JP2002207266A - Silver halide emulsion, preparation method thereof and silver halide photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide emulsion having high sensitivity and excellent pressure resistance and tone of developed silver, and to provide a preparation method of the silver halide emulsion and a silver halide photographic material. SOLUTION: The silver halide particles included in the emulsion contain the following hexagonal planar particles corresponding to 70 to 100% of the projected area of the silver halide particles. The hexagonal planer particle has the (111) principal plane and has a region including the center part substantially made of silver bromide, a silver iodobromide layer adjacent to and outside of the center part and having 0.3 to 7 mol% proportion of the silver iodide content, and a surface layer having 3 to 15 mol% proportion of the silver iodide content. The hexagonal particles have 8 to 20 average aspect ratio, 0.1 to 1 mol% average proportion of the silver iodide content and 1 to 30% coefficient of variation in the proportion of the silver iodide content.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly, to a silver halide emulsion having high sensitivity, pressure resistance and excellent color tone of developed silver, a method for preparing the same, and a method for preparing the same. It relates to a silver photographic light-sensitive material. In particular, it relates to a silver halide medical photographic material.

[0002]

2. Description of the Related Art In recent years, in the medical field, complete automation before and after photographing and up to development processing, rapid development processing, and low replenishment of development processing liquid have been advanced. In particular, an auto feeder that automatically supplies a photographed sheet film to an automatic developing machine, a take-up film that is taken out from an X-ray mono-cassette cassette, and a series of operations for automatically loading an unexposed film into the cassette are photographed by a receive supplier or a conveyor. Equipment such as a conveyor system that transports sheet film from a laboratory to an automatic processor, and a changer that automatically replaces an exposed and unexposed sheet film with an X-ray intensifying screen fixed at the shooting position have become widely used. I came. Above all, silver halide photographic materials used in connection with the rapid development processing have been reduced in silver amount and made thinner in order to improve development, fixing processability, and drying property in automatic developing machines. It is coming. In particular, in rapid processing, thinning to achieve sufficient drying properties is an important technique.

With respect to tabular silver halide grains necessary for thinning (hereinafter sometimes referred to as tabular grains), US Pat. Nos. 4,434,226 and 4,439,52
No. 4, No. 4,414,310, No. 4,433,0
No. 48, No. 4,414,306 or No. 4,45
No. 9,353 and JP-A-59-99433 or JP-A-62-209445 disclose their production methods and techniques for use, and include an increase in sensitivity including an improvement in color sensitization efficiency by a sensitizing dye. There are known advantages such as improved sharpness and improved covering power. In recent years, demands for silver halide emulsions for photography have become more and more severe, and there is a demand for higher aspect ratios of tabular grains for improving sharpness and the like.

[0004] However, the above-mentioned tabular grains having a high aspect ratio provide a high covering power, but have the disadvantage that the pressure resistance is deteriorated and the color tone of the developed silver is yellowish.

[0005] It has been known that the pressure resistance can be improved by providing a high silver iodide layer of a silver halide emulsion inside silver halide grains, as described in Japanese Patent Laid-Open No. Japanese Patent No. 99433 discloses a method for improving pressure characteristics by providing a high silver iodide layer inside tabular grains. However, in the method described in this publication, high silver iodide was not uniform in or between silver halide grains, and the pressure resistance was insufficient. Thereafter, JP-A-5-53232, JP-A-6-235988 or JP-A-9-211759 describe the position and amount of the high iodine layer inside the silver halide grains. There is a statement that the improvement in dispersibility is compatible.

Generally, an image in which the silver tone of developed silver of a silver halide photographic light-sensitive material after development is yellowish tends to give an unpleasant impression to an image observer. This yellow color is because the thickness of the developed silver decreases as the thickness of the silver halide grains decreases, the scattering of the blue light component increases, and the light component of the yellow component increases. Such a phenomenon is particularly problematic in silver halide fine grain emulsions and thin tabular grains having a thickness of 0.2 μm or less. When the tabular grains are further thinned, not only the color tone of the developed silver in the transmitted light becomes yellowish but also the color tone of the developed silver in the reflected light becomes reddish brown. Therefore, as a general technique, a color tone agent for adjusting the color tone of developed silver, for example, a certain mercapto compound or the like is often used. In addition, Japanese Patent Application Laid-Open No.
As described in JP-A Nos. 85 and 7-199394, there is also an example in which a color tone is adjusted by incorporating a dye or a pigment into a silver halide photographic light-sensitive material. However, these techniques are inadequate in dealing with the above-mentioned problems, especially the reddish-brown tint of developed silver due to reflected light, and improvements have been desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material containing a silver halide emulsion having high sensitivity, excellent pressure resistance and excellent color tone of developed silver. .

[0008]

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

(1) 70 to 100% of the projected area of all contained silver halide grains has a (111) main plane;
And a region including a center portion substantially composed of silver bromide, and the outer silver iodide content adjacent to the region including the center portion is 0.3 to 0.3%.
7 mol% silver iodobromide layer and silver iodide content of 3 to 15 mo
a hexagonal plate having a 1% surface layer, an average aspect ratio of 8 to 20, an average silver iodide content of 0.1 to 1 mol%, and a variation coefficient of silver iodide content between grains of 1 to 30%. A silver halide emulsion characterized by being grains.

(2) The region containing the central portion occupies 30 to 95% as a volume fraction of the tabular grains, and the outer silver iodobromide adjacent to the region containing the central portion contains the tabular grains. The silver halide emulsion according to (1), wherein the silver halide emulsion occupies 5 to 30% as a volume fraction of all grains.

(3) The silver iodobromide layer is 2 to 7 mol%
(1) or (2), which comprises silver iodide.

(4) The tabular grains have a maximum silver iodide content (x, mol) inside the tabular grains excluding the surface layer.
%) And the silver iodide content (y, mol%) of the surface layer has a relationship of 1 ≦ y / x ≦ 20. The silver halide emulsion according to the above.

(5) The tabular grains have a silver iodide content (a, mol) inside the tabular grains excluding the surface layer and a silver iodide content (b, mol) of the surface layer. Between 0.5
The silver halide emulsion according to any one of (1) to (4), having a relationship of ≦ b / a ≦ 2.0.

(6) The halogen according to any one of (1) to (5), wherein the silver iodide in the surface layer is formed by adding silver iodide fine particles. Silver halide emulsion.

(7) In the method for preparing a silver halide emulsion according to any one of (1) to (6), the method is represented by the following formula from the start to the end of the growth of silver halide grains. Silver iodide is formed by adding iodide ions at a time when the average intergranular distance shows a minimum value or a minimum value.

Average grain distance = (volume of reaction solution / number of growing particles in reaction solution) ^1/3 (8) A silver halide emulsion prepared by the method described in (7).

(9) A silver halide emulsion layer containing the silver halide emulsion described in (1) to (6) or (8) is coated on a transparent support with a total coated silver amount per side of 0.5 to 0.5.
A silver halide photographic light-sensitive material, characterized in that the light-sensitive material is coated at 1.5 g / m ² .

(10) The dried film thickness of all coating layers is 1 to
The silver halide photographic light-sensitive material according to (9), wherein the thickness is 3 μm.

Hereinafter, the present invention will be described in detail. The silver halide grains contained in the silver halide emulsion of the present invention are tabular silver halide grains (hereinafter sometimes referred to as tabular grains).
The layer structure from the center to the surface layer,
It has a layer structure such as a central portion, a peripheral region of the central portion, an outer region (silver iodobromide layer) adjacent to the peripheral region of the central portion, and a surface layer.

The silver halide content in the present invention is as follows:
It is based on the finished tabular grains, and is expressed simply as the content of silver halide grains or tabular grains. The term "completed tabular silver halide grains" refers to those obtained after the addition and ripening of all the halogens in the silver halide emulsion are completed.

In the constitution (1) of the present invention, the tabular grains contained in the silver halide emulsion of the present invention are (111)
A hexagonal tabular grain having a surface as a main plane and having an average aspect ratio of 8 to 20, preferably 8 to 15, and more preferably 10 to 15.

The tabular grains in the silver halide emulsion of the present invention account for 70% or more, preferably 90%, of the total silver halide grains as projected areas.
Occupy more.

Here, the (111) main plane of the silver halide grains in the present invention can be confirmed by an X-ray diffraction method or the like. The hexagonal tabular grains have a hexagonal shape when observed from a direction perpendicular to the main plane of the tabular grains, and have a maximum adjacency ratio (having a minimum length forming a hexagon). The ratio of the length of the side having the maximum length to the length of the side) is 1.0 to 2.0, and in the present invention, the maximum adjacent side ratio is 1.0 to 1.5. Is more preferred. If so, the corners may be somewhat rounded. The length of a side having a slightly rounded corner is represented by the distance between the intersection of the straight line portion of the side and the line extending the straight line portion of the adjacent side. Each side forming the hexagon of the tabular grains is 1 /
It is preferred that two or more are substantially linear, especially
It is preferable that / 5 or more be substantially a straight line.

Tabular silver halide grains are crystallographically classified as twins. A twin is a crystal having one or more twin planes in one grain. Classification of twin morphology in silver halide grains is based on a report by Klein and Moiser in Photographischche Korrespo.
ndenz, Vol. 99, p. 99 and Vol. 100, p. 57. The tabular grains according to the present invention have one or two or more twin planes parallel to each other in the silver halide grains, and these twin planes form a plane forming the surface of the tabular grains. Exists almost parallel to a plane having the largest area (also referred to as a main plane). The most preferred form of the tabular silver halide grains in the present invention is one having two parallel twin planes.

In the present invention, the aspect ratio of the tabular grains refers to the ratio of the area-converted grain size to the grain thickness (aspect ratio = grain size / thickness). Here, the area-converted particle size means the diameter of a circle having an area equal to the area when the particle is projected perpendicular to the main plane. On the other hand, the volume-converted grain size means the diameter of a sphere having the same volume as each silver halide grain. The particle thickness is a thickness of a particle in a direction perpendicular to the main plane, and corresponds to a distance between two main planes. The projected area and particle thickness of the particles for calculating the area-converted particle diameter and the volume-converted particle diameter can be obtained by the following methods. In this method, first, a polystyrene sphere particle having a known particle size serving as an internal standard and a sample containing a solution containing silver halide particles applied so that the main plane is oriented parallel to the substrate are prepared on a support, After shadowing from a certain angle by carbon vapor deposition, a replica sample is prepared by a normal replica method. Next, an electron micrograph of the sample is taken, and the projected area and thickness of each particle are determined using an image processing device or the like. The projected area of a particle is
From the projected area of the internal standard, the thickness of the particle can be calculated from the internal standard and the length of the shadow of the particle. In the present invention, the average value of the aspect ratio, the area-converted particle size, the grain thickness, and the volume-converted particle size is obtained by measuring 500 or more arbitrary silver halide grains contained in the silver halide emulsion using the above-described replica method. And the value obtained as their arithmetic average.

The average Δ1 of the tabular grains according to the present invention
The particle diameter of the 11 ° main plane is preferably 0.15 to 5.0.
μm, more preferably 0.4 to 3.0 μm, even more preferably 0.4 to 2.0 μm. The average thickness of the tabular grains according to the present invention is preferably 0.2 μm or less,
More preferably, it is 0.07 to 0.2 μm, and still more preferably 0.1 to 0.2 μm. Tabular grain thickness of 0.2
The tabular surface of silver halide grains formed below μm has a larger surface area, can adsorb more sensitizing dyes per grain, and can absorb more light per grain. Therefore, high sensitivity can be obtained. Further, the crossover light can be reduced, and the sharpness of the silver halide photographic light-sensitive material can be increased. On the other hand, as described in JP-A-6-43605 and JP-A-6-43606, when the thickness of the tabular grains is thinner than 0.1 μm, incident light is mainly emitted from the tabular grains oriented perpendicular to the tabular grains. Reflection tends to be more intense on the surface (flat surface), and as a result, the effect of increasing the light absorption of the particles even when the thickness of the tabular grains is reduced and the more sensitizing dye is adsorbed. Will fade.

The tabular silver halide grains according to the present invention are preferably monodisperse grains having a narrow particle size distribution. Specifically, when the width of the distribution is defined by the following formula: (standard deviation of particle size / average particle size) × 100 = particle size distribution (%), it is preferably 30% or less, more preferably 5 to 5%. It is 20%, particularly preferably 5 to 15%.

The tabular silver halide grains according to the present invention have a layer structure such as a region including a central portion, an outer region adjacent thereto and a surface layer, and each layer has a different silver halide composition. Having. The silver halide composition between the layers may change rapidly or may change continuously,
The silver halide composition of each layer is preferably uniform.

Here, the region containing the center is defined as the central portion of the tabular grains, which are nuclei generated in the nucleation step which is the first stage of grain production, and the same halogen as the central portion around the central portion. The outer region adjacent to the region including the silver halide composition portion refers to a silver halide composition layer different from the region including the central portion adjacent to the region including the central portion. Further, a plurality of layers having different silver halide compositions may be provided between the outer region and the surface layer, and the outer region and the surface layer may be adjacent to each other.

In the constitution (1) of the present invention, the tabular silver halide grains have a layer structure such as a region including the center portion, an outer region adjacent thereto and a surface layer, and the region including the center portion is substantially formed. It is composed of silver bromide, has a silver iodobromide layer in an outer region adjacent thereto, and has the following composition.

The region including the center of the tabular grains substantially consists of silver bromide. Substantially silver bromide means that the content of silver bromide is 99.9 mol% or more, and silver iodide and / or
Alternatively, the silver chloride content is 0.1 mol% or less. Further, in the present invention, the region including the central portion of the grains is preferably made of 100% silver bromide, and the nucleation is preferably performed under the condition that no halogen other than bromine is contained. That is, it is preferable that nucleation is performed under the condition that no halogen compound other than bromine typified by iodine and chlorine is added to the solvent in the mixing vessel for nucleation and the added halogen solution.

The tabular grains according to the present invention have a silver iodobromide layer containing 0.3 to 7 mol% of silver iodide in an outer region adjacent to a region including a central portion. Preferably it is 2 to 7 mol% (configuration (3)). Although the composition of the silver iodobromide layer may be continuously changed to near the surface layer, it is preferable that the surface layer and a region including the central portion are separated by the silver iodobromide layer. In the present invention, the silver iodobromide layer preferably has a uniform composition.

The tabular grains according to the present invention contain 3 to 15 mol%, preferably 6 to 15 mol% of silver iodide outside the above silver iodobromide layer.
It has a surface layer containing １２12 mol%. In the present invention, the content of silver iodide in the surface layer is defined as the content of silver iodide in the surface layer. The surface layer as referred to in the present invention refers to a region from the surface of the tabular grains to a depth of 50 angstroms. The surface silver iodide content is a value measured by the XPS method described below, and in the present invention, the surface layer silver iodide content value by the XPS method is obtained as follows. The sample was placed in an ultra-high vacuum of 1.33 × 10 ⁻⁶ Pa or lower at −115
Cool to below ℃, and use MgKα as X-ray for probe.
Irradiation with a source voltage of 15 kV and an X-ray source current of 40 mA, Ag
It is measured for 3d5 / 2, Br3d, and I3d3 / 2 electrons. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the halide composition on the surface is determined from the intensity ratio.
The structure relating to the halogen composition in the tabular grains is represented by X
It can be examined by a line diffraction method, a composition analysis method by EPMA, or the like.

In the present invention, the average silver iodide content with respect to all tabular grains is from 0.1 to 1 mol%, and from 0.3 to 1 mol%.
0.8 mol% is preferred.

In the silver halide emulsion of the present invention, the coefficient of variation of the silver iodide content per grain (the standard deviation of the distribution of silver iodide content among grains) is defined as the average silver iodide content. Is 1 to 30%, preferably 1 to 25%
%, More preferably 1 to 20%, and the silver iodide content of the tabular grains is preferably uniform among the grains. In the present invention, the silver iodide content of each silver halide grain is represented by X
The composition can be measured by analyzing the composition of each silver halide grain using a line microanalyzer, and it is preferable to measure at least 100 grains or more.

The method for producing tabular grains according to the present invention can be carried out by a conventionally known ripening method of silver halide grains. However, in the constitution (1) of the present invention, the silver iodobromide layer is provided in an outer region adjacent to the region including the center of the tabular grains, and the content of silver iodide in the silver iodobromide layer Is 0.3 to 7 mol%, the outer surface layer of the silver iodobromide layer has 3 to 15 mol% of silver iodide, and the variation of silver iodide content between silver halide grains. The silver iodide composition of each layer having a coefficient of 1 to 30% is particularly important in the silver halide photographic light-sensitive material having tabular grains of the present invention. It is excellent in pressure resistance and can obtain a preferable color tone of developed silver.

In the constitution (2) of the present invention, the region including the central portion of the tabular silver halide grains in (1) is defined as a volume fraction of all tabular grains, an outer region adjacent thereto, and a surface layer. Wherein the region including the central portion is substantially made of silver bromide, and a silver iodobromide layer is formed in an outer region adjacent to the region. And a surface layer containing silver iodide on the outside thereof, and has the following composition.

In the constitution (2) of the present invention, the tabular grains have a region including the central portion substantially made of silver bromide as in the case of the constitution (1), and the region including the central portion has a tabular shape. 30 to 95 as a volume percentage based on the whole silver halide grains.
%, More preferably 30 to 80%.
%. Further, the silver iodide layer in the outer region adjacent to the region including the central portion has a volume percentage of 5% of all tabular grains.
Occupies preferably 30 to 30%, more preferably 7 to 2%.
0%. The silver halide photographic light-sensitive material of the present invention having tabular grains having such a volume fraction has high sensitivity, is excellent in pressure resistance, and can obtain a favorable color tone of developed silver.

In the constitution (4) of the present invention, the tabular grains may have the maximum silver iodide content (x, mol%) inside the tabular grains excluding the surface layer and the silver iodide content of the surface layer. It is more preferable to have a relationship of 1 ≦ y / x ≦ 20 with the content (y, mol%). In the present invention, the maximum silver iodide content in tabular grains means a point at which the silver iodide content in tabular grains excluding the surface layer of all tabular grains shows the maximum value.

In the constitution (5) of the present invention, the tabular grains may have an internal silver iodide content (a, mol) excluding the surface layer of the tabular grains and the iodide content in the surface layer. It is preferable to have a relationship of 0.5 ≦ b / a ≦ 2.0 with the silver content (b, mol). Here, the silver iodide content inside the tabular grains is the total amount of silver iodide present inside the tabular grains excluding the surface layer, and when all of the silver iodobromide of the tabular grains are formed. It is a molar amount of the added iodide ion. The term "silver iodide content in the surface layer" as used herein refers to the total amount of silver iodide present in the tabular grain surface layer, and is the molar amount of iodide ions added during the formation of the tabular grain surface layer.

The formation of silver iodide in the tabular grains according to the present invention uses iodide ions. In the step of growing the tabular grains, there is no particular limitation on the method of adding iodide ions. It may be added as an ionic solution, or a method in which silver iodide fine particles are added to supply iodine ions is also preferable. In particular, a method of forming a tabular grain surface layer by adding silver iodide fine grains is preferable. The timing of adding silver iodide may be a growth step or a sensitizing ripening step.

In the present invention, the formation of a surface layer using silver iodide fine particles is described in JP-A-1-183417 and JP-A-1-183417.
Similarly to silver halide grain growth disclosed in JP-A Nos. 3644 and 1-183645, grain growth may be performed using only silver iodide fine grains.

As a method for preparing a silver halide emulsion and a method for forming tabular silver halide grains of the present invention, methods known in the art can be appropriately applied. For example,
Controlling the pAg of the reaction solution during the formation of silver halide grains,
The so-called controlled double jet method or controlled triple jet method can be preferably used. Further, a silver halide solvent can be used if necessary. Examples of the silver halide solvent useful in the present invention include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Pat. Nos. 3,271,151, 3,790,387 and 3,574,626 can be referred to.

The method for forming silver halide grains according to the present invention is not particularly limited, but an ammonia method, a neutral method using no ammonia, an acidic method, and the like can be used. From the viewpoint that fogging during silver halide grain formation can be suppressed, the pH is preferably 5.5 or less, more preferably 4.5 or less, and silver halide grains are preferably formed on the acidic side.

The silver halide emulsion of the present invention preferably contains a protective colloid as a dispersion medium together with silver halide grains, and it is preferable that the dispersion medium be present from the nucleation step to the end of the grain growth. . Dispersions useful in the present invention include gelatin and / or water-soluble polymers. Gelatin is preferably alkali-treated gelatin or oxidized gelatin having a weight-average molecular weight of about 100,000, or low-molecular-weight gelatin having a molecular weight of about 5,000 to 30,000 can be preferably used. In particular, at the time of nucleation, it is preferable to use an oxidized gelatin, an alkali-treated gelatin having a low molecular weight, or an oxidized gelatin.

The preparation of the silver halide emulsion of the present invention is not different from the usual method, but is roughly divided into a nucleation step (consisting of a nucleation step and a ripening step of nuclei) and a subsequent step of growing the nuclei. .

The nucleus forming step is a step of producing a nucleus (silver halide fine particles) capable of growing silver halide grains by mixing an alkali halide and silver nitrate. The nucleus growing step is a first growing step. , A second growth step, and so on.

The growth step of tabular silver halide grains in the present invention means all growth steps from the formation of nuclei (or seeds) to the end of grain growth. In the present invention, a nuclear emulsion (or seed emulsion) prepared in advance can be separately grown and used.

The structure (7) of the present invention comprises the structures (1) to (6)
And a method for preparing a silver halide emulsion having a tabular grain composition and a layer structure, characterized in that the silver halide composition distribution in the grains obtained by this method is narrower and the performance is improved. A silver halide photographic light-sensitive material using this silver halide emulsion has further improved sensitivity and better pressure resistance, and further has a better color tone of developed silver. The method for preparing a silver halide emulsion according to the constitution (7) of the present invention is characterized in that, during the step of growing silver halide grains contained in the silver halide emulsion, the silver halide emulsion is prepared from the start to the end of the growth of the silver halide grains. In this method, iodine ions are added at a time when the average inter-particle distance shown by the following formula is near the minimum value. Here, the start point of the growth step is referred to as the start of growth. The average distance between grains referred to in the present invention means an average value of a spatial distance between centers of gravity of silver halide grains growing in a reaction solution (silver halide emulsion) at the time of preparing a silver halide emulsion, In other words, assuming that all the growing tabular grains in the reaction solution (silver halide emulsion) each have the same space, the length of one side of the cube having the same volume as the space of one grain is defined as Say. Specifically, it is a value defined by the following equation.

[0050] In the mean distance between particles = (number growing particles in a volume / reaction of the reaction solution) ^1/3 growth step of silver halide grains, an aqueous silver salt solution and halide salt solution which is mainly subjected to the tabular grain growth With the addition of, the amount of the reaction solution in the reaction vessel increases with the growth of the particles, and at the same time, the average interparticle distance increases. As described above, the average intergranular distance in the step of growing silver halide grains is directly reflected in the volume of the reaction solution (silver halide emulsion) during the growth of silver halide grains.

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

In the present invention, there may be a plurality of the minimum values, and the iodine ion is added and prepared at a time near at least one of the minimum values including the minimum value. In the present invention, the near time is, with respect to the time point indicating the minimum value or the time point indicating the minimum value,
The time is within a range of about ± 30 minutes, preferably ± 15 minutes.
Minutes, particularly preferably ± 5 minutes. It is important to add iodine ions at a time within this range.

The tabular silver halide grains of the silver halide emulsion of the present invention preferably contain 97 mol% or more of silver bromide on average, more preferably 98 to 9 on average.
9.5 mol%.

The tabular silver halide grains according to the present invention may have dislocations. Dislocations are described, for example, in J. et al. F. Ha
Milton, Photo. Sci. Eng, 11 volumes, 5
7 (1967); Shiozawa, J .; So
c. Photo. Sci. Japan, Vol. 35, p. 213 (1972), which can be observed by a direct method using a transmission electron microscope at low temperature. That is, the tabular grains taken out so as not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for observation with an electron microscope, and the sample is placed so as to prevent damage (printout, etc.) by an electron beam. Observation is performed by a transmission method in a cooled state. At this time, since the electron beam is more difficult to penetrate as the thickness of the particles is larger, it is more clear to observe with a high-pressure electron microscope (200 kv or more for particles having a thickness of 0.25 μm). I can do it.

Hereinafter, a method for preparing a silver halide emulsion will be described. As the additives added to the silver halide emulsion layer, those described in Research Disclosure (hereinafter abbreviated as RD) can be used.

The silver halide photographic light-sensitive material of the present invention includes:
Various photographic additives can be used. Known additives include, for example, RD No. 17643 (197
No. 8 December), No. 18716 (November 1979
Month) and the same No. 308119 (December 1989).

The technique used for the silver halide emulsion of the present invention includes RD No. 308119 can be used.

The silver halide grains used in the present invention can be subjected to chemical sensitization by a method usually used. The conditions of the step of chemical ripening, that is, chemical sensitization, for example, pH, pAg, temperature, time and the like are not particularly limited, and can be performed under conditions generally used in the art. Chemical sensitization includes sulfur sensitization using a compound containing sulfur capable of reacting with silver ions and active gelatin, selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound, reduction using a reducing substance. There are a sensitization method, gold and other noble metal sensitization methods using a noble metal, and these methods may be used alone or in combination. Among them, selenium sensitization, tellurium sensitization, reduction sensitization, and the like are preferably used, and selenium sensitization is particularly preferably used. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate), and selenoureas (eg, N, N-).
Dimethylselenourea, N, N, N'-triethylselenourea, etc., selenoketones (for example, selenoacetone,
Selenoacetophenone, etc.), selenoamides (for example,
Selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), and selenophosphates (eg,
Tri-p-triselenophosphate, etc.) and selenides (diethyl selenide, diethyl diselenide, triphenylphosphine selenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenium ketones. The amount of the selenium sensitizer used is the selenium compound to be used, silver halide grains,
In general, it depends on the conditions of chemical ripening.
It is preferable to use about 10 ^-8 to 10 ^-4 mol per mol. Depending on the properties of the selenium compound to be used, the addition method may be a method in which the compound is dissolved in water or an organic solvent such as methanol, ethanol, or ethyl acetate alone or in a mixed solvent, or a method in which the compound is previously mixed with a gelatin solution and added. Or a method disclosed in Japanese Patent Application Laid-Open No. 4-140739, that is, a method of adding the compound in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

The silver halide grains in the present invention may be spectrally sensitized with a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

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

In the present invention, more useful sensitizing dyes are trimethinecyanine dyes which give spectral sensitivity to green light, and specific examples thereof are described in JP-A-7-28184, paragraphs [0014] to [0014]. Oxacarbocyanines or benzimidazolocarbocyanines described in 0024].

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 supersensitization. For example, a substituted aminostilbene compound which is a nitrogen-containing heterocyclic nucleus group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), and aromatic organic acid formaldehyde Condensates (for example, those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like may be contained.

US Pat. Nos. 3,615,613;
615,641, 3,617,295, 3,6
The combination described in 35,721 is particularly useful. The sensitizing dye may be added during or during each step of nucleation, growth, desalting, and chemical sensitization, or after chemical sensitization.

Next, the layer constitution in the silver halide photographic light-sensitive material of the present invention will be described. The silver halide photographic light-sensitive material of the present invention comprises a hydrophilic colloid layer having at least one silver halide emulsion layer on a support and containing a matting agent between the silver halide emulsion layer and the support. Having.

As a support useful for the silver halide photographic light-sensitive material of the present invention, a transparent plastic film is preferable. For example, a cellulose ester film, a polyester film, a polystyrene film and the like can be preferably mentioned. As the cellulose ester film, a cellulose triacetate film (TAC film) is preferable. As the polyester film, a polyethylene terephthalate film (PET film for short) or a polyethylene-2,6-naphthalate film is preferable. As the polystyrene film,
Syndiotactic polystyrene films are preferred.

The silver halide photographic light-sensitive material of the present invention is suitable as a silver halide medical diagnostic photographic light-sensitive material.
In handling, it is important that the silver halide photographic material has rigidity, and a PET film having a thickness of 160 to 180 μm is preferable. The support may be colored in a range in which transparency is maintained, and coloring in blue with a color density of about 0.1 to 0.2 reduces eye fatigue at the time of transmission image observation by Sharksten. It is preferable because it can be performed.

In general, an undercoat layer may be provided on the surface of these supports, or a corona discharge, ultraviolet irradiation or the like may be applied to improve the adhesion of the coating layer.

The silver halide photographic light-sensitive material of the present invention may have a silver halide emulsion layer on only one side or both sides of a support. When used for silver halide photographic materials,
It is preferred to have a silver halide emulsion layer on both sides of the support.

The silver halide emulsion layer may be multilayered and may have any structure so as to obtain sensitivity and contrast suitable for the purpose of use of the silver halide photographic material. The amount of silver applied per side of the light-sensitive material of the present invention is 0.5
１．５1.5 g / m ² (configuration (9) of the present invention).
5-1.2 g / m < ² > is more preferable.

The dried film thickness of the silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention is preferably within the range of 0.5 to 3 μm in total of all silver halide emulsion layers. The thickness ratio between the layers may be arbitrary. The total thickness of the constituent layers when dried on the side where the silver halide emulsion layer is located is preferably 1 to 3 μm (the constitution (10) of the present invention).

In the silver halide photographic light-sensitive material of the present invention, the layers constituting the silver halide photographic light-sensitive material other than the silver halide emulsion layer and the undercoat layer include a protective layer, a crossover cut layer, an antistatic layer, and an intermediate layer. , A filter dye layer and the like. Additives added to these layers include the R
Those described in D can be used.

The thickness of the protective layer after drying is 0.4 to
It is preferably about 1.0 μm, and more preferably 0.5 to 0.8 μm
Is preferred. As the additives added to the protective layer, those described in RD described later can be used.

Next, the development processing of the silver halide photographic light-sensitive material of the present invention will be described. The silver halide photographic light-sensitive material of the present invention is developed by adding an appropriate amount of a hardening agent in advance to a layer having a protective colloid in a constituent layer so as to be suitable for rapid development processing and hardening appropriately. -Fixing-The swelling ratio in the washing step can be adjusted.

The silver halide photographic light-sensitive material of the present invention preferably has a swelling ratio during development of from 100 to 200%. The swelling ratio is obtained by calculating the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, dividing the difference by the film thickness before processing and multiplying by 100.

A preferred developing solution for developing the silver halide photographic light-sensitive material of the present invention is disclosed in
-15641, JP-A-4-16841, dihydroxybenzenes such as hydroquinone, para-aminophenols such as p-aminophenol;
Examples of 3-pyrazolidones such as N-methyl-p-aminophenol and 2,4-diaminophenol include, for example, 1-phenyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone, etc., sodium erythorbate and sodium ascorbate, and paragraph No. [0022] of JP-A-10-133338 To [0024] can be used.

Preferably, a developer containing substantially no hydroquinones and containing compounds described in Paragraph Nos. [0022] to [0024] of JP-A-10-133338 in addition to sodium erythorbate and sodium ascorbate It is particularly preferable to use the compound in combination with a 3-pyrazolidone.

Preservatives may include sulphites, such as potassium sulphite, sodium sulphite, reductones, such as piperidinohexose reductatone, which are preferably from 0.2 to 1 mol / l, Preferably, 0.3 to 0.6 mol / l is used.
Also, addition of a large amount of ascorbic acids leads to processing stability.

As the alkaline agent, sodium hydroxide,
PH adjusters such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate and potassium tertiary phosphate are included. Further, buffers such as borate described in JP-A-61-28708 and saccharose, acetoxime, 5-sulfosalicylic acid, phosphate and carbonate described in JP-A-60-93439 may be used. . The content of these agents is selected so that the pH of the developer is 8.5 to 11.5, preferably the pH is 9.5 to 10.5.

As a solubilizer, diethylene glycol, triethylene glycols and esters thereof can be contained, and as a sensitizer, for example, a development accelerator such as a quaternary ammonium salt, a surfactant and the like can be contained.

Further, a silver sludge inhibitor is also used in the developing solution. As a silver sludge inhibitor, JP-A-56-
No. 106244, silver stain inhibitor, JP-A-3-
No. 51844, sulfides and disulfide compounds,
The cysteine derivatives or triazine compounds described in JP-A-5-289255 are preferably used.

Further, an organic inhibitor and an inorganic inhibitor are also used. As organic inhibitors, azole organic antifoggants such as indazole, imidazole, benzimidazole, triazole, benztriazole, tetrazole, thiadiazole, mercaptoazole (eg, 1-phenyl-5-mercaptotetrazole) ) Compounds and the like, and in particular, nitroindazole (5-nitroindazole, 6-nitroindazole) is preferably used. The preferable addition amount of nitroindazole is 0.002 to 0.2 g / l, particularly preferably 0.01 to 0.1 g / l.

As the inorganic inhibitor, sodium bromide, potassium bromide, potassium iodide and the like can be contained. in particular,
The bromine ion concentration is preferably 10 g / l or more in terms of potassium bromide.

In addition, L. F. A. Mason, "Photographic Processing Chemistry", Focal Press (1966), pages 226-229, U.S. Pat. Nos. 2,193,015 and 2,592,364, JP-A-48-64933. You may use what is described in a gazette etc. Chelating agents for concealing calcium ions mixed in tap water used in the treatment liquid include chelating agents having a chelate stabilization constant of 8 or more with iron described in JP-A-1-193853 as an organic chelating agent. It is preferably used. Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate.

As the developing hardener, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used.

The replenishment of the developer during the development processing of the light-sensitive material of the present invention is preferably from 50 to 150 ml, more preferably from 65 to 130 ml, per m ² of the light-sensitive material.

Preferred fixing solutions can include fixing materials commonly used in the art.

The fixing agent is a thiosulfate such as ammonium thiosulfate or sodium thiosulfate, and ammonium thiosulfate is particularly preferred in view of the fixing speed. The concentration of the ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / l, more preferably in the range of 0.8 to 3 mol / l.

The pH of the fixing solution is 3.8 or more, preferably 4.2 or more. In the present invention, the fixing solution may form an acidic film. In this case, an aluminum compound is preferably used as a hardener. For example, it is preferable to add in the form of aluminum sulfate, aluminum chloride, potassium alum and the like.

The fixing solution may further contain a preservative such as sulfite and bisulfite, a pH buffer such as acetic acid and boric acid, a mineral acid (sulfuric acid, nitric acid) and an organic acid (citric acid, oxalic acid, etc.), if desired. Various acids such as malic acid), hydrochloric acid and the like, pH adjusters such as metal hydroxides (potassium hydroxide and sodium hydroxide) and chelating agents having a water softening ability can be contained.

Examples of the fixing accelerator include, for example,
No. 35754, No. 58-122535, No. 58-12
Examples thereof include thiourea derivatives described in US Pat. No. 2,536, and thioethers described in US Pat. No. 4,126,459.

The replenishment of the fixing solution at the time of fixing processing of the photographic material of the present invention is preferably 50 to 150 ml, more preferably 65 to 130 ml per 1 m ² of the photographic material.

As the treatment method of the present invention, a method using a solid treating agent is preferable. To solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is sprayed on the surface of the temporarily molded photographic processing agent. Any means such as forming a coating layer can be adopted (see JP-A-4-29136 and JP-A-4-29136).
-85535, 4-85536, 4-8553
No. 3, 4-85534 and 4-172341).

A preferred tablet production method is a method in which a powdery solid processing agent is granulated and then subjected to a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet.

The granulation method for tablet formation is to use known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation. Can be done.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm.

Further, the particle size distribution is preferably such that 60% or more of the granulated particles have a deviation of ± 100 to 150 μm.
Next, when the obtained granules are compressed under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, and a briquetting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape.However, from the viewpoint of productivity and handling, or from the problem of dust when used on the user side, a cylindrical, so-called tablet is used. preferable.

More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative and the like.

The method for producing a tablet processing agent is described, for example, in JP-A-51-61837, JP-A-54-155038, and JP-A-52-55038.
-88025, British Patent 1,213,808, etc., and can be produced by a general method.
Nos. 109043, 3-39735 and 3-397
It can be produced by a general method described in the specification such as JP-A-39. Furthermore, powder processing agents are described in, for example,
4-133332, British Patent 725,892,
No. 729,862 and German Patent 3,733,861
It can be manufactured by a general method as described in the specification.

[0099] strength of the solid bulk density of the treatment agent is a solid product obtained from the viewpoint of its solubility when in tablet 1.0 to 2.5 g / cm ³ is a preferably greater than 1.0 g / cm ³ In view of the above, it is more preferable to be smaller than 2.5 g / cm ³ from the viewpoint of solubility of the obtained solid. When the solid processing agent is granules or powder, the bulk density is 0.40 to 0.95 g /
those of cm ³ is preferable.

The automatic developing machine used in the present invention is preferably a known roller-type automatic developing machine. When processing the silver halide photographic material of the present invention, the total processing time (dry to dry) is 1 using an automatic processor.
The treatment is preferably performed in 0 to 45 seconds, and more preferably in 15 to 30 seconds. Here, the time from the time when the tip of the photosensitive material to be processed is immersed in the developing tank liquid of the automatic developing machine to the time when it comes into contact with the fixing tank liquid in the next step is referred to as `` development time ''. "Fixing time" refers to the time until contact with the washing tank solution (stabilizing solution), "Washing time" refers to the time of immersion in the washing tank solution, and "Drying time" refers to the time in the drying zone of the automatic processor. In this case, the preferred development time is 3 to 15 seconds, more preferably 3 to 10 seconds, the development temperature is 25 to 50 ° C, more preferably 30 to 40 ° C, and the fixing time is 2 to 12 seconds, more preferably 2 to 2 seconds. 10 seconds, the fixing temperature is 20 to 50 ° C., more preferably 30 to 40 ° C., the washing (stabilizing) time is 2 to 15 seconds, more preferably 2 to 8 seconds, and the washing (stabilizing) temperature is 0 to 50.
° C, more preferably 15 to 40 ° C, and the drying time is 3 to 12
Seconds, more preferably 3 to 8 seconds, drying temperature is 35 to 100
° C, more preferably 40-80 ° C. The silver halide photographic light-sensitive material of the present invention is developed, fixed and washed (or stabilized), dried with a squeeze roller after squeezing out water.

[0101]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

All the emulsions shown below were prepared in JP-A-11-2
It was prepared in a reaction vessel having a volume of 32 l using the silver halide emulsion production equipment described in FIG. As an ultrafiltration unit, Asahi Kasei SIP-101
3. DAIDO Rotary P as circulation pump
Ump was used. The volume of the emulsion circulation part in the ultrafiltration step was 1.2 l, and 15 l / min. The emulsion was circulated at a constant flow rate. The control of the distance between particles in the particle growth process was performed by appropriately controlling the permeation flux in the ultrafiltration step.

Example 1 <Preparation of Emulsion Em-1> Solution A1 Ossein gelatin 75.5 g Potassium bromide 64.7 g Finished with water to 10800 ml Solution B1 1.3 mol / l aqueous silver nitrate 410 ml solution C1 3.5 mol / l Silver nitrate aqueous solution 1500 ml Solution D1 1.3 mol / l potassium bromide aqueous solution 410 ml solution E1 3.5 mol / l potassium bromide aqueous solution The following silver potential (pAg) control amount Solution F1 ossein gelatin 125 g EO compound HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) ₁₇ (CH ₂ CH ₂ O) _n H (m + n = 5.7, molecular weight 1700) (10% aqueous ethanol solution) 6.78 ml water 4000 ml [nucleation step] Using a mixing and stirring device described in JP-A-62-160128, at 35 ° C. and a rotation speed of 400 rpm
The solution B1 and the solution D1 are added to the solution A1 while stirring.
The entire amount was added by the simultaneous mixing method over 1 minute to perform nucleation. After the addition of the solution B1 and the solution D1, the solution F1
Was added and the reactor temperature was raised to 60 ° C. in 30 minutes. Further, 30 ml of a 10% aqueous ammonium nitrate solution was added, the mixture was ripened for 10 minutes with a 10% aqueous KOH solution at pH 9.4, and the pH was adjusted to 6.0 with acetic acid.

[Growth Step] The solution C1 and the solution E1 were pAg
Was maintained at 9.2 at the same time as the critical growth rate. The emulsion was not circulated in the ultrafiltration step. After the addition was completed, soluble salts were desalted and removed by a precipitation method.

The emulsion thus obtained was used as an emulsion Em-
It was set to 1. Emulsion Em-1 had an average circle equivalent diameter of 1.42 μm,
The equivalent circle diameter distribution is 25%, the average thickness is 0.14 μm, the average thickness distribution is 28%, and 82% of the total grain projected area is (1).
11) Hexagonal tabular grains having a main plane and an average aspect ratio of 10.1

<Preparation of Emulsion Em-2> In the preparation of Emulsion Em-1, when 50% of the solution C1 in the growth step was consumed, the following solution E2 was added in its entirety in place of the solution E1, and then the solution E1 was added again. And added. During this time the solution C
No. 1 was continuously added and simultaneously added and mixed at a rate commensurate with the critical growth rate while maintaining the pAg at 9.2.

Solution E2 114.6 g potassium bromide 4.8 g potassium iodide Make up to 283 ml with water.

The emulsion thus obtained was used as emulsion Em-
And 2. Emulsion Em-2 had an average equivalent circle diameter of 1.35 μm,
The distribution of the equivalent circle diameter is 28%, the average thickness is 0.15 μm, the distribution of the average thickness is 29%, and 86% of the total grain projected area is (1).
11) Hexagonal tabular grains having a main plane and an average aspect ratio of 9.0.

<Preparation of Emulsion Em-3> Emulsion Em-3 was prepared in the same manner as Emulsion Em-2, except that the following solution E3 was used in place of E2.

Solution E3 31.1 g potassium bromide 4.8 g potassium iodide Make up to 83 ml with water.

Emulsion Em-3 had an average equivalent circle diameter of 1.31 μm.
m, distribution of circle equivalent diameter is 32%, average thickness is 0.16μ
m, average thickness distribution is 33%, 81% of total grain projected area
Were hexagonal tabular grains having a (111) major plane and an average aspect ratio of 8.2.

<Preparation of Emulsion Em-4> In the preparation of Emulsion Em-1, silver iodide fine particles having an average particle diameter of 0.05 μm were prepared from the time when 50% of the solution C1 in the growth step was consumed.
9 mol equivalent was added in 1 minute. During this time, the solution C1 and the solution E1 were continuously added, and simultaneously added and mixed at a speed commensurate with the critical growth rate while maintaining the pAg at 9.4.
The emulsion thus obtained was designated as Emulsion Em-4. Emulsion Em-4 has an average equivalent circle diameter of 1.28 μm, a distribution of equivalent circle diameters of 30%, an average thickness of 0.16 μm, an average thickness distribution of 32%, and 75% of the total grain projected area is (111) major plane. And hexagonal tabular grains having an average aspect ratio of 8.0.

<< Preparation Method of Silver Iodide Fine Particles >> 0.06 mol
6.64 l of a 5.0% by mass aqueous gelatin solution containing potassium iodide, 7.06 mol of silver nitrate and 7.06 m
ol of an aqueous solution containing potassium iodide,
Added over 0 minutes. During the formation of 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 solution of sodium carbonate.

<Preparation of Emulsion Em-5> In the preparation of Emulsion Em-4, the silver iodide fine particles having an average grain size of 0.05 μm and having a particle size of 0.02% were consumed after 50% of the solution C1 in the growth step was consumed.
9 mol equivalent was added at a constant flow rate for 10 minutes. The emulsion thus obtained was named Emulsion Em-5. Emulsion Em
-5 is the average circle equivalent diameter of 1.45 μm, and the distribution of the circle equivalent diameter is 2
5%, average thickness 0.13 μm, average thickness distribution 28
%, And 86% of the total grain projected area were hexagonal tabular grains having an average aspect ratio of 11.2 and having (111) major planes.

<Preparation of Emulsion Em-6> In the preparation of Emulsion Em-4, from the point in time when 50% of the solution C1 in the growth step was consumed, 0.02 silver iodide fine particles having an average grain size of 0.05 μm were used.
9 mol equivalent was added at a constant flow rate for 25 minutes. The emulsion thus obtained was named Emulsion Em-6. Emulsion Em
-6 is the average circle equivalent diameter of 1.51 μm, and the distribution of the circle equivalent diameter is 2
3%, average thickness 0.12 μm, average thickness distribution 27
%, And 85% of the total grain projected area were hexagonal tabular grains having an average aspect ratio of 12.6 and having a (111) major plane.

<Preparation of Emulsion Em-7> In the preparation of Emulsion Em-4, silver iodide fine particles having an average grain size of 0.05 μm were prepared from the time when 20% of the solution C1 in the growth step was consumed.
9 mol equivalent was added at a constant flow rate for 10 minutes. The emulsion thus obtained was named Emulsion Em-7. Emulsion Em
-7 is an average circle equivalent diameter of 1.41 μm, and the distribution of the circle equivalent diameter is 2
4%, average thickness 0.14 μm, average thickness distribution 26
%, And 80% of the total grain projected area were hexagonal tabular grains having an average aspect ratio of 10.1 having a (111) major plane.

<Preparation of Emulsion Em-8> In the preparation of Emulsion Em-4, silver iodide fine particles having an average grain size of 0.05 μm were prepared from the time when 70% of the solution C1 in the growth step was consumed.
9 mol equivalent was added at a constant flow rate for 10 minutes. The emulsion thus obtained was named Emulsion Em-8. Emulsion Em
-8 is the average equivalent circle diameter of 1.59 μm, and the distribution of equivalent circle diameter is 2
2%, average thickness 0.11 μm, average thickness distribution 28
%, And 78% of the total grain projected area were hexagonal tabular grains having an average aspect ratio of 14.5 and having (111) major planes.

<Preparation of Emulsion Em-9> In the preparation of Emulsion Em-4, 0.029 mol of silver iodide fine particles having an average grain size of 0.05 μm was used from the time when 85% of the solution C1 in the growth step was consumed until the addition was completed. Was added at a constant flow rate. The emulsion thus obtained was named Emulsion Em-9. Emulsion Em
-9 is the average equivalent circle diameter of 1.61 μm, and the distribution of equivalent circle diameter is 2
8%, average thickness 0.11 μm, average thickness distribution 30
% And 74% of the total grain projected area were hexagonal tabular grains having an average aspect ratio of 14.6 and having (111) major planes.

<Preparation of Emulsion Em-10> In the preparation of Emulsion Em-4, the silver iodide fine particles having an average particle size of 0.05 μm were added from the time when 50% of the solution C1 in the growth step was consumed.
Equivalent to 58 mol was added at a constant flow rate for 25 minutes. The emulsion thus obtained was designated as Emulsion Em-10. Emulsion Em-10 had an average equivalent circle diameter of 1.28 μm, a distribution of equivalent circle diameters of 32%, an average thickness of 0.17 μm, an average thickness distribution of 35%, and 72% of the total grain projected area was (111) major plane. And hexagonal tabular grains having an average aspect ratio of 7.5.

<Preparation of Emulsion Em-11> In the preparation of Emulsion Em-4, silver iodide fine grains having an average grain size of 0.05 μm were added from the time when 20% of the solution C1 in the growth step was consumed.
17 mol equivalent was added at a constant flow rate for 50 minutes. The emulsion thus obtained was designated as Emulsion Em-11. Emulsion Em-11 had an average equivalent circle diameter of 1.42 μm, the distribution of equivalent circle diameters was 27%, the average thickness was 0.14 μm, the average thickness distribution was 30%, and 75% of the total grain projected area was (111) major plane. And hexagonal tabular grains having an average aspect ratio of 10.1.

<Preparation of Emulsion Em-12> In the preparation of Emulsion Em-5, the reaction solution in the reaction vessel was circulated to the ultrafiltration unit during the growth step to carry out concentration, whereby the whole area of the grain growth step was performed. The emulsion Em-5 was prepared in the same manner as the emulsion Em-5, except that the average intergranular distance over the range was maintained at the average intergranular distance at the start of the grain growth step. In this case, the silver iodide fine particles are added when 50% of the solution C1 having the minimum average intergranular distance is consumed. The emulsion thus obtained was designated as Emulsion Em-12. Emulsion Em-12
Is an average equivalent circle diameter of 1.46 μm, and the distribution of equivalent circle diameters is 18.
%, The average thickness is 0.13 μm, and the distribution of the average thickness is 19
% And 85% of the total grain projected area were hexagonal tabular grains having an average aspect ratio of 11.2 and having a (111) major plane.

<Preparation of Emulsion Em-13> In the preparation of Emulsion Em-6, the reactant solution in the reaction vessel was circulated to the ultrafiltration unit during the growth step to carry out concentration, whereby the whole area of the grain growth step was achieved. The emulsion Em-6 was prepared in the same manner as in the preparation of the emulsion Em-6, except that the average intergranular distance was maintained at the average intergranular distance at the start of the grain growth step. In this case, the silver iodide fine particles are added when 50% of the solution C1 having the minimum average intergranular distance is consumed. The emulsion thus obtained was named Emulsion Em-13. Emulsion Em-13
Is the average equivalent circle diameter of 1.52 μm, and the distribution of equivalent circle diameter is 10
%, The average thickness is 0.12 μm, and the average thickness distribution is 13
%, And 89% of the total grain projected area were hexagonal tabular grains having an average aspect ratio of 12.7 and having (111) major planes.

<Preparation of Emulsion Em-14> Emulsion Em-12
Was prepared in the same manner as for the emulsion Em-12, except that the growth was carried out while maintaining the pAg during the growth of the grains at 9.72. Therefore, in this case, the silver iodide fine particles are added when 50% of the solution C1 having the minimum average intergranular distance is consumed. The emulsion thus obtained was used as emulsion Em
−14. Emulsion Em-14 has an average equivalent circle diameter of 1.66.
μm, circle equivalent diameter distribution: 15%, average thickness: 0.10μ
m, average thickness distribution 19%, total grain projected area 84%
Has an average aspect ratio of 16.6 having a (111) major plane.
Of hexagonal tabular grains.

<Preparation of Emulsion Em-15> Emulsion Em-12
Was prepared in the same manner as for the emulsion Em-12, except that the growth was carried out while maintaining the pAg during the growth of the grains at 9.83. In this case, the silver iodide fine particles are added when 50% of the solution C1 having the minimum average intergranular distance is consumed. The emulsion thus obtained was named Emulsion Em-15. Emulsion Em-15 had an average equivalent circle diameter of 1.84 μm, a distribution of equivalent circle diameters of 19%, an average thickness of 0.08 μm, an average thickness distribution of 23%, and 80% of the total grain projected area (11).
1) Hexagonal tabular grains having a main plane and an average aspect ratio of 23.0.

Next, chemical sensitization and spectral sensitization will be described. After the emulsions Em-1 to Em-15 were heated to 60 ° C., 10 minutes after the spectral sensitizing dye was added as a dispersion of solid fine particles, adenine, ammonium thiocyanate,
A mixed aqueous solution of chloroauric acid and sodium thiosulfate and a dispersion of triphenylphosphine selenide were added, and silver iodide fine particles were added, followed by aging for a total of 2 hours. At the end of ripening, 4-hydroxy-6-methyl-
A predetermined amount of 1,3,3a, 7-tetrazaindene was added.

The dispersion of the solid fine particles of the spectral sensitizing dye was prepared by a known method. That is, a predetermined amount of the above-mentioned spectral sensitizing dye was added to water whose temperature had been previously adjusted to 27 ° C., and the mixture was stirred at 3,500 rpm for 30 to 120 minutes by high-speed stirring (dissolver).

A dispersion of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., and the mixture was stirred and completely dissolved. 3.8 kg of photographic gelatin on the other hand
Was dissolved in 38 kg of pure water, and 93 g of a 25% by mass 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 a dispersion blade peripheral speed of 40 m / sec at 50 ° C. for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was reduced to 0.3.
Ethyl acetate was removed while stirring until the amount became less than mass%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. A portion of the dispersion thus obtained was fractionated and applied to the above emulsion.

1 mol of silver iodide fine silver halide emulsion
The amounts added per unit are those shown in Table 1, and other additives were adjusted to the optimum amounts for each emulsion.

As described above, the emulsion E before the chemical sensitization was used.
m-1 to m-15 were chemically sensitized as described above, and the following additives were added to prepare chemically sensitized emulsions Em-AU.
The measured values of these silver halide emulsions and silver halide grains are shown in Tables 1 and 2.

[Preparation of silver halide photographic light-sensitive material] <Preparation and application of undercoat liquid> Minute concentration 10
(% By mass), using two slide hopper coaters as shown in Table 3 on both sides of a colored PET film support having a thickness of 175 μm and a blue density of 0.20, as shown in Table 3. The coating was performed simultaneously at a speed of 120 m / min and dried for 2 min / 20 sec. Nos. 1-27 were produced.

The first layer was coated simultaneously with the following first to third layers from the side closer to the support. <Coating Amount of First to Third Layers> (First Layer: Composition and Coating Amount of Coating Solution for Crossover Light-Cut Layer) Gelatin 0.1 g / m ² Filter Dye A (solid dispersion) 70 mg / m ² polystyrene Sodium sulfonate (average molecular weight 500,000) 4mg / m ²

[0132]

Embedded image

(Second Layer: Composition and Coating Amount of Silver Halide Emulsion Layer Coating Solution) The following various additives were added to each of the chemically sensitized emulsions obtained above.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg / m ² t-butyl-catechol 130 mg / m ² Polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / M ² sodium polystyrene sulfonate 80 mg / m ² trimethylolpropane 150 mg / m ² nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² sodium 1,3-dihydroxybenzene-4-sulfonate 400 mg / m ² 2-mercaptobenz Sodium imidazole-5-sulfonate 6 mg / m ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² Dextran (average molecular weight 40,000) 0.5 g / m ² colloid Silica (Ludox AM: Dupo 0.5 g / m ² gelatin Amount to achieve the film thickness shown in Table 2 (third layer: composition and coating amount of protective layer coating solution) Gelatin 0.4 g / m ² polyacrylamide (Average molecular weight 10,000) 0.1 g / m ² Sodium-di (n-hexyl) sulfosuccinate 5 mg / m ² NaO ₃ SCH (COOC ₅ H ₁₁ ) (CH ₂ COOC ₁₀ H ₂₁ ) 3 mg / m ² C ₈ H ₁₇ (C ₆ H ₄ ) O (CH ₂ CH ₂ O) _n SO ₃ Na (n = 4-5) 17 mg / m ² C ₁₆ H ₃₃ O (CHCH ₂ O) ₁₀ H 14 mg / m ² C ₁₁ H ₂₃ CON ((CH ₂ CH ₂ O) _m H) ((CHCH ₂ O) _n H) (m + n = 10) 43 mg / m ² NaO ₃ SCH (COOCH ₂ (CF ₂ CF ₂ ) ₃ H) (CH ₂ COOCH _{2 (CF 2 CF 2) 3 H} ) 1.2mg / m 2 matting agent (main component Polymethyl methacrylate, average particle size 8 [mu] m) 10 mg / m ² preservative 1 mg / m ² Hardener: 1,2-bis (adjustment of quantity added as vinylsulfonyl acetamide) ethane swelling ratio is 150%

[0135]

Embedded image

[0136]

[Table 1]

[0137]

[Table 2]

<< Evaluation of Sensitivity >> The obtained sample was sandwiched between fluorescent intensifying screens SRO-250 (manufactured by Konica Corporation), and a tube voltage of 90 was used.
X-rays were irradiated at kVp, 20 mA for 0.05 seconds, a sensitometric curve was prepared by a distance method, and sensitivity and fog were determined. The sensitivity is X required to obtain a density of fog +1.0.
Determined as the reciprocal of the dose, the sample No. The relative sensitivity is shown assuming that the sensitivity of 1 is 100. The developing process was performed using an automatic developing machine TCX-701 (manufactured by Konica Corporation), and the developing temperature and the fixing temperature were both set to 35 ° C. in a 30-second mode. After the sample was exposed so as to have the highest density, the sample was developed in the same manner as in the evaluation of the sensitivity, and a Dmax value was obtained.

<< Tone of Developed Silver >> The prepared sample was exposed so that the transmission density after development was 1.2, and then developed using the automatic developing machine. The obtained developed sample was observed on a Schaukasten, and the silver tone due to the transmitted light and the reflected light was given a score of 5 to 1 by visual sensory evaluation.

5: Preferred color tone without redness or yellowness 4: Level with slight redness or yellowness 3: Level at which redness or yellowness is concerned 2: Level at which redness or yellowness is noticeable 1: The level is so red and yellow that the image observer feels uncomfortable.

<< Evaluation of Pressure Resistance (Blackening of Scratch) >> After the prepared sample was allowed to stand in an atmosphere of 80% RH and 23 ° C. for 3 months, an unexposed sample was subjected to a 10-minute test using a commercially available nylon scourer.
After rubbing with a load of 0 g / cm ² , the developed film was visually evaluated for blackened silver streaks (scratching caused by pressure fogging and blackening of the developed streaks).

The evaluation criteria are as follows. 5: Almost no black streaks 4: Slightly black streaks 3: Slightly black streaks 2: Black streaks are noticeably generated 1: Black streaks are extremely And the concentration is high.

Sample No. The sensitivity, fog, maximum density (Dmax), color tone of developed silver, and pressure resistance (blackening of scratches) were evaluated for each of Nos. 1 to 27, and the results are shown in Table 3.

[0144]

[Table 3]

(Results) The sensitivity of the sample of the silver halide photographic material using the silver halide emulsion of the present invention was improved.
The maximum density (Dmax) was high, the fog was small, the color tone of the developed silver was satisfactory to the image evaluator, and the pressure resistance was good. On the other hand, in the comparative sample, any of the above evaluation items was deteriorated, and it was found that the present invention was excellent in that satisfactory results were obtained in all the items.

[0146]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity and excellent in color tone and pressure resistance of developed silver was obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/015 G03C 1/015 1/74 1/74

Claims (10)

[Claims] 1. A region containing 70 to 100% of the projected area of all silver halide grains contained therein having a (111) major plane and including a central portion substantially composed of silver bromide. Silver iodide content adjacent to the region containing
It has a 1% silver iodobromide layer and a surface layer having a silver iodide content of 3 to 15 mol%, and has an average aspect ratio of 8 to 20, an average silver iodide content of 0.1 to 1 mol%, and iodide between grains. A silver halide emulsion comprising hexagonal tabular grains having a silver content coefficient of variation of 1 to 30%. 2. The region containing the central portion occupies 30 to 95% as a volume fraction of all the tabular grains, and the outer silver iodobromide adjacent to the region containing the central portion contains the tabular grains. 2. The silver halide emulsion according to claim 1, wherein the total volume fraction accounts for 5 to 30%. 3. The silver halide emulsion according to claim 1, wherein the silver iodobromide layer contains 2 to 7 mol% of silver iodide. 4. The tabular grains have the maximum silver iodide content (x, mol%) inside the tabular grains excluding the surface layer and the silver iodide content (y, mol%) of the surface layer. ) And 1 ≦
4. The silver halide emulsion according to claim 1, wherein a relationship y / x ≦ 20 is satisfied. 5. A method according to claim 1, wherein said tabular grains have a silver iodide content (a, mol) in said tabular grains excluding a surface layer and a silver iodide content (b, mol) in said surface layer. 0.5 ≦ b /
2. The relationship of a ≦ 2.0 is satisfied.
5. The silver halide emulsion according to any one of claims 1 to 4. 6. The silver halide emulsion according to claim 1, wherein the silver iodide in the surface layer is formed by adding fine silver iodide particles. . 7. The method for preparing a silver halide emulsion according to claim 1, wherein the average grain represented by the following formula from the start to the end of the growth of the silver halide grains: A method for preparing a silver halide emulsion, characterized in that iodine ions are added to form silver iodide at a time when the distance between them shows a minimum value or a minimum value. Average distance between particles = (volume of reaction solution / number of growing particles in reaction solution) ^1/3 8. A silver halide emulsion prepared by the method according to claim 7. 9. A transparent support comprising a silver halide emulsion layer containing the silver halide emulsion according to claim 1 and a total amount of silver coated on one side of the silver halide emulsion of 0.5 to 1.5 g / m 2. ^Two
A silver halide photographic light-sensitive material, characterized in that it is coated so that 10. The dried film thickness of all coating layers is 1 to 3 μm.
10. The silver halide photographic light-sensitive material according to claim 9, wherein