JPH08122952A - Silver halide photographic emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide emulsion and a silver halide photographic sensitive material high in sensitivity and superior in rapid processing aptitude and pressure resistance and small in safe light fog. CONSTITUTION: The silver halide photographic emulsion and the silver halide photographic sensitive material contain silver halide grains each having at least 2 parts having a maximum silver iodide content of >=4mol% inside and a silver iodide content of >=4mol% in the uppermost surface and an average silver iodide content of <=1.0mol%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion and a silver halide photographic light-sensitive material, and more specifically, it has excellent pressure resistance, has a low fog property due to a safelight for dark rooms, and has high sensitivity and rapid processability. The present invention relates to an improved silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for rapid processing of silver halide photographic light-sensitive materials. Especially in the medical field, the number of X-ray photographs taken will increase due to the rapid increase in examinations including general examinations, regular physical examinations, and medical checkups, which will increase the number of X-ray photographs taken. There is a strong demand for further speeding up of development processing.

For rapid processing, development, fixing, washing with water,
It is necessary to shorten the processing time of each processing step such as drying. However, if the developing time is simply shortened, for example, in a conventional light-sensitive material, the image density is lowered, that is, the sensitivity is lowered and the gradation is lowered. Further, if the fixing time is shortened, the fixing of silver halide becomes incomplete, which causes deterioration of image quality and storability. Therefore, in order to solve such a problem, it is necessary to increase the developing speed and fixing speed of the silver halide grains themselves. It is well known to reduce the silver iodide content of silver halide grains in order to accelerate the developing speed and fixing speed.

However, when the average silver iodide content is lowered, the intrinsic sensitivity of silver halide is lowered, and when the silver iodide content on the surface of silver halide grains is lowered, the adsorption of the sensitizing dye is deteriorated. The spectral sensitization cannot be increased.
Further, it is known that a low silver iodide ratio causes a problem that pressure fog is likely to occur during handling and processing of the light-sensitive material.

It is widely known that the silver iodide contained in the silver halide grains as described above affects various photographic performances and physical properties. For example, the silver iodide content in the silver halide grains can be controlled. Regarding the distribution and its characteristics, many patents and documents are disclosed in JP-A-4-107442.

By the way, in recent years, many techniques for improving sensitivity and image quality using tabular silver halide grains have been disclosed, for example, JP-A Nos. 58-111935, 58-111936, and 58-111936.
-111937, 58-113927, 59-99433, etc.

These tabular silver halide grains are hexahedral,
Compared with so-called normal crystal silver halide grains such as octahedron, since the surface area is large in the same volume, it is possible to increase the adsorption amount of the sensitizing dye on the grain surface.
There is an advantage that high sensitivity can be obtained. Further, in JP-A-63-92942, a technique of providing a core having a high silver iodide content inside a tabular silver halide grain, or in JP-A-63-151618, hexagonal tabular silver halide grains are used. Technology is disclosed,
It is said that high sensitivity can be obtained in both cases.

However, these tabular grains are liable to cause serious troubles in handling such as pressure fog and pressure desensitization peculiar to tabular grains, and are not preferable from a practical point of view.

Further, both the patent and the literature cited in Japanese Patent Laid-Open No. 4-107442 relating to the distribution of the silver iodide content inside the silver halide grains described above can achieve high sensitivity, but they are not necessarily resistant to pressure. It has not reached the point of meeting the request.

When handling the light-sensitive material, the light-sensitive material is stable for a long time with respect to safe light used for a dark room and should not cause fog or desensitization.
However, if the sensitivity of silver halide grains is increased, the safelight resistance is deteriorated and fog is apt to occur.

As a technique for improving the safelight resistance, many proposals have been made for a long time. For example, Japanese Patent Publication No. 45-8831 using gold mercaptide and No. 56-24937 using thiosuccinimide are disclosed. Has been done.

However, these techniques have not been able to sufficiently improve the safelight resistance. In addition, many proposals have been made for improving pressure resistance,
For example, Japanese Patent Application Laid-Open No. 3-220238 discloses a technique relating to a transition line, and Japanese Patent Application Laid-Open No. 1-131541 discloses a technique of circular tabular grains as means for improving pressure characteristics.

Further, JP-A-59-99433 and 60-147727
JP-A-2-193138 and the like disclose techniques relating to the layer constitution of a layer having a high silver iodide content, but if the layer constitution is such that a sufficient effect is obtained, the average silver iodide content is high. As a result, the processing time is not necessarily shortened, and the above-mentioned safe write resistance is not excellent.

It is possible to cope with the recent extremely rapid processing,
Further, as a silver halide photographic light-sensitive material capable of obtaining high sensitivity and high image quality, further improvement of pressure resistance and safelight resistance has been desired.

[0015]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic emulsion and a silver halide photographic light-sensitive material having high sensitivity, rapid processability, excellent pressure resistance, and less safe light fog. Is.

[0016]

The objects of the present invention have been achieved by the methods described in (1) to (4) below.

(1) The silver iodide-containing silver halide grains have a silver iodide-containing portion having a maximum value of 4 mol% or more in at least two places inside and the silver iodide-containing silver halide grains on the outermost surface of the silver halide grains. A silver halide photographic emulsion characterized by containing silver halide grains having a ratio of 4 mol% or more and an average silver iodide content of 1.0 mol% or less.

(2) The silver halide photographic emulsion as described in (1) above, wherein the silver halide grains are tabular silver halide grains having an average aspect ratio of 3.0 or more.

(3) At least one of the silver halide emulsion layers
A silver halide photographic light-sensitive material characterized by containing the silver halide photographic emulsion described in the above item (1) in a layer.

(4) At least one of the silver halide emulsion layers
A silver halide photographic light-sensitive material characterized by containing the silver halide photographic emulsion described in the above item (2) in a layer.

The present invention will be described in detail below.

In the silver halide emulsion of the present invention, silver iodobromide, silver iodochloride, silver chloroiodobromide and the like can be used as the silver halide, and particularly silver iodobromide and silver chloroiodobromide are usable. Preferably there is. When silver iodobromide is used, the content of silver iodide is the average silver iodide content of the entire silver halide grains.
It is preferably 1.0 mol% or less, particularly preferably 0.8 mol% or less. The lower limit is preferably 0.1 mol%.

In the present invention, the silver iodide content and the average silver iodide content of individual silver halide grains are determined by the EPMA method (Elec
tron Probe Micro Analyzer method). In this method, a sample in which emulsion grains are well dispersed so as not to come into contact with each other is prepared, and an X-ray analysis is performed by irradiating an electron beam and exciting with an electron beam. Elemental analysis of extremely minute portions can be performed. By determining the characteristic X-ray intensities of silver and iodine emitted from each grain by the method, the silver halide composition of each grain can be determined. When the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content can be determined from the average thereof.

The tabular silver halide grains of the present invention preferably have a more uniform silver iodide content between grains. When the distribution of the silver iodide content between grains is measured by the EPMA method, the relative standard deviation is preferably 35% or less, more preferably 20% or less.

In the present invention, the silver iodide content on the outermost surface of silver halide grains is 4 mol% or more, preferably 4 mol% or more.
It is not less than mol% and not more than 20 mol%. The silver iodide content of the outermost surface is preferably higher than the silver iodide content of the adjacent interior. There is no limitation on the magnitude of the silver iodide content in the innermost surface and the content in the outermost surface, and optimization may be performed from the viewpoint of sensitivity, suitability for rapid processing, and pressure characteristics.

The outermost surface silver iodide content referred to here is X.
The silver iodide content of a portion up to a depth of about 50Å analyzed by the PS method (X-ray Photoelectron Spectroscopy), which can be determined as follows.

The sample is placed in an ultrahigh vacuum of 1 × 10 ^-8 torr or less-
Cool down to 110 ° C or below and use MgKα as X-ray for the probe.
Irradiation with a source voltage of 15 kv and an X-ray source current of 40 mA, Ag3d5 /
2, Br3d, I3d 3/2 electrons are measured. Sensitivity factor (Sensitivity Facto
r) and calculate the halide composition of the outermost surface from these intensity ratios. The purpose of cooling the sample is to eliminate measurement errors caused by destruction of the sample (decomposition of silver halide and diffusion of halide (particularly iodine)) due to X-ray irradiation at room temperature, and to improve measurement accuracy. If cooled to -110 ° C, sample destruction can be suppressed to a level that does not hinder measurement. The silver halide grain according to the present invention is characterized in that at least two locations inside the silver halide grain have a site where the silver iodide content has a maximum value of 4 mol% or more.

The inside of the silver halide grain means a portion inside from the surface of the grain to a depth of 100Å. Further, the maximum value is the maximum value in the chart (horizontal axis: distance from the measurement starting point, vertical axis: silver iodide content) obtained by the method for measuring the halogen composition in the silver halide grains shown below, The maximum value of a peak whose peak width (half-value width) is 150 nm or less on a straight line parallel to the horizontal axis that passes through the midpoint of the vertical line from the apex of the peak to the horizontal axis.

The upper limit of the full width at half maximum is 150 nm, preferably 100 nm, and the lower limit is 5 nm, preferably 10 nm.

In the present invention, the pure silver bromide portion preferably accounts for 90% or more of the total grain volume. The volume of the pure silver bromide portion means the volume of the portion where silver iodide is not detected.

In the present invention, the halogen composition distribution inside the silver halide grain is obtained by pretreating the grain into ultrathin slices and then observing and analyzing with a transmission electron microscope while cooling. Specifically, after taking out silver halide grains from the emulsion, they are embedded in a resin and cut with a diamond knife to prepare a slice having a thickness of 60 nm. While cooling this section with liquid nitrogen, observation and point analysis were performed with a transmission electron microscope equipped with an energy dispersive X-ray analyzer, and it was obtained by quantitative calculation (Inoue, Nagasawa: Photographic Society, 1987) Conference abstracts p
62).

In the case of a hexagonal tabular silver halide grain, the position cut with a diamond knife is a distance of 100 n to the left and right from the diagonal line of a hexagon (a straight line connecting a certain apex and its three adjacent apexes).
Any region may be cut as long as it is parallel to the diagonal line perpendicular to the main plane in a region sandwiched by two straight lines parallel to the diagonal line separated by m.

The silver halide grains of the present invention preferably have an average aspect ratio of 3.0 or more. The lower limit of the aspect ratio of the tabular silver halide grains is 3.0, the upper limit is preferably 20, and more preferably 10. The upper limit of the average grain size of the tabular silver halide grains of the present invention is preferably 3.
It is 0 μm, more preferably 2.5 μm. The lower limit is preferably 0.2 μm, more preferably 0.4 μm. The upper limit of the average thickness of the tabular silver halide grains of the present invention is preferably 1.0 μm, more preferably 0.80 μm, still more preferably 0.60 μm. The lower limit is preferably 0.05 μm.

The tabular silver halide grains referred to here are
A particle having two parallel main planes facing each other, and having an average ratio of particle diameter to particle thickness (hereinafter referred to as an aspect ratio) of more than 1.3. Further, the grain size of the silver halide grain means an average projected area diameter, and is a circle equivalent diameter of the projected area of the tabular silver halide grain (diameter of a circle having the same projected area as the silver halide grain). Indicated, thickness refers to the distance between two parallel major planes forming the tabular silver halide grains.

The particle size and thickness can be optimized to optimize sensitivity, pressure characteristics and the like. Optimum particle size and thickness depending on other factors (sensitivity of hydrophilic colloid layer, film hardness, chemical ripening conditions, sensitivity of photosensitive material setting, coating silver amount, etc.) that influence sensitivity and pressure characteristics. Different.

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

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

The tabular silver halide grains of the present invention are crystallographically classified as twins. A twin is a silver halide crystal having one or more twin planes in one grain, but the morphology of twins is classified by Klein and Moiser (Phot).
ographishe Korrespondenz) 99, 99, 100, 57.

The tabular silver halide grain of the present invention has two or more twin planes parallel to the main plane. The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, a photosensitive silver halide emulsion is coated so that the main planes of the tabular silver halide grains contained are oriented substantially parallel to the support, and a sample is prepared. It is cut with a diamond cutter to a thickness of 0.1.
Obtain a thin section of about μm.

The presence of twin planes can be confirmed by observing this section with a transmission electron microscope.

In the present invention, the average value of the distance between twin planes is preferably 0.008 μm or more, and more preferably
It is 0.010 μm or more and 0.05 μm or less. Here, the distance between twin planes represents the distance between the twin planes when there are two twin planes,
When the number of twin planes is three or more, it means the longest distance among the twin planes. In the present invention, the average value of the distance between twin planes can be obtained as follows. That is, observation of the section using the above transmission electron microscope, arbitrarily select 100 or more tabular silver halide grains showing a cross section cut substantially perpendicular to the main plane, twin for each grain The face-to-face distance can be measured and the average can be obtained.

In the present invention, the tabular silver halide grains are preferably hexagonal. The hexagonal tabular grains mean that the main plane {(111) face} is hexagonal and the maximum adjacent side ratio is 1.0 to 2.0. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. In the present invention, the hexagonal tabular grain has a maximum adjacent side ratio of
If it is 1.0 to 2.0, it is preferable that the corners are rounded. The length of a side when the corner is rounded is represented by the distance between the straight line portion of the side and the intersection with the line obtained by extending the straight line portion of the adjacent side. It is also preferable that the tabular grains are further rounded and have a substantially circular shape.

In the present invention, it is preferable that each side forming the hexagon of the hexagonal tabular grain has a straight line at least ½ of each side. In the present invention, the ratio of adjacent sides is 1.0 to
It is more preferably 1.5.

The halogenated grains of the present invention may have dislocations. The rearrangement is, for example, JF Hamilton, Phot.Sci.En.
g, 57 (1967), T.Shiozawa, J.Soc.Phot.Sci.Japan,
It can be observed by a direct method using a transmission electron microscope at low temperature described in 35, 213 (1972). That is, the silver halide grains, which were taken out carefully so as not to apply dislocation pressure to the grains from the emulsion, were placed on a mesh for electron microscope observation, and the sample was placed to prevent damage (printout etc.) due to electron beams. Observation is carried out by the transmission method in the cooled state. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough, so it is possible to observe more clearly using a high-pressure electron microscope (200 kv or more for particles having a thickness of 0.25 μm). .

The silver halide emulsion of the present invention is preferably grown by a method of precipitating silver halide on seed grains. For example, in a method for producing a silver halide photographic emulsion, which comprises supplying a water-soluble silver salt solution and a water-soluble halide solution to the presence of a protective colloid to obtain a tabular silver halide emulsion of the present invention, Silver halide content 0-5 mol%
From the beginning of the formation of silver halide precipitate in
Providing a nuclear particle generation step to keep the pBr of the mother liquor at 2.5 to -0.7,
(B) Subsequent to the step of forming core particles, the mother liquor contains a silver halide solvent in an amount of 10 ^{−5 to} 2.0 mol per mol of silver halide, and is a substantially monodisperse spherical twin crystal silver halide seed particle. Or a seed grain forming step of forming a silver halide twin seed grain by raising the temperature of the mother liquor to 40 to 80 ° C., or providing a seed grain forming step of forming a seed grain forming step. (C) Next, a method of providing a growth step of growing a seed grain by adding a water-soluble silver salt solution and a water-soluble halide solution and / or silver halide fine particles is preferably used.

Here, the mother liquor is a liquid (including a silver halide emulsion) that is used for the preparation of silver halide emulsions up to the completed photographic emulsion.

The silver halide grains formed in the nucleus grain forming step are twin grains having an average silver iodide content of 0 to 5 mol%.

A water-soluble silver salt may be added for the purpose of controlling ripening during the seed grain forming step of the present invention.

The step of growing the silver halide seed grains comprises:
PAg, p during Ostwald ripening during precipitation of silver halide
Control H, temperature, concentration of silver halide solvent and silver halide composition, addition rate of silver salt and halide solution.
It is achieved by In preparing the emulsion of the present invention, a known silver halide solvent such as ammonia, thioether or thiourea may be present during the seed grain forming step and the seed grain growth.

The conditions for growing the produced seed grains in order to obtain the tabular silver halide grains of the present invention include, for example, JP-A Nos. 51-39027, 55-142329 and 58-113928.
No. 54-48521 and No. 58-49938, a water-soluble silver salt solution and a water-soluble halide solution are added by the double jet method, and the rate of addition depends on the growth of grains to form new nuclei. The rate at which no new nucleation occurs, and the size distribution does not spread due to Ostwald ripening.
There is a method of gradually changing it in the range of 30 to 100%.

As another condition for further growing seed particles,
As can be seen on page 88 of the 1983 Annual Meeting of the Photographic Society of Japan, a method of growing by adding silver halide fine particles and dissolving and recrystallizing is preferably used. Particularly, silver iodide fine particles, silver bromide fine particles, silver iodobromide fine particles and silver chloride fine particles are preferably used.

The silver halide grains according to the present invention may be so-called halogen conversion type grains. Halogen conversion amount is 0.2 mol% to silver amount
1.0 mol% is preferable, and the conversion time may be either physical ripening or after physical ripening. As a method of halogen conversion,
Usually, an aqueous halogen solution or silver halide fine particles having a smaller solubility product with silver than the halogen composition on the grain surface before conversion to halogen is added. The particle size at this time is 0.
It is preferably 2 μm or less, and more preferably 0.02 to 0.1 μm. As a method for adjusting the silver iodide content on the outermost surface of the silver halide grain of the present invention, a method of simultaneously adding a silver nitrate solution and a solution containing iodide to an emulsion containing tabular grains as a base, A method of adding fine silver halide grains such as silver iodide, silver iodobromide or silver chloroiodobromide, a method of adding potassium iodide or a mixture of potassium iodide and potassium bromide, and the like can be applied. Among these, the method of adding fine silver halide grains is preferable. Especially preferred is the addition of fine silver iodide grains.

The time for adjusting the silver iodide content on the outermost surface is from the final step of the silver halide crystal production step to the chemical ripening step, and further from the completion of the solution preparation step immediately before the coating of the silver halide emulsion. Although it can be selected in the meantime, it is preferable to adjust it by the end of the chemical ripening step. The term "chemical ripening step" as used herein refers to a point from the time when physical ripening and desalting operations of the silver halide emulsion of the present invention are completed, to the time when a chemical sensitizer is added and then the operation for stopping the chemical ripening is performed. Up to. Further, the addition of silver halide fine grains may be carried out several times with a time interval, or another chemically ripened emulsion may be added after the addition of the fine grains. The temperature of the emulsion of the present invention when adding silver halide fine grains is
The range of 30 to 80 ° C is preferable, and the range of 40 to 65 ° C is particularly preferable. Further, the present invention is preferably carried out under the condition that the silver halide fine particles to be added partially or wholly disappear after the addition and immediately before coating. More preferable condition is 20% of the added silver halide fine particles. The above is the disappearance just before coating.

In producing the silver halide emulsion of the present invention, stirring conditions during production are extremely important. As the stirring device, the additive liquid nozzle shown in JP-A-62-160128,
A device installed in the liquid near the mother liquid suction port of the stirrer is particularly preferably used. At this time, the stirring rotation speed is 100 to 1
It is preferably 200 rpm.

The silver halide grains contained in the silver halide emulsion of the present invention include a cadmium salt, a zinc salt, a lead salt, a thallium salt and an iridium salt (including a complex salt) in the process of forming and / or growing the grains. ), A rhodium salt (including a complex salt), and an iron salt (including a complex salt), at least one metal ion can be added to contain these metal elements inside and / or on the surface of the particle.

In the present invention, it is also preferable to add a silver halide solvent before the desalting step in order to accelerate the developing rate. For example, it is preferable to add a thiocyanate compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) in an amount of 1 × 10 ^{−3 to} 3 × 10 ⁻² mol per mol of silver.

In the present invention, it is preferable to use gelatin as the dispersion medium for the protective colloid of silver halide grains, and as the gelatin, alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 20,000 to 100,000),
Modified gelatin such as phthalated gelatin is used. Other hydrophilic colloids can also be used. Specific examples thereof include those described in Research Disclosure Magazine (hereinafter abbreviated as RD) Vol. 176, No. 17643 (December 1978).

The silver halide emulsion of the present invention may remove unnecessary soluble salts during the growth of silver halide grains,
Alternatively, it may remain contained. The soluble salts can be removed by the method described in RD Vol. 176, No. 17643.

The silver halide emulsion according to the present invention can be chemically sensitized. Chemical ripening, that is, chemical sensitization process conditions, such as pH, pAg, temperature, time, etc., are not particularly limited, and the conditions generally used in the art can be used. For chemical sensitization, a sulfur sensitizing method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitizing method using a selenium compound, a tellurium sensitizing method using a tellurium compound, and a reducing substance are used. The reduction sensitization method, gold or other noble metal sensitization method using a noble metal can be used alone or in combination, and among them, the selenium sensitization method,
A tellurium sensitization method, a reduction sensitization method and the like are preferably used.

In the case of selenium sensitization, the selenium sensitizer used may be a wide variety of selenium compounds. For example, U.S. Patents 1,574,944, 1,602,592, 1,623,49
9, JP 60-150046, JP 4-25832, 4-10924
No. 0, No. 4-147250, etc. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N,
N'-triethylselenourea, N, N, N'-trimethyl-N'-
Heptafluoroselenourea, N, N, N′-trimethyl-N′-
Heptafluoropropylcarbonyl selenourea, N, N,
N'-trimethyl-N'-4-nitrophenylcarbonyl selenoureas, etc.), selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), seleno Carboxylic acids and selenoesters (for example, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (for example, tricarboxylic acid)
-p-triselenophosphate, etc.) and selenides (diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenium ketones.

Specific examples of the technique of using these selenium sensitizers are, for example, US Pat. Nos. 1,574,944, 1,602,592 and 1,62.
3,499, 3,297,446, 3,297,447, 3,320,069
No. 3,408,196, 3,408,197, 3,442,653,
No. 3,420,670, No. 3,591,385, French Patent No. 2,693,
No. 038, No. 2,093,209, Japanese Patent Publication No. 52-34491, No. 52-34492
No. 53-295, 57-22090, JP-A-59-180536,
59-185330, 59-181337, 59-187338, 59-
192241, 60-150046, 60-151637, 61-24673
No. 8, JP 3-4221, 3-24537, 3-111838, the same
3-116132, 3-148648, 3-237450, 4-16838
No. 4-52832, 4-32831, 4-96059, 4-109
No. 240, No. 4-140738, No. 4-140739, No. 4-147250,
4-149437, 4-184331, 4-190225, 4-9171
No. 29, No. 4-195035, British Patent Nos. 255,846, 861,984, etc. are used. HE Spencer et al., Journal of Photographic Science, Vol. 31, 158-16
It is also disclosed on page 9 (1983).

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used. The addition method is, depending on the properties of the selenium compound used, water or a method of adding by dissolving in an organic solvent such as methanol or ethanol alone or in a mixed solvent, or a method of adding in advance by mixing with a gelatin solution. , The method disclosed in JP-A-4-140739, that is,
A method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer may be used.

The temperature of chemical ripening using a selenium sensitizer is 40
~ 90 ℃ range is preferred, more preferably 45 ℃ or more, 8
It is 0 ° C or lower. The pH is preferably in the range of 4 to 9 and the pAg is preferably in the range of 6 to 9.5.

Regarding the tellurium sensitizer and the sensitizing method, for example, US Pat. Nos. 1,623,499, 3,320,069 and 3,772,031 are cited.
No. 3,531,289, No. 3,655,394, British Patent No. 235,21
No. 1, 1,121,496, 1,295,462, 1,396,696,
Canadian Patent No. 800,958, Japanese Patent Laid-Open No. 4-204640, 4-333043
No., etc. Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyl tellurourea,
Tetramethyl tellurourea, N-carboxyethyl-N, N'-
Dimethyl tellurourea, N, N'-dimethyl-N'phenyl tellurourea, phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl)
-Diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (for example, telluroacetamide, N, N-dimethyl tellurobenzamide), telluroketones, telluroesters, isotelloocyanates and the like.

The technique for using the tellurium sensitizer is similar to that for the selenium sensitizer.

It is also preferable to carry out so-called reduction sensitization by providing reduction sensitizing nuclei inside the grain and / or on the grain surface by placing in a suitable reducing atmosphere.

Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and their derivatives. Other preferred reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

The amount of reducing agent added is such as the type of reduction sensitizer, the grain size of silver halide grains, the composition and crystal habit, the temperature of the reaction system, and p.
Although it is preferable to change it depending on the environmental conditions such as H and pAg, for example, in the case of thiourea dioxide, as a rough guide, a preferable result is obtained by using about 0.01 to 2 mg per mol of silver halide. In the case of ascorbic acid,
A range of about 50 mg to 2 g per mol of silver halide is preferred.

As conditions for reduction sensitization, the temperature is about 40 to 70.
C, time about 10-200 minutes, pH about 5-11, pAg about 1-1
A range of 0 is preferred. (Here, pAg value is the logarithm of the reciprocal of Ag ion concentration).

Silver nitrate is preferred as the water-soluble silver salt. By adding a water-soluble silver salt, so-called silver ripening, which is a kind of reduction sensitization technique, is performed. The pAg during silver ripening is suitably 1-6, preferably 2-4. The conditions such as temperature, pH and time are preferably within the above-mentioned reduction sensitization condition range. As a stabilizer for a silver halide photographic emulsion containing reduction-sensitized silver halide grains, a general stabilizer described below can be used, but the stabilizer disclosed in JP-A-57-82831 is used. And / or VS Gahler's paper "Zeitshrift f
ur wissenschaftliche Photographie Bd. 63, 133 (196
9) ”and the thiosulfonic acids described in JP-A-54-1019 are often used together with good results. The addition of these compounds may be carried out at any stage of the emulsion production process from crystal growth to the preparation process immediately before coating.

In the present invention, selenium sensitization, tellurium sensitization,
Reduction sensitization and the like may be used in combination, and other sensitization methods,
For example, it is preferable to use it in combination with a noble metal sensitization method.

The silver halide emulsion of the present invention may contain a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone in the emulsion layer or a layer having other layers. Good.

The hydrophilic colloid of the silver halide emulsion layer and the non-photosensitive layer of the light-sensitive material of the present invention preferably contains an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate etc.), aldehydes (eg formaldehyde, glyoxal, glutaraldehyde etc.), N-methylol compounds (eg dimethylol urea, methylol dimethylhydantoin etc.), dioxane derivatives (2,3-dihydroxydioxane) Etc.), active vinyl compounds (eg 1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N′-methylenebis {β- (vinylsulfonyl) propionamide}), etc., Active halogen compounds (2,4
-Dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (eg mucochloric acid, mucophenoxycycloric acid etc.), isoxazoles, 2-chloro-6-hydroxytriazinylated gelatin etc. alone or in combination. Can be used. Among them, JP-A-53-41221,
The active vinyl compounds described in JP-A-53-57257, JP-A-59-162456 and JP-A-60-80846 and the active halogen compounds described in US Pat. No. 3,325,287 can be preferably used.

Polymeric hardeners can also be used effectively. For example, dialdehyde starch, polyacrolein, US Pat.
A polymer having an aldehyde group such as an acrolein copolymer described in 396,029, a polymer having an epoxy group described in U.S. Patent 3,623,878, U.S. Patent 3,362,827,
Polymers having a dichlorotriazine group described in RD magazine 17333 (1978), polymers having an active ester group described in JP-A-56-66841, JP-A-56
-142524, U.S. Pat.No. 4,161,407, JP-A-54-65033,
Polymers having an active vinyl group described in RD magazine 16725 (1978) or a group serving as a precursor thereof are preferable, and an active vinyl group having a long spacer as described in JP-A-56-142524 is particularly preferable. Alternatively, a polymer in which a group serving as the precursor thereof is bonded to the polymer main chain is particularly preferable.

In the photographic light-sensitive material of the present invention, an appropriate amount of a hardening agent is added in advance in the step of applying the light-sensitive material so as to be suitable for rapid processing, and the water absorption amount of the light-sensitive material in the developing-fixing-washing step is increased. It is preferable to reduce the water content in the light-sensitive material before the start of drying by adjusting. The silver halide light-sensitive material of the present invention preferably has a swelling ratio of 150 to 250% and a film thickness after swelling of 70 μm or less. Swelling rate is 250
If it exceeds%, poor drying occurs, for example, automatic processor processing,
In particular, in rapid processing, conveyance failure is likely to occur. If the swelling ratio is less than 150%, uneven development and residual color tend to be deteriorated during development.

The term "swelling ratio" as used herein means the hydrophilicity before and after immersion of the silver halide photographic light-sensitive material in distilled water at 25 ° C for 1 minute by measuring the thickness of the hydrophilic colloid layer of the silver halide photographic light-sensitive material. The thickness of the colloid layer is measured, the difference in thickness is determined, and the difference is divided by the thickness of the hydrophilic colloid layer and multiplied by 100.

Examples of the support that can be used in the light-sensitive material of the present invention include the above-mentioned RD17643, page 28 and R.
Examples thereof include those described on page 1009 of D-308119.

A suitable support is a polyethylene terephthalate film, and the surface of these supports is provided with an undercoat layer or corona discharge to improve the adhesion of the coating layer.
You may give ultraviolet irradiation.

The silver halide photographic light-sensitive material of the present invention may further contain various additives depending on the purpose. Examples of additives and the like used include RD magazine No. 17643
(December 1978), 18718 (November 1979) and 308119
(December 1989). The places where they are written are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Next, preferable development processing of a light-sensitive material using the emulsion of the present invention will be described.

As a preferred developing solution for developing a light-sensitive material using the emulsion of the present invention, a developing agent is disclosed in JP-A-4-15641.
No. 4, 4-16841 and the like dihydroxybenzenes such as hydroquinone, as para-aminophenols such as p-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc., as 3-pyrazolidones For example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone, etc. may be used, and ascorbic acids may be used. May be. These developing agents are preferably used in combination. The amount of these main agents contained in the treatment liquid constituent components is preferably such that the total number of moles of dihydroxybenzenes, paraaminophenols and 3-pyrazolidones is 0.1 mol / liter or more.

The preservative may include sulfites such as potassium sulfite, sodium sulfite, reductones such as piperidinohexose reductone, and these are preferably 0.2 to 1 mol / liter, more preferably 0.3. It is recommended to use ~ 0.6 mol / liter. In addition, adding a large amount of ascorbic acid also leads to processing stability.

The alkaline agent includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate. Further, borate described in JP-A-61-28708, 60-93439
Buffers such as saccharose, acetoxime, 5-sulfosalicylic acid, phosphates and carbonates described in No. 1 may be used.

These agents can be selected so that the pH of the developer is 9.0 to 13.0, preferably 10 to 12.5.

As a dissolution aid, diethylene glycol,
Sensitizers such as triethylene glycols and their esters may contain, for example, quaternary ammonium salts, development accelerators, surfactants and the like.

As a silver sludge inhibitor, JP-A-56-10624
The silver stain-preventing agent described in No. 4, the sulfide or disulfide compound described in JP-A-3-51844, the cysteine derivative or the triazine compound described in Japanese Patent Application No. 4-92947 can be preferably used.

As an organic inhibitor, an azole organic antifoggant, for example, an indazole type, an imidazole type, a benzimidazole type, a triazole type, a benztriazo type, a tetrazole type, a thiadiazole type, a mercaptoazole type (for example, 1-phenyl-5- A mercaptotetrazole) compound or the like is used. The inorganic inhibitor may contain sodium bromide, potassium bromide, potassium iodide and the like. LFA Menson, "Photographic Processing Chemistry," published by Focal Press (1966), pages 226 to 229, U.S. Pat. No. 2,193,015.
And JP-A Nos. 2,592,364 and JP-A-48-64933 may be used.

As a chelating agent for masking calcium ions mixed in tap water used as a treatment liquid, a chelating agent having a chelate stabilization constant of 8 or more as an organic chelating agent described in JP-A 1-193853 is used. Is preferably used. Sodium hexametaphosphate as an inorganic chelating agent,
Examples include calcium hexametaphosphate and polyphosphate.

As the development hardening agent, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used. However, for rapid processing, it is preferable that the hardener is allowed to act in the coating step of the photosensitive material in advance as described above, rather than the hardener is allowed to act in the development processing step.

The processing temperature of the preferred developing solution for developing the silver halide photographic light-sensitive material according to the present invention is preferably 25-50.
C., more preferably 30 to 40.degree. Development time is 4-9
It is 0 second, more preferably 6 to 60 seconds. Processing time is Dry
to Dry is preferably 15 to 210 seconds, more preferably 30 to 90
Seconds. Replenishment of the processing solution is performed by replenishing the processing agent fatigue and oxidation fatigue, evaporation, and film carry-out. As the replenishment method, replenishment by width and feed rate described in JP-A-55-126243, area replenishment described in JP-A-60-104946, and JP-A-1
-Area replenishment controlled by the number of continuous treatments described in No. 149156 may be used, and the preferable replenishment amount is 80cc to 500cc / m.
² The fixing solution may include fixing materials commonly used in the art. The pH of the fixer is 3.8 or higher,
It is preferably 4.2 or more. The fixing agent is a thiosulfate such as ammonium thiosulfate or sodium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The concentration of ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / liter, more preferably 0.8 to 3 mol / liter. The fixer may be an acid hardening agent. In this case, aluminum ions are preferably used as the hardener. For example, it is preferably added in the form of aluminum sulfate, aluminum chloride, potassium alum, or the like. Preservatives such as sulfites and bisulfites, pH buffers such as acetic acid and boric acid, mineral acids (sulfuric acid, nitric acid), organic acids (citric acid, oxalic acid, malic acid, etc.), hydrochloric acid, etc. PH adjusting agents such as various acids and metal hydroxides (potassium hydroxide, sodium hydroxide) and chelating agents having a water softening ability can be included. As the fixing accelerator, for example, thiourea derivatives described in JP-B Nos. 45-35754, 58-122535 and 58-122536, and thioethers described in US Pat. No. 4,126,459 may be used.

[0091]

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

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

A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 potassium bromide 841 g 2825 ml of D1 1.75N potassium bromide aqueous solution with water At the following silver potential control amount of 42 ° C., each of solution B1 and solution C1 is added to solution A1 using the mixing stirrer shown in JP-B-58-58288 and 58-58289.
Nucleation was performed by adding 464.3 ml by the double-sided mixing method over 1.5 minutes.

After the addition of the solutions B1 and C1 was stopped, it took 60 minutes to raise the temperature of the solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then add the solution B1 again. Solution C1 was added by the double jet method at a flow rate of 55.4 ml / min each 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 this temperature increase from 42 ° C. to 60 ° C. and re-simultaneous mixing with the solutions B1 and C1 was +8 mv using the solution D1. And +16 mv.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. This seed emulsion has a maximum adjacent side ratio of 1.0 to 90% of the total projected area of silver halide grains.
It was confirmed by an electron microscope that the hexagonal tabular grains of 2.0 had an average thickness of 0.064 μm and an average grain size (circle diameter conversion) of 0.595 μm. The coefficient of variation of thickness is 40
%, And the coefficient of variation in the distance between twin planes was 42%.

Preparation of Em-1 A tabular pure silver bromide emulsion Em-1 was prepared using seed emulsion-1 and the following three kinds of solutions.

A2 ossein gelatin 34.03 g polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol solution) 2.25 ml seed emulsion-1 1.218 mol equivalent Water is made up to 3150 ml.

B2 Potassium bromide 1744 g Make up to 3664 ml with water.

C2 Silver nitrate 2492 g Water to make 4188 ml.

Solution A2 was vigorously stirred in the reaction vessel while maintaining it at 60 ° C., and the total amount of solution B2 and solution C2 was added thereto by the simultaneous mixing method over 65 minutes. During this time, the pH was 5.8,
The pAg was kept at 8.7 throughout.

D2 3 wt% gelatin and silver iodide fine grain emulsion (*) (average grain size 0.05 μm) (*) Preparation of fine grain emulsion To 6.64 liter of 5.0 wt% gelatin aqueous solution containing 0.06 mol of potassium iodide, Two 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. Nitric acid is used for pH during the formation of fine particles.
The temperature was controlled to 2.0 and the temperature was controlled to 40 ° C. After particle formation, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

Further, the above solution D2 was added in an amount of 0.15 with respect to the total amount of silver.
Halogen substitution was carried out by adding mol% equivalent.

After the completion of the addition, the emulsion was cooled to 40 ° C., and 1800 ml of a 13.8% (weight) aqueous solution of modified gelatin modified with phenylcarbamoyl groups (substitution rate 90%) was added as an aggregating polymer agent and stirred for 3 minutes. Then, a 56% (weight) acetic acid aqueous solution was added to adjust the pH of the emulsion to 4.6, the mixture was stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then, 9.0 l of distilled water at 40 ° C was added, and the supernatant was drained after standing with stirring, 11.25 l of distilled water was further added, and after standing with stirring, the supernatant was drained. Subsequently, a gelatin aqueous solution and a 10% (weight) aqueous solution of sodium carbonate were added to give a pH of 5.80.
The mixture was adjusted so that the mixture was stirred at 50 ° C for 30 minutes and redispersed. After redispersion, pH was adjusted to 5.80 and pAg was adjusted to 8.06 at 40 ° C.

Subsequently, after the emulsion was heated to 60 ° C., predetermined amounts of the following spectral sensitizing dyes A and B were added as a solid fine particle dispersion, and then ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added. A mixed aqueous solution and a solution obtained by dissolving triphenylphosphine selenide in a mixed solvent of methanol and ethyl acetate were added in the following amounts, respectively, and then aged for a total of 2 hours. At the end of ripening, an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

Spectral sensitizing dye A 5,5'-Dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) -oxacarbocyanine sodium salt anhydrous Spectral sensitizing dye B 5,5 ' -Di- (butoxycarbonyl) -1,1'-di-ethyl-3,
Anhydrate of 3'-di- (4-sulfobutyl) -benzimidazolocarbocyanine sodium salt The addition amount of the additive per mol of silver halide is shown below.

Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.2 mg Stabilizer (TAI) 280 mg A solid fine particle dispersion of the above-mentioned spectral sensitizing dye is disclosed in Japanese Patent Application No. 4-99.
It was prepared by a method similar to that described in No. 437.

That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature had been adjusted to 27 ° C. in advance, and the mixture was stirred by a high speed stirrer (dissolver) at 3.500 rpm for 30 to 120 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.11 μm, an average thickness of 0.25 μm, an average aspect ratio of about 4.5 and a grain size distribution of 18.1% were obtained. Met. Also, the average distance between twin planes is
It was 0.020 μm.

Preparation of Em-2 Tabular silver halide emulsion Em-2 was prepared using seed emulsion-1 and the following four kinds of solutions.

A2 (see Em-1) B3 Potassium bromide 1734 g Make up to 3644 ml with water.

C3 Silver nitrate 2478 g Water to make 4165 ml.

D3 3% by weight of gelatin and silver iodide fine grain emulsion (*) (average grain size 0.05 μm) equivalent to 0.080 mol (*) Preparation of silver iodide fine grain emulsion Silver iodide fine grain emulsion identical to Em-1 above The solution A2 was vigorously stirred in the reaction vessel while being kept at 60 ° C., and 1 part of the solution B3, 1 part of the solution C3 and the solution D
Half of 3 was added by the double-sided mixing method over 20 minutes, and then half of the remaining amount of solution B3 and solution C3 was added over 37 minutes, followed by 1 part of solution B3 and 1 part of solution C3. And the rest of Solution D3 was added over 20 minutes and finally Solution B
The rest of C3 and C3 were added over 33 minutes. Meanwhile, p
H was kept at 5.8 and pAg was kept at 8.8 throughout. Here, the addition rates of the solution B3 and the solution C3 were changed in a function-like manner with respect to time so as to match the critical growth rate.

Further, the above solution D3 was added to the total silver amount of 0.
Halogen substitution was carried out by adding 15 mol% equivalent.

After completion of the addition, insoluble salts were removed in the same manner as Em-1. Subsequently, spectral sensitization and chemical sensitization were performed in exactly the same manner as Em-1.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.09 μm, an average thickness of 0.24 μm, an average aspect ratio of about 4.5 and a grain size distribution of 18.9% were obtained. Met. Also, the average distance between twin planes is
0.020 μm, 97% (number) of all tabular silver halide grains with a twin plane distance to thickness ratio of 5 or more, 49% of 10 or more grains and 17% of 15 or more grains. Was occupied.

Preparation of Em-3 In the preparation of Em-2, first half the amount of solution D3 and 1 part of solution B and C were added for 10 minutes, second time the remaining amount of solution D3 and solution B and C were added. Em-3 was prepared in exactly the same manner as Em-2 except that 1 part of the above was added by the simultaneous mixing method over 10 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.10 μm, an average thickness of 0.24 μm, an average aspect ratio of about 4.5 and a grain size distribution of 18.5% were obtained. Met. Also, the average distance between twin planes is
0.020 μm, 97% (number) of all tabular silver halide grains with a twin plane distance to thickness ratio of 5 or more, 49% of 10 or more grains and 17% of 15 or more grains. Was occupied.

Preparation of Em-4 In the preparation of Em-2, firstly the amount of solution D3 and solution B were
5 minutes to add 1 part of C and C and the remaining amount of the second solution D3 and 15 minutes to add 1 part of solutions B and C were added by the simultaneous mixing method. Exactly like E
m-4 was prepared.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.11 μm, an average thickness of 0.25 μm, an average aspect ratio of about 4.5 and a grain size distribution of 18.1% were obtained. Met. Also, the average distance between twin planes is
It was 0.020 μm.

Preparation of Em-5 In the preparation of Em-2, first half the amount of solution D3 and 1 part of solution B and C were added for 15 minutes, second time the remaining amount of solution D3 and solution B were added. Em-5 was prepared in exactly the same manner as Em-2 except that 1 part of C was added by the simultaneous mixing method over 5 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.10 μm, an average thickness of 0.24 μm, an average aspect ratio of about 4.5 and a grain size distribution of 18.5% were obtained. Met. The average distance between twin planes was 0.020 μm, and grains having a ratio of distance between twin planes to thickness of 5 or more accounted for 97% (number) of all tabular silver halide grains.
The above particles accounted for 49%, and the particles above 15 accounted for 17%.

Preparation of Em-6 In the preparation of Em-2, first half the amount of solution D3 and 1 part of solution B and C were added for 4 minutes, second time the remaining amount of solution D3 and solution B were added. Em-6 was prepared in exactly the same manner as Em-2 except that 1 part of C was added by the simultaneous mixing method over 20 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.09 μm, an average thickness of 0.24 μm, an average aspect ratio of about 4.5 and a grain size distribution of 19.0% were obtained. Met.

Preparation of Em-7 In the preparation of Em-2, first 20 minutes to add half the amount of solution D3 and 1 part of solution B and C, 2nd time the remaining amount of solution D3 and solution B Em-7 was prepared in exactly the same manner as Em-2 except that 1 part of C was added by the simultaneous mixing method over 4 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.07 μm, an average thickness of 0.24 μm, an average aspect ratio of about 4.5 and a grain size distribution of 19.2% were obtained. Met.

Preparation of Em-8 Solution A3 was vigorously stirred in a reaction vessel while being kept at 60 ° C., and 1 part of solution B3, 1 part of solution C3 and solution D were added thereto.
The total amount of 3 was added by the simultaneous mixing method over 3 minutes, and then the remaining amounts of the solution B3 and the solution C3 were added by the simultaneous mixing method over 67 minutes. During this time, the pH was kept at 5.8 and the pH was kept at 8.8 throughout. Here, the addition rates of the solution B3 and the solution C3 were changed in a function-like manner with respect to time so as to match the critical growth rate. Otherwise, Em-8 was prepared in exactly the same manner as Em-2.

When the obtained silver halide emulsion was observed with an electron microscope, it was found to be tabular silver halide grains having an average grain size of 1.08 μm, an average thickness of 0.24 μm, an average aspect ratio of about 4.5 and a grain size distribution of 19.2%. there were.

Preparation of Em-9 Solution A3 was vigorously stirred in the reaction vessel while maintaining it at 60 ° C., and half of the solutions B3 and C3 were added thereto by the simultaneous mixing method over 38 minutes, and then the solution was continuously mixed. 1 part of B3, 1 part of solution C3 and the total amount of solution D3 were added over 3 minutes, and then the remaining amounts of solution B3 and solution C3 were added over 33 minutes by the simultaneous mixing method. During this time, the pH was kept at 5.8 and the pH was kept at 8.8 throughout. Here, the addition rates of the solution B3 and the solution C3 were changed in a function-like manner with respect to time so as to match the critical growth rate. Otherwise, Em-9 is exactly the same as Em-2.
Was prepared.

The obtained silver halide emulsion was observed by an electron microscope to find that it was tabular silver halide grains having an average grain size of 1.08 μm, an average thickness of 0.24 μm, an average aspect ratio of about 4.5 and a grain size distribution of 19.2%. there were.

Preparation of Em-10 Tabular silver halide emulsion Em-10 was prepared using seed emulsion-1 and the following four kinds of solutions.

A2 (see Em-1) B4 Potassium bromide 1736 g Make up to 3648 ml with water.

C4 Silver nitrate 2480 g Water to make 4170 ml.

D3 (see Em-2) Solution A2 was vigorously stirred in the reaction vessel while maintaining the temperature at 60 ° C., and 1 part of solution B4, 1 part of solution C4 and solution D were added thereto.
4 of the solution B4 and the solution C4 were added in half over a period of 37 minutes, and then 1 part of the solution B4 and 1 of the solution C4 were added.
Parts and the rest of the solution D3 was added over 10 minutes and finally the rest of the solutions B4 and C4 was added over 33 minutes. During this time, the pH was kept at 5.8 and the pH was kept at 8.8 throughout. Where solution B
4 and solution C4 were added in a function-wise manner with respect to time so as to match the critical growth rate.

Further, the above solution D3 was added in an amount of 0.05 based on the total silver amount.
Halogen substitution was carried out by adding mol% equivalent.

After completion of the addition, insoluble salts were removed in the same manner as Em-1. Subsequently, Em-10 was prepared by performing spectral sensitization and chemical sensitization in exactly the same manner as Em-1.

When the obtained silver halide emulsion was observed by an electron microscope, tabular silver halide grains having an average grain size of 1.09 μm, an average thickness of 0.24 μm, an average aspect ratio of about 4.5 and a grain size distribution of 19.1% were obtained. Met.

Preparation of Em-11 In the preparation of Em-10, 5 minutes for the first addition of half the amount of solution D3 and 1 part of solutions B and C, the second time for solution D3.
Em-11 was prepared in exactly the same manner as Em-10, except that the remaining remaining amount and 1 part of solutions B and C were added by the simultaneous mixing method over 15 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.09 μm, an average thickness of 0.24 μm, an average aspect ratio of about 4.5 and a grain size distribution of 19.1% were obtained. Met.

Preparation of Em-12 In the preparation of Em-10, first half the amount of solution D3 and 1 part of solutions B and C were added for 15 minutes and secondly for solution D3.
Em-12 was prepared in exactly the same manner as Em-10, except that the remaining remaining amount and 1 part of solutions B and C were added by the simultaneous mixing method over 5 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.09 μm, an average thickness of 0.24 μm, an average aspect ratio of about 4.5 and a grain size distribution of 19.1% were obtained. Met.

Preparation of Em-13 In the preparation of Em-2, first half the amount of solution D3 and 1 part of solution B and C were added for 15 minutes, the second time the remaining amount of solution D3 and solution B were added. Em-13 was prepared in exactly the same manner as Em-2 except that 1 part of C was added by the simultaneous mixing method over 15 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.09 μm, an average thickness of 0.24 μm, an average aspect ratio of about 4.5 and a grain size distribution of 18.9% were obtained. Met.

Preparation of Em-14 Tabular silver halide emulsion Em-14 was prepared using seed emulsion-1 and the following four solutions.

A2 (see Em-1) B5 Potassium bromide 1718 g Water to make 3610 ml.

C5 Silver nitrate 2455 g Water to make 4127 ml.

D5 3% by weight of gelatin and 0.215 mol of silver iodide fine grain emulsion similar to Em-1 Solution A2 was vigorously stirred in a reaction vessel while maintaining at 60 ° C., and 1 part of Solution B5 and Solution C5 were added thereto. Part 1 and solution D
Half of 5 was added by the simultaneous mixing method over 12 minutes, and then half of the remaining amount of solution B5 and solution C5 was added over 37 minutes, and then 1 part of solution B5 and 1 of solution C5 were continuously added.
Parts and the rest of the solution D5 was added over 12 minutes and finally the rest of the solutions B5 and C5 was added over 33 minutes. During this time, the pH was kept at 5.8 and the pH was kept at 9.0 throughout. Where solution B
The addition rates of 5 and solution C5 were changed in a function-like manner with respect to time so as to match the critical growth rate.

Further, the above solution D5 was added in an amount of 0.15 with respect to the total amount of silver.
Halogen substitution was carried out by adding mol% equivalent.

After the completion of the addition, insoluble salts were removed in the same manner as Em-1. Subsequently, spectral sensitization and chemical sensitization were carried out in the same manner as Em-1 to prepare Em-14.

When the obtained silver halide emulsion was observed with an electron microscope, it was found to be tabular silver halide grains having an average grain size of 1.09 μm, an average thickness of 0.24 μm, an average aspect ratio of about 4.5 and a grain size distribution of 18.9%. there were. The average distance between twin planes is 0.
020 μm, 97% (number) of all tabular silver halide grains having a twin-to-plane distance to thickness ratio of 5 or more, 49% of 10 or more grains, and 17% of 15 or more grains. Had occupied.

Preparation of Em-15 A tabular silver halide emulsion Em-15 was prepared using seed emulsion-1 and the following four kinds of solutions.

A2 (see Em-1) B6 Potassium bromide 1739 g Make up to 3654 ml with water.

C6 Silver nitrate 2485 g Water to make 4176 ml.

D6 3% by weight of gelatin and silver iodide fine grain emulsion similar to Em-1 equivalent to 0.048 mol Solution A2 was vigorously stirred in a reaction vessel while maintaining at 60 ° C., and 1 part of solution B6 and solution C6 were added thereto. Part 1 and solution D
Half of 6 was added by the double-sided mixing method over 7 minutes, then half of the remaining amount of solution B6 and solution C6 was added over 37 minutes, and then 1 part of solution B6 and 1 part of solution C6 were continuously added.
Parts and the rest of the solution D6 was added over 7 minutes and finally the rest of the solutions B6 and C6 was added over 33 minutes. During this period, pH was kept at 5.8 and pH was kept at 8.75. Here, the addition rates of the solution B6 and the solution C6 were changed in a function-like manner with respect to time so as to match the critical growth rate.

Further, the above solution D5 was added in an amount of 0.10 with respect to the total amount of silver.
Halogen substitution was carried out by adding mol% equivalent.

After completion of the addition, insoluble salts were removed in the same manner as Em-1. Subsequently, Em-15 was prepared by carrying out spectral sensitization and chemical sensitization in exactly the same manner as Em-1.

The obtained silver halide emulsion was observed with an electron microscope to find that it was a tabular silver halide grain having an average grain size of 1.09 μm, an average thickness of 0.24 μm, an average aspect ratio of about 4.5 and a grain size distribution of 18.9%. there were.

Preparation of Em-16 In the preparation of Em-2, 1 part of Solution B3 and 1 part of Solution C3.
Parts and half of the solution D3 were added by the simultaneous mixing method over 16 minutes, and then half of the remaining amounts of the solutions B3 and C3 were added over 32 minutes, and then 1 part of the solution B3 and the solution were continuously added. One part of C3 and the rest of the solution D3 were added over 16 minutes, and finally the rest of the solutions B3 and C3 were added over 28 minutes. During this period, pH was kept at 5.8 and pH was kept at 9.2 throughout.
Otherwise, Em-16 was prepared in exactly the same manner as Em-2.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.28 μm, an average thickness of 0.17 μm, an average aspect ratio of about 7.5 and a grain size distribution of 20.1% were obtained. Met.

Preparation of Em-17 In the preparation of Em-16, first half the amount of solution D3 and 1 part of solution B and C were added for 8 minutes, second time the remaining amount of solution D3 and solution B and C were added. Em-17 was prepared in exactly the same manner as Em-16 except that 1 part of the above was added by the simultaneous mixing method over 8 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.28 μm, an average thickness of 0.17 μm, an average aspect ratio of about 7.5 and a grain size distribution of 20.1% were obtained. Met.

Preparation of Em-18 In the preparation of Em-16, half the amount of solution D3 and 1 part of solutions B and C were added for 4 minutes, the second time the remaining amount of solution D3 and solution B were added. Em-18 was prepared in exactly the same manner as Em-16 except that 1 part of C was added by the simultaneous mixing method over 12 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.28 μm, an average thickness of 0.17 μm, an average aspect ratio of about 7.5 and a grain size distribution of 20.1% were obtained. Met.

Preparation of Em-19 In the preparation of Em-16, first half the amount of solution D3 and 1 part of solutions B and C were added for 12 minutes, second time the remaining amount of solution D3 and solution B were added. Em-19 was prepared in exactly the same manner as Em-16 except that 1 part of C was added by the simultaneous mixing method over 4 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.28 μm, an average thickness of 0.17 μm, an average aspect ratio of about 7.5 and a grain size distribution of 20.1% were obtained. Met.

Preparation of Em-20 In the preparation of Em-16, first half the amount of solution D3 and 1 part of solution B and C were added for 3 minutes, second time the remaining amount of solution D3 and solution B were added. Em-20 was prepared in exactly the same manner as Em-16 except that 1 part of C was added by the simultaneous mixing method over 16 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.28 μm, an average thickness of 0.17 μm, an average aspect ratio of about 7.5 and a grain size distribution of 20.1% were obtained. Met.

Preparation of Em-21 In the preparation of Em-16, first half the amount of solution D3 and part of solution B and C was added 16 minutes, second time the remaining amount of solution D3 and solution B were added. Em-21 was prepared in exactly the same manner as Em-16 except that part of C was added by the simultaneous mixing method over 3 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.28 μm, an average thickness of 0.17 μm, an average aspect ratio of about 7.5 and a grain size distribution of 20.1% were obtained. Met.

Preparation of Em-22 Solution A3 was vigorously stirred in a reaction vessel while maintaining it at 60 ° C., and 1 part of solution B3, 1 part of solution C3 and solution D were added thereto.
The total amount of 3 was added by the simultaneous mixing method in 2 minutes, and then the remaining amounts of the solutions B3 and C3 were continuously added by the simultaneous mixing method over 60 minutes. During this period, pH was kept at 5.8 and pH was kept at 9.2 throughout. Other than that, Em-22 is the same as Em-2.
Was prepared.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.28 μm, an average thickness of 0.17 μm, an average aspect ratio of about 7.5 and a grain size distribution of 20.1% were obtained. Met.

Preparation of Em-23 Solution A3 was vigorously stirred in a reaction vessel while maintaining it at 60 ° C, and 1 part of solution B3 and half the amount of solution C3 were added thereto by the simultaneous mixing method over 32 minutes. Then, 1 part of the solution B3, 1 part of the solution C3 and the total amount of the solution D3 were added over 2 minutes, and subsequently, the remaining amounts of the solution B3 and the solution C3 were added over 28 minutes by the simultaneous mixing method. During this time, pH was 5.8 and pAg
Kept at 9.2 throughout. Otherwise, Em-23 was prepared in exactly the same manner as Em-2.

When the obtained silver halide emulsion was observed with an electron microscope, it was found to be tabular silver halide grains having an average grain size of 1.28 μm, an average thickness of 0.17 μm, an average aspect ratio of about 7.5 and a grain size distribution of 20.1%. there were.

Preparation of Em-24 In the preparation of Em-2, 1 part of solution B3, 1 part of solution C3 and half the amount of solution D3 were added by the simultaneous mixing method over 12 minutes, and subsequently solution B3 was added. Half the remaining amount of solution C3 was added over 45 minutes, and then 1 part of solution B3, 1 part of solution C3 and the rest of solution D3 were added over 12 minutes, and finally solutions B3 and C3. The entire remaining amount was added over 28 minutes. During this time, the pH was kept at 5.8 and the pH was kept at 8.6. Otherwise, Em-24 was prepared in exactly the same manner as Em-2.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 0.886 μm, the average thickness was 0.36 μm,
The tabular silver halide grains had an average aspect ratio of about 2.5 and a grain size distribution of 16.1%.

Preparation of Em-25 In Em-14, the pAg during addition of solutions B, C and D was 8.8.
Em-25 was prepared in the same manner as Em-14 except that the above was maintained.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 0.886 μm, the average thickness was 0.36 μm,
The tabular silver halide grains had an average aspect ratio of about 2.5 and a grain size distribution of 16.1%.

As described above, the average aspect ratio (AR) of the obtained emulsions Em-1 to Em-25, the average silver iodide content, the maximum value of the silver iodide content inside the grain, and the silver iodide content on the outermost surface are contained. The results of measuring the rate are shown in Table 1 below.

The silver iodide content on the outermost surface was determined as follows.

Emulsion proteolytic enzyme (pronase)
0.05% by weight aqueous solution was added and the mixture was stirred at 45 ° C for 30 minutes to decompose gelatin. This is centrifuged to precipitate the emulsion particles, and the supernatant is removed. Next, distilled water is added to disperse the emulsion particles in distilled water, followed by centrifugation to remove the supernatant.
Further, the emulsion particles are redispersed in water and thinly coated on a mirror-polished silicon wafer to obtain a measurement sample.

By using the sample thus prepared, X
The surface silver iodide was measured by PS. In order to prevent the sample from being destroyed by the X-ray irradiation, the sample was cooled to -110 to -120 ° C in the XPS measurement chamber. As an X-ray for the probe,
Irradiate MgKα with X-ray source voltage of 15kV and X-ray source current of 40mA,
Measurements were made for 3d5 / 2, Br3d, and I3d3 / 2 electrons.

The integrated intensity of the measured peak was corrected with a sensitivity factor (Sensitivity Factor), and the halide composition of the outermost surface was obtained from the intensity ratio of these.

[0182]

[Table 1]

Additives described below were added to the obtained 25 kinds of emulsions to prepare emulsion layer coating solutions. At the same time, a protective layer coating solution described below was also prepared. Using both coating solutions, two slide hopper type coaters were used so that the coated amount was 2.0 g / m ² per side and the amount with gelatin was 3.1 g / m ^2, and it was supported at a speed of 80 m / min. Both sides were simultaneously coated on the body and dried in 2 minutes and 20 seconds to obtain sample Nos. 1 to 25.

Glycidimethacrylate 50 is used as the support.
The concentration of the copolymer composed of three kinds of monomers of 10% by weight, 10% by weight of methyl acrylate and 40% by weight of butyl methacrylate is 10% by weight.
A polyethylene terephthalate film base colored blue with a concentration of 0.15 for an X-ray film of 175 μm was used as an undercoating solution of the copolymer aqueous dispersion obtained by diluting the resulting copolymer to a concentration of 0.1%.

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 70 mg t-Butyl-catechol 400 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg 1 2,3-Dihydroxybenzene-4-sulfonate ammonium 2g

[0187]

Embedded image

C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1-phenyl-5-mercaptotetrazole 15 mg Protective Layer Solution Next, the following was prepared as a protective layer coating solution. The additives are shown in the amount per liter of coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 1 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (area average particle size 1.2 μm matting agent) 0.5 g (CH ₂ = CHSO ₂ CH ₂ ) ₂₀ (hardening agent) 500 mg C ₄ F ₉ SO ₃ K 2mg C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0190]

Embedded image

Photographic properties were evaluated using the obtained sample Nos. 1 to 25. First, the sample is sandwiched between two intensifying screens (KO-250), and the tube voltage is 80 kvp and the tube current is 100 m through the aluminum wedge.
A, X-ray of 0.05 second was irradiated and exposed. Next, using an automatic developing machine (SRX-503), processing was performed with a developing solution and a fixing solution having the following formulations.

Developer Formulation Part-A (for 12 liter finish) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium bicarbonate 132 g Boric acid 40 g 5-Methylbenzotriazole 1.4 g 5-Nitro Benzimidazole 0.4 g 1-Phenyl-5-mercaptotetrazole 0.25 g 4-Hydroxymethyl-4-methyl-1-phenylpyrazolidone 102 g Hydroquinone 390 g Diethylene glycol 550 g Add water to make 6000 ml.

Part-B (for 12 l finishing) Glacial acetic acid 70 g 5-Nitroindazole 0.6 g Glutaraldehyde (50% solution) 8.0 g N-acetyl-DL-penicillamine 1.2 g Starter glacial acetic acid 120 g Potassium bromide 225 g H0 (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH 1.0 g CH ₃ N (C ₃ H ₆ NHCONHCH ₂ SC ₂ H ₅ ) ₂ 1.0 g 5-methylbenzotriazole 1.5 g Add water to make 1.0 liter .

Fixer formulation Part-A (for finishing 18.3l) Ammonium thiosulfate (70wt / vol%) 4500g Sodium sulfite 450g Sodium acetate trihydrate 450g Boric acid 110g Tartaric acid 60g Sodium citrate 10g Gluconic acid 70g 1- (N , N-Dimethylamino) -ethyl-5-mercaptotetrazole 18g Glacial acetic acid 330g Aluminum sulfate 62g Add water to make 7200ml.

The developer is prepared by adding Part A and Part B to approximately 5 liters of water.
Was added at the same time, water was added while dissolving with stirring, the pH was adjusted to 12.53 with 12 g of glacial acetic acid. This is used as a development replenisher.

20 ml / l of the aforesaid starter was added to 1 liter of this development replenisher to adjust the pH to 10.30 to prepare a working solution.

To prepare the fixing solution, Part A was simultaneously added to about 5 liters of water, and water was added while stirring and dissolving to make 18.3 liters. The pH was adjusted to 4.6 using sulfuric acid and NaOH. This is the fixing replenisher. The processing temperature is 35 ℃ for development, 33 ℃ for fixing,
Washing with water was 20 ° C., drying was 50 ° C., and processing time was dry to dry for 25 seconds.

After the treatment, the sensitivity was measured. Sensitivity is expressed as the reciprocal of the exposure dose that gives a density of fog + 0.5. Sample No. 1
The relative sensitivity is shown when the sensitivity of is set to 100.

A load of 5 g was applied to each of the unexposed samples with a scratch hardness meter having a needle having a needle head of 0.3 mm, and then the same development processing as above was performed, and the density of pressure fog generated was measured with a microdensitometer. did. The degree of fog is shown as a relative value when the increase in fog of Sample No. 1 is 100.

The safelight property was evaluated by passing each sample through a red filter having the transmittance shown in FIG. 1 at a relative humidity of 50% and a temperature of 23 ° C.
It was irradiated from m for 30 minutes, and the same development processing as above was performed to measure the increase value of fog to obtain safe light fog. The smaller the value, the better the safelight property.

The results obtained are shown in Table 2.

[0202]

[Table 2]

As is clear from Table 2, sample No. 1 and sample N
Comparing o.3 to 5 and 13, the samples of the present invention having two maximal values of 4 mol% or more are highly sensitive, as compared with those having no maximal value of silver iodide content inside the grain, Also, it can be seen that there is little pressure fog.

Further, even when compared with the sample No. 2 having a maximum value of less than 4 mol%, it is found that the samples No. 3 to 5 and 13 of the present invention are also excellent.

Comparing Sample Nos. 6 to 9 with Samples 3 to 5 and 13, even if only one of the two maximum values is 4 mol% or more, the sensitivity is not high and the safelight property is deteriorated. I understand. Comparing Sample Nos. 10 to 12 with Samples 3 to 5 and 13, it can be seen that when the silver iodide content on the surface is low, the sensitivity is low and the safelight property is not good.

Further, it can be seen that Sample No. 15 has excellent safelight resistance even if the average AgI content is slightly lower than Nos. 3 to 5 and 13, and has high sensitivity and little pressure fog.

Further, it can be seen that in Samples Nos. 14 and 25, if the average silver iodide content of silver halide grains is high, fixing failure occurs in rapid processing. Sample No. 24 shows low sensitivity when the aspect ratio is low. Sample No. 16 and Sample No. 17 ~
Sample No. 2 and Sample No. 19 above have high aspect ratios.
High sensitivity, low pressure fog, and excellent safelight property, similar to the comparison of 3 to 5 and 13.

The sample Nos. 20 to 23 and the sample Nos. 17 to 19 have the above-mentioned sample Nos. 6 to 9 and the sample Nos. 3 to 5 even if the aspect ratio is high.
Similar to the comparison of 13, only one of the two maxima is 4
It can be seen that the sensitivity does not increase even if the amount is more than mol% and the safelight property deteriorates.

[0209]

According to the present invention, a silver halide photographic emulsion having high sensitivity, low pressure fog and low safelight fog property and a silver halide photographic light-sensitive material using the same can be obtained. The silver halide photographic light-sensitive material of the present invention had suitability for rapid processing.

[Brief description of drawings]

FIG. 1 is a transmittance curve of a red filter used in an example.

Front Page Continuation (72) Inventor Yoko Kobayashi Konica Co., Ltd. 1 Sakura-cho, Hino-shi, Tokyo

Claims (4)

[Claims] 1. A silver iodide content on the outermost surface of the silver halide grain having at least two sites inside the silver halide grain having a maximum silver iodide content of 4 mol% or more. Is 4 mol% or more and the average silver iodide content is 1.0 mol% or less, and the silver halide photographic emulsion is characterized by containing. 2. The silver halide grains have an average aspect ratio of 3.
The silver halide photographic emulsion according to claim 1, which is 0 or more tabular silver halide grains. 3. A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion according to claim 1 in at least one of the silver halide emulsion layers. 4. A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion according to claim 2 in at least one of the silver halide emulsion layers.