂ Potassium bromide 1734 g Make up to 3644 ml with water. Finish to 4165 ml with 2478 g of C ₂ silver nitrate water. Fine-grain emulsion having 3% by mass of D ₂ gelatin and silver iodide grains (average particle size: 0.05 μm) ^(*) Equivalent to 0.080 mol (*) 5.0 mass containing 0.06 mol of potassium iodide %
2 liters of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added to 6.64 liters of the gelatin aqueous solution over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are formed, the pH is adjusted using an aqueous sodium carbonate solution.
Was adjusted to 6.0.

The solution A ₂ was vigorously stirred in the reaction vessel while maintaining the temperature at 60 ° C., and a part of the solution B _2, a part of the solution C ₂ and half the amount of the solution D ₂ were mixed simultaneously for 5 minutes. , And then half of the remaining amount of the solution B ₂ and the solution C ₂ are added over 37 minutes, and then a part of the solution B _2, a part of the solution C ₂ , and the remaining amount of the solution D ₂ It was added over 15 minutes, and finally the remaining total amount of the solution B ₂ and C ₂ was added over 33 minutes. During this time, the pH was kept at 5.8 and the pAg was kept at 8.8 throughout. Here, the addition rates of the solution B ₂ and the solution C ₂ were changed as a function of time in accordance with the critical growth rate.

When the obtained silver halide emulsion was observed with an electron microscope, the (1,1,1) plane was a main plane, the average circle equivalent diameter was 0.984 μm, the average thickness was 0.22 μm, and the average aspect ratio was about 4 And tabular silver halide grains having a particle size distribution of 18.1%. The average of the distance between twin planes was 0.020 μm, and the grains having a ratio of the distance between twin planes to the thickness of 5 or more accounted for 97% (number) of all tabular silver halide grains and 10 or more grains. Is 49% and particles of 15 or more are 17
Accounted for%.

(Preparation of Emulsion Em-2)
Melting was performed at 0 ° C., and pAg was adjusted to 7.5 by simultaneously adding a silver nitrate solution and a potassium iodide solution. At this time, the silver nitrate solution and the potassium iodide solution were added in such a ratio that the silver iodide content of silver halide precipitated in a small amount during this preparation was 12 mol%.

Next, a 2 mol% sodium chloride solution was added to the first emulsion Em-1, and then 0.6 mmol of the sensitizing dye (A) and 0.1 mol of the sensitizing dye (B) per mol of silver were added. 00
6 mmol (all per mole of silver) was added as a dispersion in the form of solid fine particles, and thereafter, calcium chloride, sodium bromide, and silver iodide fine particle emulsions (the same as those used for adjusting Em-1) , And silver nitrate solution were added in this order. The amount of silver nitrate added was 6 mol% based on the total silver amount of the silver halide grains. After all this Em-2
The composition ratio (mol%) of the halide added by the adjustment of C is C
l: Br: I = 42: 42: 16 was added.

After completion of the addition, the emulsion was cooled to 40 ° C. and subjected to an ultrafiltration module (manufactured by Asahi Kasei Kogyo Co., Ltd., molecular weight cut off 1).
After performing ultrafiltration desalting with a type ALP-1010) using a 3000 polyacrylonitrile membrane, 10%
A gelatin solution was added and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, at 40 ° C., the pH was 5.80 and the pAg was 8.
06.

A solid particulate dispersion of the spectral sensitizing dye was prepared by a method according to the method described in JP-A-5-297496. That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been previously adjusted to 27 ° C., and a high-speed stirrer (dissolver) is used for 3,5.
Obtained by stirring at 00 rpm for 30-120 minutes.

Sensitizing dye (A): 5,5'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine-sodium salt sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl- 3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride The obtained emulsion Em-2 was observed with an electron microscope, and the periphery of the main plane ((1,1,1) plane) was observed. Silver halide projections epitaxially adhered to the portions were observed. That is, since the silver halide projections were formed after the growth was completed, the average intergranular distance at this time was maximized.

(Preparation of Emulsion Em-3) In the preparation of Emulsion Em-2, after forming the host tabular grains, the silver halide emulsion was subjected to an ultrafiltration module (a polyacrylonitrile film having a molecular weight cut off of 13,000, manufactured by Asahi Kasei Kogyo KK). For ultrafiltration through type ALP-1010). Preparation of Emulsion Em-3 Except that the volume of the emulsion was circulated to 1/5 and that the sensitizing dyes (A) and (B) were not added, the preparation of Emulsion Em-3 was carried out in the same manner as Emulsion Em-2. Was done.

When the obtained emulsion Em-3 was observed by an electron microscope, silver halide projections epitaxially adhered to the periphery of the main plane (1,1,1) were observed.

That is, since the silver halide projections were formed by reducing the volume of the emulsion to 1/5, the average intergranular distance at this time was minimized.

Table 2 shows the circle equivalent diameters and thicknesses of these emulsions and the average intergranular distances when silver halide projections were formed.
Shown in

[0130]

[Table 2]

(Chemical sensitization of emulsion Em-2) After the obtained emulsion Em-2 was heated to 60 ° C, a mixed aqueous solution of adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate and triphenylphosphine selenide were used. A dispersion was added, and after 30 minutes, a silver iodide fine grain emulsion was added, and a total of 2
Aged for hours. At the end of aging, an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

The above additives and their amounts (per mole of silver) are shown below. Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.2 mg Stabilizer (TAI) 500 mg The above dispersion of triphenylphosphine selenide was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., stirred and completely dissolved. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25 mass% aqueous solution of sodium dodecylbenzenesulfonate was added thereto.
Was added. Next, these two liquids are mixed to obtain a diameter of 10c.
m with a high-speed stirring type disperser having a dissolver of 50 m.
Dispersion was performed at a dispersion blade peripheral speed of 40 m / sec at 30 ° C. for 30 minutes. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3% by mass or less. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg. A part of the dispersion thus obtained was fractionated and used in the above experiment.

(Chemical Sensitization of Emulsions Em-1 and 3) Emulsion Em
In the chemical sensitization of -2, adenine, except that the emulsion was heated to 60 ° C. and then the sensitizing dyes (A) and (B) were added in the following amounts as solid fine particle dispersions per mol of silver,
A mixed aqueous solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate and a dispersion of triphenylphosphine selenide were added in the same manner as for emulsion Em-2 to obtain emulsion Em-
Chemical sensitization of 1 and 3 was performed.

Sensitizing Dye (A) 0.6 mol Sensitizing Dye (B) 0.006 mol (Preparation and coating of coating solution) Then, a polyethylene terephthalate film base (thickness: 0.15 blue) for X-rays for X-rays 175 μm) on both sides of a support having the following first crossover cut layer previously coated thereon, and the following emulsion layer and protective layer were coated on both sides from the support side so that the following coating amounts were obtained. Simultaneous multi-layer coating, drying, sample No.
1-1 to 1-12 were obtained. The additives used for each coating solution are as follows. The amount of addition is shown per 1 m ^{2 on} one side of the photosensitive material. First layer (crossover cut 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 (silver halide 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) ₂ 350 mg / m ² Compound (P) 0.2 g / m ² Compound (Q) 0.2 g / m ² Third layer (protective layer) Gelatin 0.6 g / m ² Matting agent comprising polymethyl methacrylate (Area average particle size 7.0 μm) 50 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 polyacrylamide (average Molecular weight 10,000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (SI) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (K) 15 mg / m ² compound (O) 50 mg / m ² compound (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 Hardener (B) 60 mg / m ²

[0136]

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[0137]

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[0138]

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[0139]

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The amount of the above-mentioned material is equivalent to one side.
The coating amount of the emulsion layer was adjusted so that the amount of silver per side was 1.3 g / m ² . (Preparation of solid processing agent) A developing tablet and a fixing tablet were prepared according to the following operations (A) to (D).

Operation (A) Preparation of Tablet A for Developing Agent 13,000 g of sodium erythorbate as a developing agent
Is ground to a mean particle size of 10 μm in a commercially available bantam mill. 4877 g of sodium sulfite, 1
-Phenyl-3-pyrazolidone (phenidone) to 975
g, diethylenetriaminepentaacetic acid pentasodium (DTP
A.5Na), 1635 g, mixed in a mill for 30 minutes, 30 minutes at room temperature for about 10 minutes in a commercial stirring granulator.
After granulation by adding 1 l of water, the granules are dried in a fluidized bed drier at 40 ° C. for 2 hours to remove almost completely the moisture of the granules.

The granules thus prepared were uniformly mixed with polyethylene glycol # 6000 or 2167 g of the polyhydric alcohol described in Table 3 in a room conditioned at 25 ° C. and 40% RH for 10 minutes using a mixer. After that, the obtained mixture was mixed with Kikusui Seisakusho Co., Ltd. Tough Presto Collect 152.
Using a modified tableting machine of 7HU, the tablet was filled at a pressure of 8.715 g and compression tableting was carried out to produce 2500 tablets A for development.

Operation (B) Preparation of tablet B for development 19500 g of potassium carbonate, 8.15 g of 1-phenyl-5-mercaptotetrazole, 3250 g of sodium carbonate
g, 650 g of glutaraldehyde sulfite adduct, polyethylene glycol # 6000 or 1354 g of the polyhydric alcohol shown in Table 3 are ground and granulated in the same manner as in the operation (A). The amount of water added was 30.0 ml and after granulation,
After drying for 0 minutes, the water content of the granules is almost completely removed.

The mixture thus obtained was subjected to compression tableting using the same tableting machine as described above, with the filling amount per tablet being 9.90 g, to produce 2500 developing tablet B preparations.

Operation (C) Preparation of Tablet C for Fixing Example 18560 g of ammonium thiosulfate, 1392 g of sodium sulfite, 580 g of sodium hydroxide, and 2.32 g of disodium ethylenediaminetetraacetate were pulverized and granulated in the same manner as in the operation (A). After adding 500 ml of water and granulating, the granulated material is dried at 60 ° C. for 30 minutes to almost completely remove the water content of the granulated material.

The mixture thus obtained was compressed and tableted with the above tableting machine at a filling amount of 8.214 g per tablet to produce 2500 fixing tablet C preparations.

Operation (D) Preparation of tablet D for fixing: 186 g of boric acid, 6500 aluminum sulfate / 18-hydrate
g, 1860 g of glacial acetic acid, and 925 g of sulfuric acid (50% by mass) are pulverized and granulated in the same manner as in the operation (A). Water addition amount is 10
After the granulation, the mixture is dried at 50 ° C. for 30 minutes to remove the moisture of the granulated product almost completely.

The mixture thus obtained was compressed and tableted using the above-mentioned tableting machine at a filling amount of 4.459 g per tablet to produce 2500 fixing tablets D.

(Preparation of Developing Solution) A developing solution of 16.5 was prepared by using 127 prepared A tablets and 254 B tablets.
One liter was prepared. A starter 330 having the following composition was added to 16.5 liters of the obtained pH 10.70 developer.
The mixture was added to a pH of 10.45 to prepare a development start solution.

Composition of development starter (amount per liter) Potassium carbonate 120.0 g Sodium erythorbate 40.0 g DTPA · 5Na 5.0 g 1-Phenyl-5-mercaptotetrazole 0.05 g Sodium bicarbonate 20.0 g Phenidone 3 1.0 g Sodium sulfite 15.0 g Polyethylene glycol # 6000 or polyhydric alcohol described in Table 2 15.0 g Glutaraldehyde sulfite adduct 4.0 g (Preparation of developer starter) 210 g glacial acetic acid and KBr
Water was added to 530 g to make 1 liter.

(Preparation of Fixing Initiation Solution) Using 237 of the above prepared fixing agents C and 149, 11 liters of a fixing solution having the following composition was prepared and used as a fixing initiation solution. The pH of the resulting fixing start solution was 4.80.

Fixing start solution composition (amount per liter) Ammonium thiosulfate 160.0 g Sodium sulfite 12.0 g Boric acid 1.0 g Sodium hydroxide 5.0 g Glacial acetic acid 10.0 g Aluminum sulfate / 18-hydrate 35.0 g Sulfuric acid ( 5.0 g Disodium ethylenediaminetetraacetate / dihydrate 0.02 g (Preparation of replenisher) Both replenisher for the developer and the fixer is supplied to the replenishment tablet inlet with each of the above-mentioned developer tablet and fixer tablet. Each packaging bag is opened and set, and tablets are poured into the respective built-in chemical mixers at the same time that the prescribed amount of the development initiator is charged, and at the same time, a necessary amount of hot water at 25 to 30 ° C. is injected, and the dissolving time is 25 minutes while stirring and dissolving. The solution was adjusted to 3.0 liters per minute and used as a replenisher for development and fixing.

(Evaluation of Sample) <Sensitivity> The obtained sample was sandwiched between two intensifying screens KO-250 (manufactured by Konica Corporation) and X-rays were applied at a tube voltage of 100 mA for 0.05 seconds through an aluminum wedge. Irradiated, the automatic developing machine SRX-502 (manufactured by Konica Corporation) was modified so as to satisfy the following processing conditions, the sample was processed using the above processing agent, and the sensitivity was measured by a standard method.

The sensitivity value is represented by the reciprocal of the exposure amount that gives a density of fog + 1.0. The sensitivity of 1-1 is 10
The relative sensitivity was shown as 0.

[0155] <Evaluation of Silver Tone> Each sample was subjected to X-ray exposure as a silver tone evaluation sample so that the density at the time of performing the above-mentioned processing was 1.1 ± 0.05. The silver tone was evaluated according to the following evaluation criteria.

Evaluation Criteria A: Pure black B: Slightly yellowish C: Yellowish felt These results are summarized in Table 3.

[0157]

[Table 3]

Table 3 shows that the sample of the present invention is superior in both sensitivity and silver tone as compared with the comparative sample.

Example 2 In the same manner as in Example 1, the sample No. 2-1 to 2-12
Was prepared.

(Preparation of solid processing agent) In the preparation of the solid processing agent in Example 1, after adding polyethylene glycol # 6000 or a polyhydric alcohol to the developing tablet A and B, the general formula (1) Compound 3) to Agent A
The same solid processing agent as in Example 1 was added except that 00g and 340g were added to the B agent, respectively, and the filling amount per tablet of the A agent was 8.835g and the filling amount per tablet of the B agent was 10.0g. It was prepared and the sample was evaluated in the same manner as in Example 1.

Table 4 summarizes the results.

[0162]

[Table 4]

Table 4 shows that the sample of the present invention is superior in both sensitivity and silver tone as compared with the comparative sample.

[0164]

According to the present invention, a rapid processing method of a photosensitive material having excellent sensitivity and silver tone can be provided.

[Brief description of the drawings]

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 5/26 520 G03C 5/26 520

Claims (6)

[Claims] A silver halide photographic material having a hydrophilic colloid layer containing tabular silver halide grains satisfying the following conditions is processed with a developing solution containing a polyhydric alcohol. Processing method of photographic photosensitive material. Conditions of Tabular Silver Halide Grains The (1,1,1) plane is the main plane, and the average equivalent circle diameter is 0.
5 to 3.0 μm, average thickness of 0.07 to 0.7 μm, including epitaxially deposited silver halide projections of a face-centered cubic lattice structure forming an epitaxy junction, wherein the silver halide projections are Under the condition that the average inter-grain distance shown below has a minimum value between the start of the growth and the end of the growth, the silver halide protrusion is located at a time near the minimum value. Form. The average interparticle distance is (volume of reaction solution / number of growing particles in reaction solution) ^1/3 . 2. A silver halide photographic material having a hydrophilic colloid layer containing tabular silver halide grains satisfying the above conditions is processed with a developer containing a compound represented by the following general formula (1). A method for processing a silver halide photographic material. Formula (1) RSO ₃ M (R represents a linear or branched alkyl group having 4 to 12 carbon atoms, M represents a monovalent metal atom.) 3. A method for processing a silver halide photographic material, comprising processing with a developer containing the polyhydric alcohol and the compound represented by the general formula (1). 4. A method for processing a silver halide photographic material having a hydrophilic colloid layer containing tabular silver halide grains which has been ultrafiltered between the start of growth and the end of growth. Item 4. The method for processing a silver halide photographic light-sensitive material according to any one of Items 1 to 3. 5. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the processing is performed with a developer prepared from a solid processing agent. 6. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the processing is performed in a period of 90 seconds or less.