JP2000347333A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure good dryability and silver tone even in rapid processing and to improve silver tone, pressure fog and residual color by disposing a hydrophilic colloidal layer containing specified flat platy silver halide grains and carrying out hardening with a vinylsulfone hardening agent. SOLUTION: The silver halide photographic sensitive material has one or more hydrophilic colloidal layers containing specified flat platy silver halide grains and is hardened with a vinylsulfone hardening agent. The flat platy silver halide grains have (1, 1, 1) faces as principal planes, 0.5-3.0 μm equivalent circular diameter and 0.07-0.7 μm thickness and contain epitaxially deposited silver halide protrusions forming epitaxial joined parts and having a face- centered cubic lattice structure. The silver halide protrusions are situated on the peripheral edge parts of the host flat platy grains. During the time from the beginning of growth to the end, the silver halide protrusions are formed under the condition that the average distance between grains represented by the equation (the average distance between grains)=[(the volume of a reactive solution)/(the number of growing grains in the reactive solution)]1/3 has the minimum value and at the time when it becomes near to te minimum.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material suitable for rapid processing.

[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. There is a demand for further rapid development processing.

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, JOURNAL OF IMAGI
NNG SCIENCE Vol. 32, no. 4 (1
1988, July and August), JP-A-8-171164, and the like, including a tabular silver halide containing epitaxially deposited silver halide projections having a face-centered cubic lattice structure forming an epitaxy junction. High sensitivity technology using particles is introduced. 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 a disadvantage that the silver tone of the image after the development processing is significantly deteriorated.

On the other hand, in order to reduce the load of the drying step in rapid processing, it is essential to reduce the water content of the photographic material during processing. If the amount of binder is simply reduced, fog failure occurs due to external pressure during processing or handling of the photosensitive material. As a technique for improving pressure fog, for example, techniques using latex are disclosed in U.S. Pat. Nos. 2,376,005 and 3,325,386.
These are disclosed in JP-B-45-5331 and JP-B-46-2506, and JP-A-51-130217. However, although the pressure fog is improved to some extent by these disclosed techniques, there is a disadvantage that the residual color after processing is deteriorated.

[0006] Further, increasing the hardener of the photographic material to reduce the water content also contributes to the reduction of the drying load. However, this method also has a disadvantage that fog caused by drying tends to increase when the amount is simply increased. Have.

[0007]

Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material having good dryability and silver tone and low fog even in rapid processing, and silver tone, pressure fog and residual color after processing. To provide an improved silver halide photographic light-sensitive material.

[0008]

The above object of the present invention is achieved by the following constitution.

(1) A halogenated composition comprising at least one hydrophilic colloid layer containing tabular silver halide grains satisfying the following conditions and being hardened with a vinyl sulfone hardener. Silver photographic photosensitive material.

<Conditions of Tabular Silver Halide Grains> The (1,1,1) plane is a main plane, and the equivalent circle diameter is 0.5.
３3.0 μm, thickness 0.07-0.7 μm.

[0011] Includes epitaxially deposited silver halide protrusions of a face centered cubic lattice structure forming an epitaxy junction.

The silver halide projections are located at the periphery of the host tabular grains.

From the start of the growth to the end of the growth, under the condition that the average intergranular distance represented by the following formula has a minimum value,
The silver halide projection is formed at a time near the minimum value.

Average intergranular distance = (volume of reaction solution / number of growing particles in reaction solution) ^1/3 (2) Hydrophilicity containing tabular silver halide grains satisfying the above-mentioned tabular silver halide grain conditions A silver halide photographic material comprising at least one hydrophilic colloid layer and at least one layer containing a tabular silica compound.

(3) The tabular silver halide grains are:
3. The silver halide photographic light-sensitive material according to the above 1 or 2, wherein the material is ultrafiltered from the start to the end of the growth.

Hereinafter, the present invention will be described in 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 equivalent circle diameter is 0.5 to 3.0 μm, preferably 0.5 to 2.0 μm.
μm. The thickness is 0.07 to 0.7 μm, preferably 0.1 to 0.7 μm. The method for producing these tabular silver halide grains is a known technique, and is described in U.S. Pat. Nos. 4,434,226, 4,439,520, 4,414,310, and 5,314,793. Nos. 5,334,495, 5,358,840, and 5,372,927. In the present invention, the term "tabular host grains" refers to such tabular silver halide grains prepared by a known technique.

The silver halide grains of the present invention, after preparing the above-described tabular host grains, comprise epitaxially deposited silver halide projections having a face-centered cubic lattice structure forming the epitaxy junction. The silver protrusion is
It is obtained by preparing so as to be located at the periphery of the tabular host grains.

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 preferably 0.25 mol% to 10 mol%, more preferably 0.25 mol% to 6 mol%, and particularly preferably 0.4 mol% to 2 mol%. . It is possible for tabular silver halide grains to contain a small amount of silver chloride. For example, US Pat. No. 5,372,927 discloses that the silver chloride content is 0.4 to 2%.
It describes 0 mol% silver chlorobromide tabular grains.

In the present invention, the circle-equivalent diameter means an average projected area diameter (hereinafter, referred to as a particle diameter), and is a circle-equivalent diameter of the projected area of the tabular silver halide grains (the same as the silver halide grains). (Diameter of a circle having a projected area), and the thickness indicates a 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 surrounded by the outer periphery of the main plane of the tabular grain and a line segment indicated by a set of points whose distance from the outer periphery is 10% of the equivalent circle diameter of the tabular grain. The range of

In the present invention, the silver halide projection (hereinafter referred to as silver halide projection) has a halogen composition of any one of silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide. Is preferred. When silver iodide is contained, the silver iodide content is 0.1 mol%
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 the salt with silver. . 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, the addition of halide ions in a preferred order will increase the chance of chloride ions adhering near the junction. Get higher. In the present invention, the silver halide projections are located closest to the peripheral portion of the tabular host grains and less than 50% of the (1,1,1) main surface of the tabular grains, preferably the tabular grains. Greater effectiveness is obtained when restricted to a portion that occupies a much smaller proportion of the (1,1,1) major surface, less than 20%, more preferably less than 10%, and most preferably less than 5%. 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 limited to the periphery of the tabular grains. Is preferred.

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

When the halogen ions are introduced, the temperature of the emulsion containing the tabular host grains is introduced at an arbitrary temperature of 35 ° C. to 70 ° C. Moreover, pAg is 6-8.5, pH
Is preferably in the range of 4 to 9.

When silver halide projections are deposited on tabular host grains, a spectral sensitizing dye is usually added as a site director when the silver halide projections are epitaxially adhered before the introduction of 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, the average intergranular silver halide distance is set at 0.1 at the start of growth.
It is preferable to control it to 60 times or more and 1.00 times or less,
More preferably, it is controlled to be 0.60 times or more and 0.80 times or less.

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

In general, the step of preparing a silver halide emulsion is roughly classified into a nucleation step (consisting of a nucleation step and a nucleation 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. The start of growth in the present invention refers to the start of the growth process. The term “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, in a reactant (silver halide emulsion) solution, one side of a cube having a volume equal to the space of one grain, assuming that all the grown grains have the same space. I say the head.
Specifically, it is a value defined by the following equation.

Average intergranular distance = (volume of reaction solution / number of growing particles 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 is carried out. 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 during the growth process of silver halide grains is directly reflected in the volume of a reactant (silver halide emulsion) solution during the growth of silver halide grains.

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

There may be a plurality of the minimum values, and it is preferable to add 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.
It is preferably within a range of 30 minutes, more preferably within a range of ± 15 minutes, and particularly preferably within a range of ± 5 minutes.
It is important to add iodide ions at a time within this range.

In the present invention, it is preferable to perform ultrafiltration on a part or all of the tabular silver halide grains from the start to the end of the growth.

In the present invention, ultrafiltration is performed before or after imparting a certain function to silver halide grains. An example of a production apparatus applicable to this is described with reference to FIG.

The reaction vessel 1 initially contains a dispersion medium 3. The apparatus comprises a reaction vessel 1 and a silver addition line 4 for adding at least one aqueous solution of a silver salt, preferably an aqueous solution of silver nitrate, and at least one aqueous solution of a halide salt, preferably an alkali metal such as bromine, iodine or chlorine. It has a halide addition line 5 for adding an aqueous salt solution, an aqueous ammonium salt solution, or a mixture thereof. Further, it has a stirring mechanism 2 for stirring the dispersion medium and the reactant solution (a mixture of the dispersion medium and the silver halide grains) in the process of preparing the silver halide emulsion. The stirring mechanism can be in any conventional manner. Silver salt aqueous solution is silver addition line 4
From the reaction vessel at a flow rate controlled by the silver addition valve 20. The halide aqueous solution is added to the reaction vessel from the halide addition line 5 at a flow rate controlled by the halide addition valve 21. The addition of the solution through the silver addition line 4 and the halide addition line 5 may be performed 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 halide salt solution with a dispersion medium, and enables the soluble silver salt to react with the soluble halide salt to produce silver halide. During the first stage of silver halide formation, i.e., in the nucleation step, a dispersion (reactant solution) containing the underlying silver halide nucleus particles 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 solution is continued, the second stage of silver halide formation, that is, the growth process stage, is performed, and additional silver halide produced as a reaction product in the process is first formed. Deposited on the coated silver halide nucleus grains to increase the size of these grains. In the present invention, during the particle formation process by adding the aqueous silver salt solution and the aqueous halogen salt solution to the reaction vessel, a part of the reactant solution in the reaction vessel is sent to the ultrafiltration unit 12 through the liquid take-out line 8 by the circulation pump 13. It is sent and returned to the reaction vessel through the liquid return line 9. At that time, the pressure applied to the ultrafiltration unit 12 is adjusted by a pressure adjusting valve 18 provided in the middle of the liquid return line 9 to partially remove the water-soluble salt solution contained in the reaction solution. It is separated by a filtration unit and discharged out of the system through a permeated liquid discharge line 10.

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

In the present invention, it is preferable that the circulation flow rate through the ultrafiltration step is sufficiently high. Specifically, the residence time in the ultrafiltration unit including the liquid take-out line and the liquid return line of the silver halide reactant solution is:
It 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, the circulation pump 13 and the like is preferably 30% or less of the volume of the reaction vessel, and 20% or less. It is more preferably at most 10%, particularly preferably at most 10%.

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

In the present invention, there are no particular restrictions on the ultrafiltration module and the circulating pump which can be used in carrying out the ultrafiltration, but they may act on the silver halide emulsion and adversely affect photographic performance and the like. It is preferable to avoid any material and structure. 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 (%) ) Is preferably 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 growing, a method of growing by adding silver halide fine particles, dissolving and recrystallizing is also preferably used. In particular, silver iodide fine grains, silver bromide fine grains, silver iodobromide fine grains, and silver chloride fine grains are preferably used.

The tabular silver halide grains of the present invention may be so-called halogen conversion type (conversion type) grains. The halogen conversion amount is preferably from 0.2 mol% to 0.5 mol% with respect to the silver amount, and the conversion may be performed during physical ripening or after completion of physical ripening. As a method for halogen conversion, an aqueous halogen solution or fine silver halide particles having a solubility product with silver smaller than the halogen composition on the grain surface before the halogen conversion is usually added. The fine particle size at this time is preferably 0.2 μm or less, more preferably 0.1 μm or less.
02 to 0.1 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. In this case, the rotation speed of the stirring is preferably set to 100 to 1200 rpm.

The silver halide grains of the present invention may have dislocations. The dislocation is described, for example, in J. Mol. F. Hamilto
n, Photo. Sci. Eng, 57 (1967),
T. Shiozawa, J .; Soc. Photo. Sc
i. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the 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.

The tabular silver halide grains of the present invention can be used in the step of forming and / or growing grains in the course of forming cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts). A metal ion is added using at least one selected from a complex salt and an iron salt (including a complex salt), and these metal elements can be contained inside the particle and / or on the surface of the particle.

Next, the compound having a vinyl sulfone group that can be used in the present invention will be described. In the present invention, any compound having a vinylsulfone group and having a hardening action can be used arbitrarily, but in the practice of the present invention, the following specific compounds can be preferably used.

[0054]

Embedded image

[0055]

Embedded image

The amount of these compounds to be added to the hydrophilic colloid layer is arbitrary, but usually 0.01 to 1 g of gelatin.
The range is preferably from 1.0 to 1.0 mmol, more preferably from 0.03 to
A range of 0.5 mmol is preferred.

Next, the tabular silica compound used in the hydrophilic colloid layer of the present invention will be described.

The tabular silica-based compound referred to in the present invention is:
Layered silicate containing alkali, alkaline earth metal, aluminum, etc., that is, tabular silicate, such as kaolin mineral, mica clay mineral, smectite and the like. Kaolin minerals include kaolinite, deckite, nacrite, halloysite, serpentine and the like. Pyrophilite, talc, and mica clay minerals
Examples include muscovite, swellable synthetic fluoromica, sericite, and chlorite. Examples of the smectite include smectite, vermiculite, and swellable synthetic fluorine vermiculite.

Among these, smectite having swelling property and ion exchange property is preferable. There are two types of smectites, natural products and synthetic products. Examples of natural products include montmorillonite and beidellite, which are obtained as clays called bentonite, acid clay, etc. These are used as non-photosensitive hydrophilic agents as antistatic agents. Examples of the use for a hydrophilic colloid layer are described in JP-A-60-202438,
No. 0-239747.

However, synthetic compounds are most preferably used because of their excellent transparency, and there are also compounds containing fluorine for the purpose of further improving heat resistance.

Specific examples of the synthetic smectite include Lucentite SWN manufactured by Corp Chemical Co., Ltd.
(Referred to as STT-1 in the present invention), Lucentite S
WF (referred to as STT-2 in the present invention, containing 2 to 5% by weight of fluorine) and the like. The particle size, thickness, and aspect ratio are as follows.

[0062] It is preferable that these tabular silica-based compounds have an aspect ratio of 2 or more in 50% or more of the total projected area of all the silica used.

The term “aspect ratio” as used herein refers to the ratio of the diameter of a circle having the same area as the projected area of a tabular silica-based compound to the distance between two parallel planes. In the present invention, the aspect ratio is preferably 2 or more and less than 100, particularly preferably 2 or more and less than 50.

The thickness of the tabular silica compound according to the present invention is preferably 1.0 μm or less, more preferably 0.5 μm or less. The distribution of tabular grains is represented by a frequently used variation coefficient (100 times the value S / D obtained by dividing the standard deviation S of the grain size obtained by approximating the projected area into a circle by the average grain size D) by 30.
%, Especially 20% or less, is not essential.

The hydrophilic colloid layer to which the tabular silica compound according to the present invention is added is not particularly limited as long as it is a hydrophilic colloid layer constituting a silver halide photographic light-sensitive material. It can be added to a layer, a protective layer, an intermediate layer, a dye layer, and the like, but is preferably a silver halide emulsion layer and / or a hydrophilic colloid layer above the silver halide emulsion layer with respect to the support.

The preferred amount of the tabular silica-based compound of the present invention used in these layers is 0.05 to 1% by dry weight relative to, for example, the amount of gelatin used as a binder for the hydrophilic colloid layer. 0, particularly preferably 0.1 to 0.6. Further, a colloidal silica and a tabular silica compound may be used in combination.

The tabular silica compound used in the present invention is generally added as an aqueous dispersion to a coating liquid for a hydrophilic colloid layer, and its preparation method is to apply a predetermined amount of water with a sufficient shearing force. It is preferable to add and disperse the tabular silica-based compound little by little while stirring with a high-speed stirrer such as a homomixer or an impeller. When preparing the dispersion, sodium pyrophosphate, polyphosphates such as sodium hexametaphosphate, trimethylolpropane,
A dispersant such as a polyhydric alcohol such as trimethylolethane or trimethylolmethane, or a nonionic polymer such as polyethylene glycol alkyl ester can be appropriately added.

In the present invention, the coating amount of the hydrophilic colloid layer containing the tabular silica compound is 3.0 g / m ² or less, particularly 2.0 g, per one side of the support as a binder amount.
To 0.1 g / m ² is preferably used. Gelatin, dextran, dextrin, and hydrophilic binder
Hydrophilic colloid materials such as natural or synthetic hydrophilic polymers such as polyacrylamide can be used.

The tabular silver halide grains used in the present invention are spectrally sensitized by methine dyes and the like. As the sensitizing dye used in the light-sensitive material of the present invention, cyanine, merocyanine, composite cyanine, composite merocyanine, holopolar, hemicyanine, styryl, and hemioxonol dyes can be used. Particularly useful dyes are those belonging to cyanines, merocyanines and complex merocyanines.

As these dyes, any of the nuclei usually 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-thiooxazolidine-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.

The addition can be made at any time after the formation of the silver halide projections and before the preparation of the emulsion coating solution.

In the present invention, the 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, and useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (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 varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally 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.

When the silver halide photographic light-sensitive material of the present invention is subjected to development processing, it is preferably processed by an automatic processor, and the steps from development to drying are preferably completed within 15 to 120 seconds. That is, the time from when the leading edge of the photosensitive material starts to be immersed in the developing solution to when the leading edge comes out of the drying zone through a processing step (so-called Dry to Dry time) is within 15 seconds to 120 seconds. And more preferably within 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, hot air of usually 35 to 100 ° C., preferably 40 to 80 ° C. may be blown, or a drying zone provided with heating means by far infrared rays may be provided in the automatic developing machine.

An automatic developing machine having 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) may be used. Further, a device capable of adjusting a developing solution or a fixing solution may be incorporated.

When developing the silver halide photographic light-sensitive material of the present invention, the replenishment amounts of the developing solution and the fixing solution are each 18
The treatment is preferably performed at 0 ml / m ² or less, more preferably 8 to 160 ml / m ² , particularly 10 to 100 m / m ^2.
It is preferably processed at 1 / m ² .

When the silver halide photographic light-sensitive material of the present invention is subjected to development processing, the developing agent used may be any of reductones, phenidones, hydroquinone, and any other commonly used photographic processing agents. Particularly preferred are reductones.

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.
It is also preferable to add a cyclodextrin compound.
Compounds described in -124853 are particularly preferred. 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 the development accelerator include, for example, thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, and other 1-phenyl-
If necessary, 3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added.

As an antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant 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.

When developing the silver halide photographic light-sensitive material of the present invention, a compound known as a fixing agent can be added as a fixing agent. Fixing agents, chelating agents, pH buffers, hardeners, preservatives, and the like can be added. These are described in, for example, JP-A-4-242246 (page 4) and JP-A-5-136.
No. 32 (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 alkaline earth metal such as KBr, an organic inhibitor, and a development accelerator are used.

In the emulsion used in the silver halide photographic light-sensitive material of the present invention, various photographic additives can be used 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. 3
Various compounds described in 08119 (December 1989) can be used. These three (RD)
The types and locations of the compounds described in are described below.

[0096]

[Table 1]

The support used in the 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 surface of the support is coated. In order to improve the adhesiveness of the layer, an undercoat layer may be provided, or corona discharge or ultraviolet irradiation may be applied.

[0098]

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) Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 bromide 841 g of potassium 2825 ml of water D1 1.75 N aqueous solution of potassium bromide The following silver potential control amount: 42 ° C, JP-B-58-58288, 58-5828
The solution B1 was added to the solution A1 using the mixing stirrer shown in No. 9.
Then, 464.3 ml of each of the solution C1 and the solution C1 were added by the simultaneous mixing method over 1.5 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, the temperature of the solution A1 was raised to 60 ° C. for 60 minutes, the pH was adjusted to 6.0 with 3% KOH, and then the solution was again added. The B1 and the solution C1 were each mixed with 55.4 by a simultaneous mixing method.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was measured using the solution D1.
It was controlled to be 8 mV and +16 mV.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and the mixture was immediately desalted and washed with water. 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 0.064 μm. Diameter (converted to circle diameter)
Was confirmed to be 0.595 μm by an electron microscope. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

(Preparation of Tabular Host Grains) Tabular host grains were prepared by using Seed Emulsion-1 and the following four kinds of solutions.

A2 Ossein gelatin 34.03 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous solution of ethanol) 2.25 ml Seed emulsion-1 1.722 mol equivalent Equivalent to 3150 ml with water.

B2 Make up to 3644 ml with 1734 g potassium bromide water.

C2 Silver nitrate 2478 g Make up to 4165 ml with water.

D2 Fine grain emulsion (*) consisting of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) Equivalent to 0.080 mol * 5.0 weight containing 0.06 mol of potassium iodide To 6.64 liters of an aqueous gelatin solution, 2 liters each of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. During the formation of the fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

In the reaction vessel, the solution A2 was vigorously stirred while maintaining it at 60 ° C., and a part of the solution B2, a part of the solution C2 and half of the solution D2 were added thereto by a double jet method over 5 minutes. Then, half of the remaining amount of the solution B2 and the solution C2 are added over a period of 37 minutes, and a part of the solution B2, a part of the solution C2, and the entire remaining amount of the solution D2 are added over 15 minutes. The total amount of the remaining solutions B2 and C2 was added thereto over 33 minutes. During this time, the pH was 5.8 and the pAg was
It was kept at 8.8 throughout. Here, the addition rates of the solution B2 and the solution C2 were changed as a function of time in accordance with the critical growth rate.

When the obtained flat host particles were observed with an electron microscope, the average particle diameter was 0.984 μm and the average thickness was 0.2.
2μ, average aspect ratio about 4.5, width of particle size distribution 1
It was 8.1% tabular silver halide grains. The average of the twin plane distance is 0.020 μm, and the grains having a twin plane distance to thickness ratio of 5 or more are 97% (number) of all tabular silver halide grains and 10 or more grains. Occupied 49%, and 15% or more of the particles occupied 17%.

(Preparation of Em-1) The above-mentioned tabular host grain emulsion was melted at 40 ° C., and the 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 have a silver iodide content of silver halide which precipitates in a small amount during the preparation.
It was added in such a ratio as to give mol%.

Next, based on the amount of the first tabular host grains,
After addition of a 2 mol% sodium chloride solution, 0.6 mmol of sensitizing dye (A) and 0.1 mol of sensitizing dye (B) per mole of silver.
006 mmol (each amount per mole of silver) was added as a dispersion in the form of solid fine particles.
Sodium bromide, silver iodide fine grain emulsion (the same as used in the preparation of tabular host grains), 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, the composition ratio (mol%) of the halide added in the preparation of Em-1 was added so that Cl: Br: I = 42: 42: 16.

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 fine particle 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 adjusted to 27 ° C. in advance, and 3.5 is added by a high-speed stirrer (dissolver).
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 Obtained Em-1 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 substrate were observed. Since the silver halide projections were formed after the growth was completed, the average intergranular distance at this time was the maximum.

(Preparation of Em-2) In the preparation of Em-1, after forming the host tabular grains, the silver halide emulsion was subjected to an ultrafiltration module (manufactured by Asahi Chemical Industry Co., Ltd., molecular weight cut off 13).
Type A using 000 polyacrylonitrile membrane
Em-2 was prepared in the same manner except that the emulsion was circulated through LP-1010) until the volume of the emulsion became 1/5, and the sensitizing dyes (A) and (B) were not added.

Observation of the obtained Em-2 with an electron microscope revealed that silver halide projections epitaxially adhered to the periphery of the main plane ((1,1,1) plane).

Since the silver halide projections were formed by reducing the volume of the emulsion to 1/5, the average distance between grains at this time was extremely small.

The particle diameters and thicknesses of the prepared Em-1 and Em-2, and the average intergranular distance at the time of forming silver halide projections are summarized below.
It looks like this:

Emulsion No. Equivalent diameter of circle (μm) Thickness (μm) Average distance between grains when forming AgX projections Em-1 0.984 0.22 Maximum Em-2 0.984 0.22 Extremely small (Chemical formula of Em-1 Sensitization) After the obtained Em-1 was heated to 60 ° C., a mixed aqueous solution of adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate and a dispersion of triphenylphosphine selenide were added. Fine grain emulsion was added and ripening was performed for a total of 2 hours.
At the end of aging, an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

The above-mentioned 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 dispersion of triphenylphosphine selenide described above is as follows. Prepared. 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 wt% 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 wt% 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 Em-2) In the chemical sensitization of Em-2, the sensitizing dyes (A) and (B) were added as the following solid fine particle dispersions after the emulsion was heated to 60 ° C. Em-2 was chemically sensitized in the same manner as above except that adenine, ammonium thiocyanate, a mixed aqueous solution of ammonium chloroaurate and sodium thiosulfate and a dispersion of triphenylphosphine selenide were added.

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 and coating sample N
o. 1-1 to 1-14 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) Emulsion obtained above The following 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 polyacrylamide (average molecular weight 10,000) 0.1 g / m ² Sodium polyacrylate 30 mg / m ² Polysiloxane (S1) 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 3mg / m 2 C 8 F 17 SO 2 N- (C 3 H 7) (CH 2 CH 2 O) 15 H 2mg / m 2 C 8 F 17 SO 2 N- (C _{3 H 7) (CH 2 CH} 2 O) 4 (CH 2) ₄ SO ₃ Na 1mg / m ² Hardener Table 2

[0126]

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[0127]

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[0128]

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[0129]

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Note that 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) <Preparation of solid developer-1> Granules (A) 500 g of 1-phenyl-3-pyrazolidone, 10 g of N-acetyl-D, L-penicillamine, 500 g of boric acid, Glutaraldehyde sodium bisulfite adduct 1000g
Are ground in a commercially available bantam mill to an average of 10 μm.

To this fine powder, 300 g of DTPA · 5Na (diethylenetriaminepentaacetic acid · pentasodium), 300 g of dimezone S (1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone), 400 g of ascorbic acid
0 g, sodium sulphite 1600 g, 1-phenyl-5
-7.0 g of mercaptotetrazole, 400 g of binder mannitol are added and mixed in a mill for 30 minutes, and granulated by adding 30 ml of water in a commercial stirring granulator at room temperature for about 10 minutes, The granulated product is subjected to 40
After drying at 2 ° C. for 2 hours, the water content of the granules is almost completely removed.

Granulated product (B) 11000 g of potassium carbonate, 2000 of sodium bicarbonate
g are each ground in a commercially available bantam mill to an average of 10 μm. 800 g of binder mannitol is added to each fine powder, mixed in a mill for 30 minutes, and granulated by adding 30 ml of water at room temperature for about 15 minutes in a commercially available stirring granulator, and then granulating. The material is dried in a fluidized drier at 40 ° C. for 2 hours to almost completely remove the water content of the granulated material.

The granules (A) and (B) thus obtained were mixed with 100 g of sodium lauryl sulfate at 25 ° C.
Using a mixer in a room conditioned to 40% RH or less
After uniformly mixing for 1 minute, the obtained mixture was subjected to compression tableting with a tableting machine modified from Kikusui Seisakusho's Tough Presto Collect 1527HU to a filling amount of 10 g per tablet,
An ascorbic acid-based developing tablet was prepared.

The method for preparing the working solution is to add water to 24 solid developers to make 1 liter of working solution.

<Preparation of Solid Fixing Agent> Granulated product (C) Ammonium thiosulfate / sodium thiosulfate (90/1
15000 g), 1500 g of β-alanine, and 4000 g of sodium acetate are pulverized in a commercially available bantam mill to an average of 10 μm.

To this fine powder were added 500 g of sodium sulfite, 750 g of sodium persulfate, and 1300 mannitol binder.
g, adding water to 50 ml and performing stirring granulation,
The granulate is dried at 40 ° C. in a fluidized bed drier to remove water almost completely.

Granules (D) 700 g of boric acid, aluminum sulfate / 18-hydrate 1500
g, 1200 g of succinic acid are ground as in (A). 200 g of sodium hydrogen sulfate was added to this fine powder, and the amount of water added was 3
The mixture is adjusted to 0 ml and stirred and granulated.

The granules (C) and (D) thus obtained were mixed with 150 g of sodium lauryl sulfate at 25 ° C.
Using a mixer in a room conditioned to 40% RH or less
After uniformly mixing for 1 minute, the obtained mixture was subjected to compression tableting with a tableting machine modified from Kikusui Seisakusho's Tough Presto Collect 1527HU to a filling amount of 10 g per tablet,
A fixing tablet was prepared. In the preparation method of the working solution, water was added to 28 solid fixing agents to make 1 liter of the working solution to obtain a fixing solution-1.

The developer-1 and the fixer-1 prepared as described above were placed in an automatic developing machine TCX-201 (manufactured by Konica Corporation), and
The running process was performed in the 0 second mode under the following conditions.

The developing temperature and the fixing temperature are both 36 ° C.
Photo developer and fixer photosensitive material 1 m ² per 150ml
Each sample was processed while being replenished one by one. At the start of processing, acetic acid was used as a starter in the developing tank of the automatic developing machine, and potassium bromide was added in an amount to make the developing pH 10.00.
An amount giving a concentration of 2.2 g / l was added to obtain a new solution.

(Evaluation of Samples) (1) Evaluation of Fog Each of the obtained samples was processed with the above-mentioned TCX-201 without exposure, and then the density was measured. The smaller the value, the lower the fog.

(2) Evaluation of silver color tone For evaluation of silver color tone, first, the obtained sample was exposed to X-rays so that the density after processing was 1.1 ± 0.05, and after the same processing as in (1). The following three stages were visually evaluated.

A: Cool black B: Slightly yellowish but acceptable level C: Very yellowish.

(3) Evaluation of dryness For the evaluation of dryness, each of the obtained samples was exposed in the same manner as in (2), and 70 samples of 4 samples in each sample were used for (1).
(2) The same processing was performed, and the 70th sample immediately after the processing was evaluated with the following three grades by touch.

A: Satisfactory drying, slips when samples are stacked and tilted B: Slightly wet, but does not stick even when samples are stacked C: Poor drying, sticks when samples are stacked Would.

Table 2 shows the results.

[0148]

[Table 2]

It can be seen that the sample of the present invention has good fog, silver tone and dryness.

Example 2 Sample No. 1 was prepared in the same manner as in Example 1 except that the silver halide photographic light-sensitive material was prepared by adding the tabulated silica or latex shown in Table 3 to the added layer shown in Table 3 in the same amount as in Table 3. 2-1 to 2-22 were produced. As the hardener, a mixture of glyoxal and formalin in a molar ratio of 6: 4 was added to 0.4 mmol / m ² protective layer.

(1) Evaluation of pressure fog (roller mark) Each of the obtained samples was subjected to the same X-ray exposure as in (2) Evaluation of silver tone in Example 1, and the same processing was performed. However, the development rack and the transition rack from development to fixing are approximately 1
A roller having unevenness of about 0 micron on the entire surface was used. A sample with poor pressure resistance has a small spot-like fog failure due to the pressure caused by the unevenness.

The spot-like fog (roller mark) of each sample after the treatment was visually evaluated in the following three stages.

A: No spots were generated. B: A small number of spots were generated, but the level was acceptable for practical use. C: A considerable number of spots were generated, and this was a practically problematic level.

(2) Evaluation of Residual Color Each of the unexposed samples was subjected to the same treatment as in (1) Evaluation of fog in Example 1, and was visually evaluated in the following three stages.

A: There is no residual color contamination (color residual). B: There is a little residual color, but it is not bothersome. C: There is considerable residual color, and it is hard to see.

(3) Evaluation of Silver Tone Evaluation was made in the same manner as in (2) Evaluation of Silver Tone in Example 1. Table 3 shows the results.

[0157]

[Table 3]

[0158]

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It can be seen that the sample of the present invention has good sensitivity and silver tone.

[0160]

According to the present invention, a silver halide photographic material having good dryability and silver tone and low fog even in rapid processing, and a silver halide having improved silver tone, pressure fog, and residual color after processing. A photographic light-sensitive material could 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 manufacturing equipment of the present invention.

[Explanation of symbols]

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/30 G03C 1/30 1/32 1/32 1/95 1/95

Claims (3)

[Claims] Claims: 1. It has at least one hydrophilic colloid layer containing tabular silver halide grains satisfying the following conditions,
A silver halide photographic material characterized by being hardened with a vinyl sulfone hardener. <Conditions of Tabular Silver Halide Grains> The (1,1,1) plane is the main plane, and the equivalent circle diameter is 0.5.
３3.0 μm, thickness 0.07-0.7 μm. Includes epitaxially deposited silver halide protrusions in a face centered cubic lattice structure forming an epitaxy junction. The silver halide projections are located at the periphery of the host tabular grains. From the start to the end of the growth, under the condition that the average intergranular distance represented by the following formula has a minimum value, the silver halide projection is formed at a time near the minimum value. Average distance between particles = (volume of reaction solution / number of growing particles in reaction solution) ^1/3 2. The method according to claim 1, wherein the at least one hydrophilic colloid layer containing tabular silver halide grains satisfying the conditions for the tabular silver halide grains and at least one layer containing a tabular silica-based compound are provided. A silver halide photographic light-sensitive material comprising: 3. The silver halide photographic light-sensitive material according to claim 1, wherein the tabular silver halide grains are subjected to ultrafiltration from the start to the end of the growth.