JPH10301219A - Silver halide photographic sensitive material and processing method for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart high sensitivity and rapid processability to a photographic sensitive material and to prevent uneven processing from being generated even in a system in which a small amt. of a processing soln. is replenished. SOLUTION: This silver halide photographic sensitive material is provided with at least one silver halide emulsion layer on a substrate. The silver halide emulsion layer is made to contain a silver halide emulsion contg. silver halid particles in which the host particles are platelike silver halide particles, the epitaxial formed parts are provided and the silver halide emulsion is reduced and sensitized or the silver halide emulsion layer is made to contain the platelike silver halide emulsion particles in which the principal planes are (1, 0, 0) planes, the silver chloride contents are made to >=30 mol.%, the aspect ratio is >=2 and the silver halide emulsion is reducted and sensitized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the provision of a silver halide photographic material and a method for processing a silver halide photographic material, and more particularly, to a high sensitivity and rapid processing suitability and a replenishing amount of a processing solution. The present invention relates to the provision of a silver halide light-sensitive material which does not cause processing unevenness even in a system having a small amount of light, and a processing method thereof.

[0002]

2. Description of the Related Art Since 1995, the disposal of photographic processing wastewater into the ocean has been prohibited, and incineration has been carried out. However, land-based processing of processing wastewater causes an increase in energy and cost, and the amount of replenishment is reduced in order to suppress the processing wastewater. It has been desired to reduce this. However, the reduction of the processing waste liquid increases the stagnation time of the liquid in the processing tank, causes oxidative fatigue of the processing liquid, lowers the density and gamma of the photosensitive material to be processed, or causes uneven density, resulting in deterioration of processing stability. Having.

In addition, from the viewpoint of emergency medical care, prompt provision of image information is required in order to quickly grasp the condition of a patient and take prompt treatment, and there is a strong demand for rapid processing of photosensitive materials. .

In order to meet these demands, the covering silver amount is increased by increasing the covering power of developed silver by a method such as reducing the average grain size or using tabular grains having a high aspect ratio and a small grain thickness. It is known to lower. However, when the particle size is reduced, the sensitivity is reduced, so that sensitization is necessary to maintain the conventional sensitivity. Until now, various silver sensitization technologies have been used to reduce the amount of silver in photosensitive materials, and have been working to speed up processing time and reduce processing waste liquid. However, in order to further speed up and / or reduce processing waste liquid, Further sensitization technology is required.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide light-sensitive material which has high sensitivity and rapid processing suitability and does not cause processing unevenness even in a system in which the replenishing amount of a processing solution is small. And a processing method therefor.

[0006]

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

(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer has tabular silver halide grains as host grains and is formed epitaxially. A silver halide photographic light-sensitive material comprising a silver halide emulsion containing silver halide grains having a portion, wherein the silver halide emulsion is reduction-sensitized.

(2) The silver halide photographic material as described in (1) above, wherein the silver halide grains having an epitaxially formed portion satisfy the following conditions (i) to (iii).

(I) The host particles are tabular particles having a (1,1,1) plane as a main plane, and have a circle equivalent diameter of 0.5 to
5.0 μm and a thickness of 0.07 to 0.3 μm, (i
i) including epitaxially deposited silver halide protrusions of a face centered cubic lattice structure forming an epitaxy junction;
(Iii) The silver halide projections are located at the periphery of the host tabular grains.

(3) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer has a main plane of (1,0,0).
Surface tabular silver halide grains having a silver chloride content of 30 mol% or more and an aspect ratio of 2 or more, and the silver halide emulsion is reduction-sensitized. Silver halide photographic light-sensitive material.

(4) The halogenation according to the above (3), wherein the silver halide emulsion layer and / or the other hydrophilic colloid layer contains at least one compound represented by the following general formula (1). Silver photographic photosensitive material.

[0012]

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[In the formula, R ₁ represents an aryl group substituted by at least one or more sulfo group, carboxy group, amino group, hydroxy group or a salt thereof or a boron residue. When two or more substituents are present, they may be the same or different. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium, or a group in which M can be a hydrogen atom or an alkali metal under alkaline conditions. (5) The above-mentioned item (1), wherein the processing is carried out by an automatic developing system in which the replenishment amounts of the developing solution and the fixing solution are 200 ml or less per 1 m ^{2 of the} silver halide photographic material to be processed.
5. The method for processing a silver halide photographic light-sensitive material according to any one of items 1 to 4,

Hereinafter, the present invention will be described in detail. The host tabular silver halide grains in the present invention are those commonly used. A description of tabular silver halide grains meeting this criterion is given in Wilgus et al., US Pat. No. 4,434,434.
No. 226; Kofron et al., US Pat.
No. 9,520; Solver et al., US Pat.
No. 433,048; U.S. Pat. No. 4,672,027 to Yamada et al .; U.S. Pat. No. 4,665,012 to Sugimoto et al .; U.S. Pat. No. 4,679,745 to Yamada et al. Writing; Maska
No. 4,713,320 to Sky; No.
U.S. Pat. No. 4,722,886 totorf;
Sugimoto U.S. Pat. No. 4,755,456; Goda U.S. Pat. No. 4,755,617; Ellis U.S. Pat. No. 4,801,522; Ikeda et al. U.S. Pat. No. 806,461; Ohashi et al., U.S. Pat. No. 4,835,095.
US Patent No. 4,835,3 to Makino et al.
No. 22, U.S. Pat. No. 4,914,014 to Daubendiek et al .; U.S. Pat. No. 4,962,015 to Aida et al .; U.S. Pat. No. 4,985,350 to Ikeda et al. U.S. Pat. No. 5,061,609 to Piggin et al .; U.S. Pat. No. 5,061,616 to Piggin et al .; U.S. Pat. No. 5,147,771 to Tsaur et al .; Tsur
U.S. Patent No. 5,147,772; Tsau.
U.S. Pat. No. 5,147,773 to R. et al .; Tsa
U.S. Pat. No. 5,171,659 to Ur et al .; Su
U.S. Patent No. 5,300,413 totton et al .;
U.S. Patent No. 5,310,644 to Delton; U.S. Patent No. 5,314,793 to Chang et al .; U.S. Patent No. 5,334,495 to Black et al .; U.S. Patent No. to Chaffee et al. 5,358,8
No. 40 and Delton US Pat. No. 5,37.
2,927 and the like.

The tabular silver halide grains according to claim 1 of the present invention are prepared by preparing the host tabular silver halide grains and then performing epitaxy growth. Hereinafter, the silver halide grains at the time of preparing the host tabular silver halide grains will be referred to as “host tabular grains”.

The halogen composition of the host tabular 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 0.1 mol% to 10 mol%, more preferably 0.2 mol%.
-6 mol% is more preferable, and 0.4 mol%-2 mol% is particularly preferable. It is possible for tabular silver halide grains to contain small amounts of silver chloride, for example, US Pat.
No. 372,927 describes silver chlorobromide tabular grains having a silver chloride content of 0.4 to 20 mol%.

One embodiment of the tabular silver halide grain according to claim 1 of the present invention has two opposing parallel main planes, and the main plane is a (1,1,1) plane. The equivalent circle diameter is 0.5 to 5.0 μm, preferably 0.5 to 2.0 μm
It is. The thickness is 0.07 to 0.7 μm, preferably 0.1 to 0.7 μm.

Here, the equivalent circle diameter means an average projected area diameter (hereinafter referred to as a grain diameter), and is a circle equivalent diameter of the projected area of the tabular silver halide grains (the same projected area as the silver halide grains). And the thickness indicates the distance between two parallel main planes forming tabular silver halide grains.

The tabular silver halide grains according to claim 1 of the present invention are preferably monodisperse emulsions having a narrow particle size distribution, specifically, (standard deviation of particle size / average particle size) × 100 = particle size distribution. When the breadth of distribution is defined by the breadth (%), it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

The tabular silver halide grains according to claim 1 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 the tabular silver halide grains according to claim 1 of the present invention, the silver halide projections may be formed on the main plane or the peripheral portion of the host tabular grain. It is more preferable to form them. 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

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 preferably from 0.1 mol% to 13 mol%, more preferably from 0.1 mol% to 10 mol%.

When the silver halide projections are deposited on the host tabular grains, halide ions are introduced. When a plurality of halide ions are introduced, those having a high solubility of a salt with silver may be added. preferable.

Since the solubility of silver iodide is lower than that of silver bromide and the solubility of silver bromide is lower than that of silver chloride, when halide ions are added in a preferred order,
Chloride ions are most likely to adhere near the joint. In some cases, the projections form a clear layer and can detect regions with high and low chloride ion concentrations, but sometimes cannot be detected when halides are added in a preferred order. This is because both bromide and iodide ions have the ability to replace the chloride of silver chloride deposited earlier to some extent.

In the present invention, the silver halide epitaxy is formed in the vicinity of the periphery of the host tabular grains and in less than 50% of the (1,1,1) plane of the tabular grains, preferably in the (1,1) plane of the tabular grains. It is preferred to limit the fraction to a much smaller proportion of the 1,1) plane, preferably less than 25%, most preferably less than 10% and optimally less than 5%. When the tabular grains include a central region with low iodide concentration and regions located on the sides with high iodide concentration, silver halide epitaxy is typically applied to the edges and corners of the tabular grains. Is preferably limited to the tabular grains formed by the regions arranged on the side portions containing

In practicing the present invention, a nominal amount of silver halide epitaxy is effective at about 0.05 mol% based on the total silver (including silver in the host and epitaxy). It is preferred to limit silver halide epitaxy to less than 50% of total silver. Generally, a silver halide epitaxy concentration of 0.3 to 25 mol% is preferred, and a concentration of about 0.5 to 15 mol% is generally optimal for sensitization.

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

When the silver halide projections are formed on the periphery of the host tabular grain, before introducing the halide ions, a compound (site) having an action to limit the site where the silver halide projections are epitaxially attached. Director: hereafter referred to as the site director). Without the addition of the site director, the silver halide projections were not only at the periphery of the host tabular grains,
Precipitates over the entire main plane.

The site director preferably used in the present invention may be any of compounds generally known in the art as spectral sensitizing dyes for silver halide grains, and specific examples thereof include cyanine, merocyanine, complex cyanine, and complex merocyanine. , Holopolar, hemicyanine, styryl, hemioxanol dyes and the like are preferred. In particular, green and red absorbing cyanine dyes are preferred. Further, as a site director of the inorganic compound, iodide, thiocyanide, selenocyanide and the like can also be used.

When the site director is introduced, the temperature of the emulsion containing the host tabular grains is introduced at an arbitrary temperature of 35 to 70 ° C. Preferably it is 35-60 degreeC.

When the site director is introduced, the emulsion containing host tabular grains has a pAg of 6 to 8.5, and a pH of 6 to 8.5.
Is preferably in the range of 4 to 9.

A third aspect of the present invention is a tabular silver halide in which 50% or more of the total projected area of silver halide grains contained in the emulsion layer has a (1,0,0) plane as a main plane. It is characterized by being composed of particles, but preferably at least 70%, more preferably at least 90%.

In the present invention, the shape of the main plane of the tabular silver halide grains having the (1,0,0) plane as the main plane is a shape of a rectangular parallelogram or a rectangular parallelogram with rounded corners. The adjacent side ratio of the right-angled parallelogram is less than 10, preferably less than 5, and more preferably less than 2.
In addition, the length of a side when the corner is rounded is represented by a distance between an intersection of a line extending the straight part of the side and the straight part of the adjacent side.

The average particle diameter of the tabular silver halide grains is preferably from 0.15 to 5.0 μm, more preferably from 0.4 to 5.0 μm.
More preferably, it is 3.0 μm, most preferably 0.4 to 2.0 μm.

The average thickness of the tabular silver halide grains is preferably 0.01 to 1.0 μm, more preferably 0.02 to 0.40 μm, and still more preferably 0.02 to 0.40 μm.
2 to 0.30 μm.

Particle size and thickness can be optimized to optimize sensitivity and other photographic properties. The optimal particle size and the optimal thickness are, for example, the sensitivity, the thickness of the hydrophilic colloid layer, the degree of hardening, and other factors affecting the photographic characteristics.
It depends on the conditions of chemical ripening, the setting sensitivity of the photosensitive material, the amount of silver, and the like.

The tabular silver halide grains having a (1,0,0) plane as the main plane of the present invention are also preferably monodisperse emulsions having a narrow particle size distribution. In this case, the content is preferably 25% or less, more preferably 20% or less.
%, Particularly preferably 15% or less. It is preferable that the thickness distribution is small. Specifically, when the width of the distribution described above is defined, it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

The silver chloride tabular silver halide grains having a (1,0,0) plane as a main plane according to the present invention include silver chloride, silver chlorobromide, silver iodochloride, silver chloroiodobromide and the like as silver halide. Can be used. The silver iodide content is preferably not more than 1.0 mol%, more preferably not more than 0.5 mol%, as the average silver iodide content in the whole silver halide grains.

The tabular silver halide grains referred to in the present invention are grains having two opposing parallel main planes.
Ratio of particle size to particle thickness (hereinafter referred to as aspect ratio)
Mean greater than 1.3. Here, the grain size means an average projected area diameter (hereinafter referred to as a grain size), and is a circle equivalent diameter of a projected area of the tabular silver halide grains (a diameter of a circle having the same projected area as the silver halide grains). ), And the thickness refers to the distance between two parallel main planes forming tabular silver halide grains.

The aspect ratio of the silver chloride tabular silver halide grains having the (1,0,0) plane as the main plane in the present invention is 2 or more, preferably 2.0 or more and less than 15.0.
Particularly, it is preferably 4 or more and less than 8. The silver halide grains can have various halogen compositions, but preferably contain 30 mol% or more, more preferably 50 mol% or more of silver chloride.

The tabular silver halide grains having a (1,0,0) plane as a main plane according to the present invention are disclosed in US Pat. No. 5,320,938.
Can be prepared by the method described in the above item. That is, (1,
It is preferable to form nuclei at low pCl in the presence of iodine ions under conditions that facilitate formation of the (0,0) plane. After nucleation, Ostwald ripening and / or growth is performed to obtain tabular silver halide grains having a desired grain size and distribution.

For example, first, a silver salt solution, a halide solution containing iodide ions, and a protective colloid solution are added to a first container to form nuclei. After the nuclei are formed, the mixed solution is transferred to a second container. Therefore, a method of growing is preferably used.

At this time, the growth may be temporarily stopped in the middle, and then the seed grains may be used as seed grains to grow silver halide on the seed grains. Specifically, an aqueous solution and a seed particle containing a protective colloid are pre-existing in a reaction vessel, and silver ions, halide ions, or silver halide fine particles can be supplied as needed to grow the seed particles.

In order to prepare tabular silver halide grains having a (1,0,0) plane as a main plane according to the present invention, the pCl of the protective colloid solution may be in the range of 0.5 to 3.5. Preferably, 1.0 to 3.0 is more preferable, and 1.5 to 2.5 is most preferable.

In the preparation of tabular silver halide grains having a (1,0,0) plane as a main plane according to the present invention, nucleation is started from the time when a silver salt solution is added to a protective colloid solution. The iodide ion is preferably added at the same time as or before the silver salt solution, and most preferably, it is added before the silver salt solution.

In the preparation of tabular silver halide grains having a (1,0,0) plane as a main plane according to the present invention, iodine can be introduced up to the solid solution limit of silver iodide and silver chloride. ,
The iodine ion concentration in the protective colloid solution at the start of nucleation is preferably 10 mol% or less, more preferably 0.1 mol% or less.
It is at least 01 mol% and at most 10 mol%, most preferably at least 0.05 mol% and at most 10 mol%.

In the preparation of tabular silver halide grains having a (1,0,0) plane as the main plane of the present invention, the addition time of the silver salt solution during nucleation is preferably 5 seconds or more and less than 1 minute. It is preferable that both a silver salt solution and a halide solution are added during nucleation. In particular, iodine ions are preferably added.

Further, bromine ions in the protective colloid solution at the time of nucleation may be present as long as chloride ions are present in an amount of 50 mol% or more.

In the present invention, the silver chloride content of the core is 50%.
It is at least 70 mol%, more preferably at least 90 mol%. PH during nucleation is 2
To 8 are preferred. The temperature is preferably 30 to 90 ° C.,
35-70 ° C is more preferred.

The amount of silver added during nucleation is 0.1% of the total silver.
Preferably it is 1 mol% to 10 mol%.

In the preparation of tabular silver halide grains having a (1,0,0) plane as a main plane according to the present invention, ammonia,
Known silver halide solvents such as thioether and thiourea can be present. In the preparation of tabular silver halide grains having a (1,0,0) plane as a main plane according to the invention,
During the growth, the silver salt solution and the halide solution are added by the double jet method, and the addition rate is such that the new nucleation does not occur and the size distribution does not spread due to Ostwald ripening according to the growth of the grains, that is, the new nuclei are added. 3 of generated speed
Particles having a desired particle diameter and distribution can be obtained by a method of gradually changing the particle diameter in the range of 0 to 100%. 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. In particular, silver iodide fine grains, silver bromide fine grains, silver iodobromide fine grains, and silver chloride fine grains are preferably used.

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

In the silver halide emulsion of the present invention,
Tabular silver halide grains having a (1,1,1) plane or a (1,0,0) plane as a main plane (hereinafter sometimes abbreviated as a tabular silver halide grain of the present invention) are intergranular. Is preferably more uniform in halogen content. EPMA
When the distribution of the halogen content between grains is measured by the method, the relative standard deviation is preferably 35% or less, more preferably 20% or less.

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

At this time, since the electron beam becomes more difficult to penetrate as the thickness of the particles becomes larger, it is more clear to observe using a high-pressure electron microscope (200 kV or more for particles having a thickness of 0.25 μm). can do.

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% based on the silver amount, and the conversion may be carried out during physical ripening or after physical ripening.

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

When silver iodide on the outermost surface of the tabular silver halide grains of the present invention is contained, a silver nitrate solution and a solution containing iodide ions are added to an emulsion containing tabular grains as a base. Simultaneous addition method, addition method of silver iodide, silver iodobromide or silver chloroiodobromide fine particles, potassium iodide or a mixture of potassium iodide and potassium bromide, organic compound releasing iodide ion A method of adding a compound or the like can be applied.

Of these, a preferred method is to add silver halide fine particles. Particularly preferred are the addition of silver iodide fine grains and the addition of an organic compound that releases iodide ions. The timing of adjusting the silver iodide content on the outermost surface is selected from the final stage of the silver halide crystal production process to the chemical ripening process and further to the end of the solution preparation process immediately before the application of the silver halide emulsion. However, it is preferable to adjust by the end of the chemical ripening step. The chemical ripening step referred to here is a point in time when physical ripening and desalting of the silver halide emulsion of the present invention are completed, when a chemical sensitizer is added, and thereafter, an operation for stopping chemical ripening is performed. Up to. Further, the addition of silver halide fine particles may be carried out in several times at intervals, or after the addition of the fine particles,
Further chemically ripened emulsions may be added.

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

In producing the tabular silver halide grains of the present invention, stirring conditions during production are extremely important. As the stirrer, an apparatus disclosed 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 stirring rotation speed is preferably set to 100 to 1200 rpm.

The tabular silver halide grains of the present invention may be formed, and / or grown in the course of grain formation, in the form of cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (complex salt). ) And an iron salt (including a complex salt), and it is preferable to add a metal ion to make the inside of the particle and / or the surface of the particle contain these metal elements.

In the present invention, it is preferable to add a silver halide solvent before the desalting step in order to accelerate the developing speed. For example, a thiocyanate compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) is used in an amount of 1 × 10 ⁻³ mol or more and 3 × 10 ³ mol or more per mol of silver.
It is preferable to add ^-2 mol or less.

In the present invention, gelatin is preferably used as a dispersion medium for the protective colloid of the silver halide grains. As the gelatin, alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 20,000 to 10%) is used.
And modified gelatin such as phthalated gelatin. Other hydrophilic colloids can also be used. Specifically, Research Disclosure Magazine (Resea
rc Disclosure. RD)
76 volume No. 17643 (December 1978).

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

In the present invention, an organic solvent and / or
Alternatively, the compound is preferably spectrally sensitized with a spectral sensitizing dye having a solubility of 2 × 10 ⁻⁴ to 4 × 10 ⁻² mol / l at 27 ° C. in an aqueous system in the absence of a surfactant. Include the following compounds.

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Various dispersers are effectively used for mechanically pulverizing and dispersing these spectral sensitizing dyes in an aqueous solvent to obtain solid fine particles of 1 μm or less. Specifically, a high-speed stirrer, a ball mill, a sand mill, a colloid mill, an ultrasonic disperser, or the like is used. In the present invention, a high-speed stirrer is preferable.

The 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, an aminostilbene compound substituted by a nitrogen-containing heterocyclic nucleus group (for example, US Pat.
Nos. 390 and 3,635,721), and aromatic organic acid formaldehyde condensates (for example, US Pat.
743,510), cadmium salts, azaindene compounds and the like.

In the case of the epitaxial silver halide grains, the spectral sensitizing dye may be added at the time of spectral sensitization by using a site director added at the time of forming silver halide projections. It may be added at any time after the formation of the silver halide projections and before the preparation of the emulsion coating solution.

The reduction sensitization in the present invention will be described below.

The process for producing a silver halide emulsion is roughly divided into processes such as grain formation, desalting, and chemical sensitization. Particle formation is divided into nucleation, ripening, and growth. These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeatedly performed. Applying reduction sensitization during the production process of a silver halide emulsion basically means that it may be performed in any process. Reduction sensitization may be performed during nucleation, which is the initial stage of grain formation, during physical ripening, or during growth, and may be performed prior to chemical sensitization other than reduction sensitization or after this chemical sensitization. . When performing chemical sensitization in combination with gold sensitization, reduction sensitization is preferably performed prior to chemical sensitization so as not to cause undesirable fog. Most preferred is a method of reduction sensitization during growth of silver halide grains. Here, "growing" refers to a method of performing reduction sensitization in a state where silver halide grains are growing by physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide. It is also meant to include a method of further growing after performing reduction sensitization in a state.

The reduction sensitization of the present invention is a method in which a known reducing agent is added to a silver halide emulsion, or a pA called silver ripening.
Either a method of growing in a low pAg atmosphere of g1 to 7 or ripening, a method of growing in an atmosphere of high pH of 8 to 11 called high pH ripening, or a method of ripening can be selected. Also, two or more methods can be used in combination.

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

As reduction sensitizers, stannous salts, amine and polyamic acids, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. In the present invention, these known compounds can be selected for use, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide as reduction sensitizer,
Dimethylamine borane is a preferred compound. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount. However, the addition amount is 10 ^-7 to 10 ^-7 per mol of silver halide.
A range of ^-3 moles is suitable.

Ascorbic acid and derivatives can also be used as the reduction sensitizer of the present invention.

Ascorbic acid and its derivatives (hereinafter referred to as
It is called "ascorbic acid compound". The following can be mentioned as specific examples of ()).

(A-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-3) Potassium L-ascorbate (A-4) DL-ascorbic acid (A-5) D-ascorbic acid Sodium (A-6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid- 5,6-Diacetate (A-10) L-ascorbic acid-5,6-O-isopropylidene The ascorbic acid compound used in the present invention is compared with the amount of the conventional reduction sensitizer which is preferably used. It is desirable to use a large amount. For example, JP-B-57-33572
No. "The amount of reducing agent is usually 0.75 × g per silver ion.
Does not exceed 10 ^-2 meq (8 × 10 ^-4 mol / AgX mol). An amount of 0.1 to 10 mg per kg of silver nitrate (10 ^-7 to 10 ^-5 mol / AgX mol as ascorbic acid) is often effective. Is described. U.S. Pat. No. 2,487,850 states that "a tin compound can be used as a reduction sensitizer in an amount of 1 × 10 ⁻⁷ to 4 × 10 ^−7.
4 × 10 ^-6 mol ". Japanese Patent Application Laid-Open No. 57-1
No. 79835 describes that it is appropriate to use about 0.01 mg to about 2 mg of thiourea dioxide per mole of silver halide and about 0.01 mg to about 3 mg of stannous chloride. Ascorbic acid compound used in the present invention the particle size of the emulsion, the halogen composition, the temperature of emulsion preparation, pH, depends preferably amount by factors such as pAg, per mole of silver halide 5 × 10 ^-5 ~
It is desirable to select from the range of 1 × 10 ^-1 mol. More preferably, it is preferably selected from the range of 5 × 10 ⁻⁴ to 1 × 10 ⁻² mol. Particularly preferred is 1 × 10 ⁻³ to 1 × 1.
It is to choose from a range of 0 ^-2 mol.

The reduction sensitizer may be water or alcohols,
It can be dissolved in a solvent such as glycols, ketones, esters and amides and added during grain formation, before or after chemical sensitization. The compound may be added during any step of the emulsion production process, but a particularly preferable method is to add the compound during grain growth. It is good to add to the reaction vessel in advance,
It is preferable to add at an appropriate time during the particle formation. Alternatively, a reduction sensitizer may be added to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance, and particles may be formed using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

Next, the compound represented by formula (1) of the present invention will be described. In the general formula (1), R ₁ represents one or more sulfo group, carboxy group or hydroxy group,
A linear or branched alkyl group having 1 to 20 carbon atoms substituted with a boron residue (for example, a methyl group, an ethyl group, a propyl group, a hexyl group, a dodecyl group, an isopropyl group, etc.);
A cycloalkyl group having 1 to 20 carbon atoms (eg, cyclopropyl group, cyclohexyl group, etc.), R ₁ is a sulfo group, a carboxy group, a hydroxy group, an aryl group having 6 to 20 carbon atoms substituted with a boron residue (eg, phenyl) A naphthyl group).

The alkyl group (linear or branched alkyl group, cycloalkyl group) and the aryl group may be further substituted. Specifically, a halogen atom (F, Cl, Br, etc.) and an alkyl group (methyl group , An ethyl group, etc.), an aryl group (a phenyl group, etc.), an alkoxy group (a methoxy group,
Ethoxy group), aryloxy group (phenoxy group, etc.), sulfonyl group (methanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamido group, benzamide) Group), an alkoxycarbonylamino group (such as a methoxycarbonylamino group), an aryloxycarbonylamino group (such as a phenoxycarbonylamino group), an alkoxycarbonyl group (such as a methoxycarbonyl group), an aryloxycarbonyl group (such as a phenoxycarbonyl group), Cyano group, nilot group, amino group (unsubstituted amino group, dimethylamino group, etc.), alkylsulfinyl group (methylsulfinyl group, etc.), arylsulfinyl group (phenylsulfinyl group, etc.), alkylthio (Such as methylthio group), an arylthio group (phenylthio group) can be exemplified. Particularly preferred as R ₁ are a methyl group, an ethyl group, and a propyl group substituted with a sulfo group, a hydroxy group, and a carboxy group. M is a hydrogen atom, an alkali metal atom (eg, a sodium atom, a potassium atom, etc.), a quaternary ammonium group (eg, a trimethylammonium group, a dimethylammonium group, a tributylammonium group, etc.) and M becomes a hydrogen atom or an alkali metal under alkaline conditions. Groups (eg, acetyl, cyanoethyl,
Methanesulfonyl group).

The specific examples of the compounds represented by formula (1) used in the present invention are shown below, but the present invention is not limited to these compounds.

[0085]

Embedded image

The addition amount is 0.01 to 1 m ² of the light-sensitive material.
It is preferably from 100 to 100 mg, particularly preferably from 0.05 to 20 mg. The layer may be added in any layer, but is preferably added to the silver halide emulsion layer or the protective layer, and particularly preferably to the protective layer.

In the method of chemical ripening of the grains of the present invention, reduction sensitization, gold sensitization, sulfur sensitization, sensitization with a chalcogen compound, and a combination thereof are preferably used.

The chemical sensitization includes so-called sulfur sensitization,
Gold sensitization, noble metals of group VIII of the periodic table (eg Pd, Pt
And the like, and a sensitization method based on a combination thereof. Among them, a combination of gold sensitization and sulfur sensitization or a combination of gold sensitization and sensitization with a selenium compound is preferable. The addition amount of the selenium compound can be arbitrarily set, but it is preferable to use it together with sodium thiosulfate during chemical sensitization. More preferably, the molar ratio of the selenium compound to sodium thiosulfate is 2: 1 or less, more preferably 1: 1 or less.

In the case of selenium sensitization, a wide variety of conventionally known selenium compounds can be used as the selenium sensitizer used. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (e.g., allyl isoselenocyanate, etc.), selenoureas (e.g., N, N-
Dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenyl Carbonyl selenoureas), seleno ketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids, and selenoesters (eg, 2-seleno) Propionic acid, methyl-3-selenobutyrate, etc.), selenophosforts (e.g., tri-p-triselenofosfate, etc.), 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, etc., but is generally 10 ^-8 to 1 ^-8 per mol of silver halide.
About 0 ^-4 mol is used. Depending on the properties of the selenium compound to be used, the addition method may be a method in which water or an organic solvent such as methanol or ethanol is dissolved alone or in a mixed solvent. Further, a method in which the mixture is added in advance with a gelatin solution or a method in which the mixture is added in the form of an emulsified dispersion of a mixed solution with a polymer soluble in an organic solvent according to a method disclosed in JP-A-4-140739 may be used.

The temperature of chemical ripening using a selenium sensitizer is 4
The range of 0 to 90 degrees is preferable, and more preferably 45 to 8 degrees.
0 degrees. Further, the pH is preferably in the range of 4 to 9, and the pAg is preferably in the range of 6 to 9.5.

It is preferable to supply iodine ions at the time of chemical sensitization or at the end of the chemical sensitization in terms of sensitivity and dye adsorption. Particularly, a method of adding silver iodide in the form of fine grains is preferable.

It is also preferable to carry out the chemical sensitization in the presence of a compound having adsorptivity to silver halide. As the compounds, azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, azaindenes, and particularly compounds having a mercapto group and compounds having a benzene ring are preferable.

US Pat. Nos. 3,615,613 and 3,6
No. 15,641, No. 3,617,295, No. 3,63
The combinations described in US Pat. No. 5,721 and the like are particularly useful.

Gelatin is preferably used as the hydrophilic colloid and the binder used in the light-sensitive material of the present invention, but other hydrophilic colloids can also 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. In particular, it is preferable to use dextran or polyacrylamide having an average molecular weight of 5,000 to 100,000 together with gelatin.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull. Soc. Sci. Photo, Japan
an. No. 16, 30 (1966), gelatin derivatives (e.g., acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, and maleic acid) Obtained by reacting various compounds such as imide compounds, polyalkylene oxides, and epoxy compounds).

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

It is also preferred to add the dye as a solid particulate dispersion. As a method for producing a solid particulate dispersion of a dye, specifically, a fine dispersing machine such as a ball mill, a vibration mill, a planetary mill, a sand mill, a roller mill, a jet mill, and a disk impeller mill using a surfactant. Can be prepared. Also, after dissolving the dye in a weakly alkaline aqueous solution, a method of precipitating fine solid particles by lowering the pH to weakly acidic, or a weakly alkaline solution of the dye and an acidic aqueous solution are simultaneously mixed while adjusting the pH. A dispersion of the dye can be obtained by a method of producing a fine solid. The dyes may be used alone or as a mixture of two or more. 2
When a mixture of more than one species is used, they may be dispersed separately and then mixed, or they may be dispersed simultaneously.

The constituent layer to which the dye is added and contained is preferably a silver halide emulsion layer and / or a layer closer to the support, and more preferably a layer added to the coating layer adjacent to the transparent support. It is effective to do. The concentration of the dye is preferably high on the side close to the support.

The amount of the dye to be added can be changed according to the purpose of sharpness. Preferably, 0.2 to 20 m
g / m ² , more preferably 0.8 to 15 mg / m ² .

In the light-sensitive material of the present invention, when the silver halide emulsion layer is colored, a dye is added to the silver halide emulsion before coating, or to an aqueous solution of a hydrophilic colloid.
These liquids may be applied to the support directly or through another hydrophilic colloid layer by various methods.

As described above, it is preferable that the concentration of the dye is high on the side close to the support, but a mordanting agent can be used to fix the dye on the side close to the support in this way. For example, a non-diffusible mordanting agent can be used to bind to at least one of the dyes described above.

The method for bonding the non-diffusible mordant to the dye is carried out by various methods known in the art, and particularly, the method of bonding in a gelatin binder is preferably applied. In addition, a method of binding in a suitable binder and dispersing in an aqueous gelatin solution by ultrasonic waves or the like can also be applied.

Although the binding ratio is not uniform depending on the compound, usually, 0.1 part to 10 parts of the non-diffusible mordant is bound to 1 part of the water-soluble dye. Since the amount added as the water-soluble dye is bonded to the non-diffusible mordant, it can be used in a larger amount than when the dye is used alone.

When incorporated in the light-sensitive material, a constituent layer containing a combination of a dye and a non-diffusible mordant may be newly provided as a constituent layer, and its position can be arbitrarily selected. It is effective to use it as a coating layer adjacent to the support.

As the surfactant for preparing the solid fine particle dispersion, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant can be used. Anionics such as alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, and N-acyl-N-alkyl taurines Surfactants and nonionic surfactants such as saponins, alkylene oxide derivatives, alkyl esters of sugars and the like.

The amount of the anionic activator and / or the nonionic activator used is not uniform depending on the kind of the activator or the conditions of the dispersion of the dye, but usually, the amount of the dye 1
It may be 0.1 to 2000 mg per g, preferably 0.1 to 2000 mg.
It may be 5 to 1000 mg, more preferably 1 to 50 mg.
0 mg may be sufficient. The concentration in the dispersion of the dye is 0.0
It is used in an amount of 1 to 10% by weight, preferably 0.1 to 10% by weight.
1 to 5% by weight. The surfactant is preferably added at a position before the start of the dispersion of the dye, and may be further added to the dye dispersion after the completion of the dispersion, if necessary. These anionic and / or nonionic activators
Each of them may be used alone, two or more of them may be combined, or both may be used in combination.

When the silver halide emulsion of the present invention is coated on only one side of a support, it is general to provide an antihalation dye-containing layer. The antihalation dye-containing layer may be located between the emulsion and the support, or on the opposite side of the emulsion layer with the support interposed therebetween. It is preferably provided as a back layer. The transmission density of the dye-containing layer at the wavelength of the exposure light source is 0.4 to 1.5, preferably 0.45 to 1.5.
1.2. The method of adding the dye includes aqueous solution addition, micelle dispersion addition, solid dispersion addition, and the like, depending on its properties.

The processing method of the present invention will be described. In developing solutions for black-and-white silver halide photographic materials, dihydroxybenzene compounds represented by hydroquinone have been frequently used as developing agents. However,
In recent years, it has been clarified that hydroquinone is unfavorable from an ecological and toxicological point of view, and furthermore, it has been desired to take measures in consideration of the pollution load (high COD and BOD) of a developing waste solution in a laboratory.

On the other hand, enediols such as ascorbic acid have been recently attracting attention because they have been known to function as a developing agent and have no problem from the viewpoint of ecology and toxicology. .

However, a developing solution containing ascorbic acid as a principal agent is more oxidized and decomposed at a higher alkalinity (eg, pH 10.4 to 11.5) than a hydroquinone developing solution.
Since the amount of generated acid is large, there is a disadvantage that the pH is greatly lowered and the stability of developing activity is lacking.

Therefore, as a corresponding technique, for example, a method of suppressing the oxidative decomposition itself by lowering the pH of the developer and improving the stability of pH fluctuation, or a method of increasing the concentration of carbonate carbonate to 0.5 mol / liter or more. There is disclosed a method of suppressing pH fluctuation by a Bacher function.

These enediols are typically ascorbic acid or erythorbic acid or derivatives derived therefrom, and are commercially available or can be easily synthesized by a known synthesis method.

The amount of ascorbic acid or erythorbic acid or a derivative thereof according to the present invention is 0.05 to 120 g, preferably 10 to 60 g, per liter of the developing solution.
g, more preferably 40 to 50 g.

Examples of the auxiliary developer which exhibits superadditivity with enediols include a 3-pyrazolidone derivative and a p-aminophenol derivative. Hereinafter, specific examples of the auxiliary developer will be described, but the invention is not limited thereto.

1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4, 4'-dimethyl-
3-pyrazolidone, 1-p-tolyl-4,4'-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-
4'-hydroxymethyl-3-pyrazolidone, N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-amino Phenol, p-benzylaminophenol and the like.

In the method for processing a silver halide photographic light-sensitive material of the present invention, a dihydroxybenzene-based developer may be used in combination. Specific compounds include, for example, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
Although 2,5-dimethylhydroquinone and the like can be mentioned, the one that has been most commonly used is hydroquinone.

In the processing method of the present invention, the processing may be performed by using a replenisher for both the developing solution and the fixing solution. The amount of replenishment is not particularly limited, but is 6 to 90 cc per quarter of photosensitive material.
And the replenishment amount is preferably 10% for both the developer and the fixer.
A replenishment amount of ~ 40cc is sufficient.

Further, as a preservative, a developer is disclosed in
In addition to the sulfite described in JP-A-38591, an organic reducing agent can be used. In addition, a bisulfite adduct of a chelating agent or a hardener described in JP-A-6-138391 can be used. Japanese Patent Application Nos. 4-92947 and 5-961
No. 18, silver sludge inhibitor, JP-A-1-1248
It is also preferable to add a cyclodextrin compound described in No. 53 and an amine compound described in U.S. Pat. No. 4,269,929.

It is necessary to use a buffer for the developer.
Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium borate, o-
Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

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

Examples of antifoggants include alkali metal halides such as potassium iodide and benzotriazole;
6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole,
Organic antifoggants such as 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be used.

Further, the developer composition includes methyl cellosolve, methanol, acetone, dimethylformamide, cyclodextrin compound, JP-B-47-33378,
The compounds described in JP-A-44-9509 can be used as an organic solvent for increasing the solubility of the developing agent, and other stain preventing agents, sludge preventing agents and layering effect promoters can also be used.

Known compounds such as a fixing agent, a chelating agent, a pH buffer and a preservative can be used in the fixing solution. For example, those described in JP-A-4-242246 or 5-113632 can be used. it can.

As the fixing agent, thiosulfate, thiocyanate and the like are used, and may further contain a preservative, a pH adjuster, a water softener and the like.

An advantageous method for processing the silver halide photographic light-sensitive material of the present invention is to use an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank.

As the processing agent supply means, when the solid processing agent is a tablet, Japanese Unexamined Utility Model Application Publication No.
No. 97522, Japanese Utility Model Laid-Open No. 1-85732, etc., and in the case of granules or powder, Japanese Utility Model Application Laid-Open No. 62-81
964, 63-84151, JP-A 1-2923
No. 75, etc.
Nos. 59 and 63-195345, etc. can be referred to. The place where the solid processing agent is charged is in the processing tank, but it is preferably in communication with the processing section for processing the photosensitive material, where the processing liquid is flowing between the processing section and the processing section. A preferred structure is one in which there is a constant processing solution circulation amount and the dissolved components move to the processing section. Further, it is preferable that the solid processing agent is introduced into a processing liquid whose temperature is controlled.

When an automatic developing machine is used, the total processing time (D
(ry to Dry) is not particularly limited, but may be 10 to 9
The treatment is preferably performed in 0 seconds, more preferably 15 to 45 seconds, and most preferably 15 to 30 seconds.

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

[0130]

【Example】

Example 1 (Preparation of seed emulsion-1) Seed emulsion-1 was prepared as follows.

A1 Ossein gelatin 24.2 g Water 9657 ml Polypropylene oxy-polyethylene oxy-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 841 g of potassium bromide 2825 ml of water D1 1.75N 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 5.0 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 controlled so that it might be set to 8 mv and +16 mv.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and immediately, desalting and washing were 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 0.064 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 [Em-1]) Using a seed emulsion-1 and the following four kinds of solutions, a tabular silver halide emulsion [E
m-1] was prepared.

A2 Ossein gelatin 34.03 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous solution of ethanol) 2.25 ml Seed emulsion-1 equivalent to 1.722 mol Equivalent to 3150 ml with water B2 Potassium bromide 1733 g Water Finished to 3644 ml with C2 2478 g Finished with water to 4165 ml D2 Fine grain emulsion (*) consisting of 3% by weight of gelatin and silver iodide particles (average particle size 0.05μ) Equivalent to 0.080 mol * 0.06 mol To 6.64 liters of a 5.0% by weight aqueous gelatin solution containing potassium iodide, 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 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, p is added using an aqueous sodium carbonate solution.
H was adjusted to 6.0.

In the reaction vessel, the solution A2 was vigorously stirred while keeping 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.

After completion of the addition, the emulsion was cooled to 40 ° C., subjected to ultrafiltration desalting by a known method, added with a 10% gelatin solution, stirred at 50 ° C. for 30 minutes, and redispersed. After the redispersion, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size 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-2]) [Em-1]
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 12 mol% of silver halide precipitated in a small amount during this preparation.
It was added in such a ratio that

Next, after adding a 2 mol% sodium chloride solution to the first amount of [Em-1], calcium chloride,
Sodium bromide, a silver iodide fine grain emulsion (the same one used in the preparation of [Em-1]), and a 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. Eventually, the composition ratio (mol%) of the halide added in the preparation of [Em-2] was Cl: Br: I = 42: 42: 16.

Observation of the obtained [Em-2] with an electron microscope revealed that not only the periphery but also the main plane ((1,1,1)
A large number of silver halide projections epitaxially adhered on the entire surface of the surface (2) were observed.

(Preparation of [Em-3]) In the preparation of [Em-2], between the addition of sodium chloride and the addition of calcium chloride, 0.1 mol of the exemplified sensitizing dye D-3 was added per mol of silver.
6 mmol, 0.006 mmol of exemplary sensitizing dye D-4
[Em-3] was prepared in the same manner as in the preparation of [Em-2], except that (all amounts per mol of silver) was added as a dispersion in the form of solid fine particles.

A dispersion of the spectral sensitizing dye in the form of solid fine particles was prepared by adding a predetermined amount of the spectral sensitizing dye to water previously adjusted to 27 ° C. and using a high-speed stirrer (dissolver) at 3.500 rpm for 30 minutes.
Obtained by stirring for ~ 120 minutes.

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

(Chemical sensitization of [Em-1])
m-1] is 300 m per mole of silver halide.
l of pure water to 50 ° C., 20 mg of benzyladenine, and 10 minutes later the exemplified sensitizing dye (D
-3) and (D-4) were added as solid fine particle dispersions, respectively, in an amount of 0.6 mol and 0.006 mol. After 10 minutes, 3 × 10 ^-3 mol of ammonium thiocyanate was added, and a further appropriate amount was added. Chloroauric acid and sodium thiosulfate were added. 60 minutes before the completion of chemical sensitization, 4 g of silver iodide fine particles and 2 g of a triphenylphosphine selenide dispersion were added,
Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7
-An appropriate amount of tetrazaindene (TAI) was added to complete the chemical sensitization.

The above-mentioned dispersion of triphenylphosphine selenide was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to ethyl acetate 3 at 50 ° C.
It was added to 0 kg, 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. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at 50 ° C. at a peripheral speed of the dispersion blade of 40 m / sec 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.

In the case where reduction sensitization was performed as shown in Table 1, the benzyl adenine (20 mg) was added 5 minutes before the addition. The same applies to the emulsions described below.

(Chemical sensitization of [Em-2]) [Em-1]
[Em-2] was subjected to chemical sensitization in the same manner as in the above.

(Chemical sensitization of [Em-3]) Sensitizing dye D-
3, [Em-3] was chemically sensitized in the same manner as in [Em-1] except that D-4 was not added.

The resulting emulsion was added with the emulsion additives described below to prepare a prepared solution. The pH was adjusted with sodium carbonate and potassium bromide so that the pH after preparation of the photographic emulsion coating solution was 6.20 and the silver potential was 80 mV (35 ° C.).

Using this emulsion coating solution, a sample was prepared as follows. That is, the photographic emulsion layer was adjusted to 1.8 g / m ² per one side in terms of metallic silver, and the amount of gelatin was adjusted to 1.7 g / m ² per one side.

A protective layer solution was prepared using the additives described below. The protective layer has a gelatin coating weight of 0.7 g / m on one side.
^{The two} layers were simultaneously coated on the support at a speed of 80 m / min using two slide hopper type coaters together with the emulsion layer prepared above so as to obtain 2, and dried for 2 minutes and 20 seconds to obtain a sample.

The additives used in the emulsion are as follows. The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 10 mg t-butyl-catechol 70 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.0 g nitrophenyl-triphenyl Phosphonium chloride 5.0 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 2.0 g 2-Mercaptobenzimidazole-5-sodium sulfonate 1.5 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.5 g 1-phenyl-5-mercaptotetrazole 15 mg methacrylic acid-ethyl acrylate copolymer 18 g

[0155]

Embedded image

Next, the additives used in the protective layer liquid are shown. The stated weight is shown in the amount per liter of the coating solution.

Lime-treated inert gelatin 58 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 1.0 g Polymethyl methacrylate, matting agent having an area average particle size of 3.5 μm 0.4 g Silicon dioxide particles, area average Matting agent with particle size of 1.2 μm 0.7 g Ludox AM (manufactured by DuPont) (colloidal silica) 3.0 g Addition of the following surfactants (a), (b), (c) and hardener

[0158]

Embedded image

Bis-vinylsulfonyl methyl ether 0.4 g The photosensitive material was developed by modifying an automatic developing machine TCX-201 (manufactured by Konica Corporation) so that the Dry to Dry time was 40 seconds, and the developing solution and fixing were performed. The liquid used was TC-DF (manufactured by Konica Corporation). The developing / fixing solution temperature was 35 ° C., and the washing water was 20 ° C. The replenishing amount of the developing solution / fixing solution was 160 ml per 1 m ² of the photosensitive material.

<< Evaluation of Running Stability >> Sample No. 1 was cut into a large angle size, and the entire surface was uniformly exposed so that the optical density after the development process was 1.0, and a running process was performed. The running process is 50 sheets per day, the first day (starting liquid state), 250 sheets (5 days)
Sensitometric performance was determined by the following method at the time of 500 sheets (10 days), and the results are shown in Table 1. At the same time, density unevenness was evaluated by the following method.

<< Sensitometry >> Each of the obtained samples was sandwiched between fluorescent intensifying screens SRO-250 (manufactured by Konica Corporation), tube voltage 90 kVp, current 100 mA, time 0.05.
X-ray irradiation was performed under the condition of seconds, and a sensitometric curve was created by a distance method to determine the sensitivity. The sensitivity value is “Fog +
It was obtained as the reciprocal of the X-ray dose necessary to obtain "1.0".
The γ value was obtained as a slope which was a value obtained by dividing by a logarithmic value difference of an exposure amount necessary for obtaining a density difference in a density range of “fog + 0.25 to fog + 2.0”.

<< Evaluation of Density Unevenness >> The obtained sample was subjected to uniform exposure so that the optical density after the development processing became 1.0, and the first day of the running processing (state of the starting liquid) · 25
At the time of 0 sheets (5 days) and 500 sheets (10 days), the film was developed, visually observed, and evaluated on a 5-point scale based on the following criteria.

5: No density unevenness was observed. 4: Slight density unevenness was observed at the periphery of the film when gazing, but at a level that was not problematic for practical use. 3. When gazing, slight density unevenness was observed throughout the film. But no problem in practical use 2: Density unevenness clearly occurs at the edge of the film and there is a problem in practical use 1: Density unevenness occurs strongly on the entire surface of the film, making it impractical

[0164]

[Table 1]

Table 1 shows that the sample of the present invention has high sensitivity, rapid processing suitability, and excellent running stability.

Example 2 (Preparation of Seed Emulsion-2) <Solution A3> Ossein gelatin 37.5 g KI 0.625 g NaCl 16.5 g Make up to 7500 ml with distilled water <Solution B3> 1500 g of silver nitrate Make up to 2500 ml with distilled water <Solution C3> KI 4 g NaCl 140 g Distilled water to 684 ml <Solution D3> NaCl 375 g distilled water to 1816 ml At 40 ° C., the solution B3 684 ml and solution C
The total amount of 3 was added over 1 minute. EAg 149mV
And after aging for 20 minutes in Ostwald, solution A3
And the total amount of solution D3 were added over 40 minutes.
Meanwhile, EAg was controlled at 149 mV.

Immediately after completion of the addition, desalting and washing were performed to obtain a tabular seed emulsion-2. In the seed emulsion obtained, 60% or more of the total projected area of the silver halide grains consisted of tabular grains having a (1,0,0) plane as a main plane, and an average thickness of 0.07 μm.
Electron microscope observation revealed that the average diameter was 0.5 μm and the coefficient of variation was 25%.

(Preparation of Silver Chloride Tabular Emulsion [Em-4]) A tabular high silver chloride emulsion was prepared using the following four kinds of solutions.

[0169] <solution A4> ossein gelatin _{29.4g HO- (CH 2 CH 2 O} ) n - (CH [CH _{3] CH 2 O) 17 - (CH} 2 CH 2 O) m H (n + m = 5~ 7) 10% methanol aqueous solution 1.45 ml seed emulsion-2 equivalent to 1.05 mol Make up to 3000 ml with distilled water <Solution B4> 3.50 N AgNO ₃ aqueous solution 2240 ml <Solution C4> NaCl 455 g Make up to 2240 ml with distilled water <Solution D4> 1.75N NaCl aqueous solution At the following silver potential control amount at 40 ° C., using a mixing stirrer described in JP-B-58-58288, the total amount of the solution B4 and the solution C4 is simultaneously mixed with the solution A4 by a double jet method. Addition growth was performed for 110 minutes so that the flow rate at the end of the addition was three times the flow rate at the start of the addition.

During this time, the silver potential was +11 using the solution D4.
It controlled so that it might be set to 5 mV. After completion of the addition, precipitation and desalting were performed by the method described below to remove excess salts.

[0171] 1. The temperature of the reaction mixture after completion of mixing is raised to 40 ° C.
Modified with phenylcarbamoyl group (substitution rate 90%)
Add 20g / AgX1mol of modified gelatin, 56wt%
Add acetic acid to lower the pH to 4.30, and allow to stand for decantation 2. Add 1.8 L of pure water at 40 ° C./1 mol of AgX, stir for 10 minutes, then allow to stand and decant 3. 3. Repeat the above step 2 once more. Then, 15 g of post-gelatin / 1 mol of AgX, sodium carbonate and water were added to adjust the pH to 6.0 and dispersed.
Finish to 0 ml / AgX1 mol.

When about 3,000 of the obtained emulsion [Em-4] were observed and measured by an electron microscope to analyze the shape, 80% or more of the total projected area was defined such that the (1,0,0) plane was the main plane. Average diameter 1.09 μm, average thickness 0.21 μm
m and tabular grains having a coefficient of variation of 24%.

The obtained emulsion [Em-4] was chemically sensitized in the same manner as in [Em-1] of Example 1. Thereafter, a photographic material was prepared in the same manner as in Example 1 except that the compound represented by the general formula (1) was added as shown in Table 2.

The obtained sample was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[0175]

[Table 2]

From Table 2, it can be seen that the sample of the present invention has high sensitivity, rapid processing suitability, and excellent running stability.

[0177]

According to the present invention, a silver halide light-sensitive material having high sensitivity, rapid processing suitability, and having no processing unevenness even in a system with a small replenishing amount of a processing solution, and a processing method thereof can be obtained. .

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 5/31 G03C 5/31 5/395 5/395

Claims (5)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The silver halide emulsion layer contains a silver halide emulsion in which the host grains are tabular silver halide grains and contains silver halide grains having an epitaxially formed portion, and the silver halide emulsion is reduced. A silver halide photographic material characterized by being sensitized. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide grains having an epitaxially formed portion satisfy the following conditions (i) to (iii). (I) host particles are tabular particles having a (1,1,1) plane as a main plane, and have a circle-equivalent diameter of 0.5 to 5.0 μm and a thickness of 0.07 to 0.3 μm; ii) including epitaxially deposited silver halide projections of a face-centered cubic lattice structure forming an epitaxy junction, and (iii) the silver halide projections are located at the periphery of the host tabular grains. 3. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The silver halide emulsion layer contains tabular silver halide grains having a (1,0,0) major plane, a silver chloride content of 30 mol% or more, and an aspect ratio of 2 or more, And a silver halide photographic material characterized in that the silver halide emulsion is reduction-sensitized. 4. The halogenation according to claim 3, wherein the silver halide emulsion layer and / or the other hydrophilic colloid layer contains at least one compound represented by the following general formula (1). Silver photographic photosensitive material. Embedded image [In the formula, R ₁ represents an aryl group substituted by at least one or more sulfo group, carboxy group, amino group, hydroxy group or a salt thereof or a boron residue. When two or more substituents are present, they may be the same or different.
M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium, or a group in which M can be a hydrogen atom or an alkali metal under alkaline conditions. ] 5. The process according to claim 1, wherein the replenishment amounts of the developing solution and the fixing solution are not more than 200 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material to be processed. The method for processing a silver halide photographic light-sensitive material described in the above item.