JPH08201945A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide the silver halide photographic sensitive material high in sensitivity and superior in rapid processability and small in residual dye stains. CONSTITUTION: The silver halide emulsion in at least one of the silver halide emulsion layers contains silver halide grains satisfying the following conditions (1)-(4): (1) An average silver chloride content is >=10mol%, (2) the surface of each silver halide grain contains silver iodide in an amount of 1-13mol%, (3) flat silver halide grains having an average aspect ratio of >=3 is contained, and (4) a spectrally sensitizing dye is adsorbed in >=90% of the surface area of each silver halide grain.

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 light-sensitive material having high sensitivity, excellent rapid processability, and no residual color contamination.

[0002]

2. Description of the Related Art In recent years, silver halide photographic light-sensitive materials have a tendency to be rapidly processed, and therefore, silver chloride and silver bromide emulsions, which have faster developability and fixability than silver iodobromide emulsions, are used. It is getting attention. However, since silver chloride and silver chlorobromide emulsions are inferior in sensitivity to silver iodobromide emulsions, development of an efficient sensitizing method is desired.

As one of the efficient sensitizing methods for a silver chlorobromide emulsion, it is possible to enhance the spectral sensitizing property by adding an increasing amount of a sensitizing dye. However, while the addition of such a sensitizing dye in an increased amount gives a sensitizing property, increasing the amount of the dye tends to cause dye stain on the film after the treatment (so-called residual color stain). Remarkably easy to occur due to shortened rapid processing.

Various proposals have heretofore been made in order to eliminate such dye contamination. For example, a highly water-soluble spectral sensitizing dye is used, the amount of gelatin (binder) in the emulsion layer is reduced, and further, it is hardened. Methods such as loosening the film thickness to increase the film swelling property are known.

However, further improvement was required in order to obtain a silver halide photographic light-sensitive material having suitability for rapid processing, sufficient sensitization and free from residual color contamination.

[0006]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide photographic light-sensitive material having high sensitivity, excellent rapid processability, and free from residual color contamination.

[0007]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
It is achieved by:

In a silver halide photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one surface of a support, the silver halide emulsion in at least one of the silver halide emulsion layers has the following (1) , (2), (3) and (4) satisfying the conditions of silver halide grains containing a silver halide photographic light-sensitive material.

(1) The average silver chloride content is 10 mol% or more. (2) The silver halide grain surface contains 1 mol% or more and less than 13 mol% silver iodide. (3) Silver halide grain Contains tabular grains having an average aspect ratio of 3 or more. (4) The spectral sensitizing dye adsorbed on the silver halide grains is 90% or less of the grain surface area.

The present invention will be described in detail below.

The silver halide photographic light-sensitive material of the present invention has at least one photosensitive silver halide emulsion layer on at least one side of the support, and the silver halide emulsion layer is one of the supports. May be a single-sided light-sensitive material having a silver halide emulsion layer only on one side and the other side is, for example, a non-photosensitive backing layer. It may be a double-sided light-sensitive material having a silver emulsion layer.

The silver halide grains according to the present invention have an average silver chloride content of 10 mol% or more, preferably in the range of 30 mol% to 60 mol% and the rest are composed of silver bromide and silver iodide. It is a silver halide grain.

The silver halide grains account for 1 mol% on the grain surface.
As described above, it contains less than 13 mol% of silver iodide. The silver iodide content is preferably 4 mol% to 12 mol%, more preferably 8 mol% to 11 mol%.

The term "grain surface" as used herein means a region which X-rays penetrate from the surface of the silver halide grain and reach when the average silver iodide content on the surface of the silver halide grain is measured by the XPS method. It refers to the silver halide phase, and usually contains about 50 of the outermost layers that make up the silver halide grains, including the grain surface.
Corresponds to the area of Å.

The average silver iodide content on the grain surface of the silver halide grain in the present invention is a value measured by the XPS method in a state in which a sample prepared from the silver halide grain is cooled to -110 ° C or lower. is there.

Conventionally, the XPS method known in the art is usually measured at room temperature, but according to the study of the present inventors, the XPS method at room temperature was used to measure the average iodide near the outermost surface of silver halide grains. When the silver content was measured, the silver halide sample was largely destroyed by X-ray irradiation, and the obtained data cannot be said to accurately indicate the average silver iodide content near the outermost surface of the silver halide grain. There was found.

Particularly, a high silver iodide-containing phase and a low silver iodide-containing phase are localized in the outermost surface of silver halide grains having different silver halide compositions between the surface and the inside of the grain such as core / shell type grains. It has been revealed that the measured values of the silver halide grains are different from the true composition due to decomposition of the silver halide by X-ray irradiation and diffusion of halide (particularly iodine). According to a further study by the present inventors, in order to avoid such destruction of the sample and obtain the average silver iodide content in the vicinity of the outermost surface of the silver halide grain accurately and with good reproducibility, the sample should be destroyed. It has been found that the sample may be cooled to a temperature at which it rarely occurs, specifically, the sample may be cooled to −110 ° C. or lower.

The XPS method used here is as follows.

A 0.05% by weight aqueous solution of pronase (proteolytic enzyme) is added to the emulsion, and gelatin is decomposed while stirring at 45 ° C. for 30 minutes. Next, the emulsion particles are settled by centrifugation and the supernatant liquid is removed. Then, distilled water is added to disperse the emulsion particles in distilled water, and the mixture is centrifuged to remove the supernatant liquid. The emulsion particles are then redispersed in distilled water. This is thinly applied on a mirror-polished silicon wafer to obtain a measurement sample.

Using the sample thus prepared, XP
The average silver iodide content in the vicinity of the outermost surface of silver halide grains was measured by the S method. In order to prevent the sample from being destroyed by the above-mentioned X-ray irradiation, the sample was cooled to −110 ° C. to −120 ° C. using liquid nitrogen or liquid helium in the XPS measurement chamber. As the X-ray for the probe, Mg-Kα ray was irradiated at an X-ray source voltage of 13 KV and an X-ray source current of 40 mA.

Ag3d, Br3d and I3d3 / 2 electrons were detected to determine the surface halide composition near the outermost surface of the silver halide grain. The composition ratio was calculated by correcting the integrated intensity of each measured peak with a sensitivity factor (Sensitivity Factor), and calculating the average silver iodide content near the outermost surface of the silver halide grain from these intensity ratios.

The method for producing the silver halide grains according to the present invention is not particularly limited, but a typical method can be easily prepared by, for example, adding silver iodide fine grains. The silver iodide-containing layer in the vicinity of the grain surface can be formed at an appropriate time and may be formed before or after the precipitation of silver halide grains is completed. That is, any step from the growth step of silver halide grains to immediately before coating may be performed, but preferably before the chemical ripening step, more preferably before the desalting step, and a silver iodide-containing layer near the grain surface is formed. It is preferable that the time from the completion of the treatment to the chemical aging step is 10 minutes or more.

As a method for depositing silver iodide on the grain surface, a silver salt solution and a substantially iodide solution may be added onto the silver halide grains to deposit the silver iodide, or substantially silver iodide may be deposited. Alternatively, it can be deposited by adding an emulsion of silver iodobromide or silver iodochlorobromide and ripening.

The tabular silver halide grains used in the present invention are classified into twins crystallographically. Twins are silver halide crystals that have one or more twin planes in one grain.The morphology of twins is classified by Klein and Moiser in the article Photographie Correspondents (Photograp
hisches Korrespondenz) 99:99, 100: 57: 57.

The silver halide grains constituting the silver halide emulsion according to the present invention preferably have mainly two parallel twin planes, more preferably an even number, and particularly preferably two. It has a twin plane.
"Mainly having two or more parallel twin planes" means that the number of twin grains having two or more parallel twin planes is 50% or more, preferably 60% when counted from the large-sized grains. that's all,
Especially preferably, it is 70% or more.

The tabular silver halide grains used in the present invention have an average value (average aspect ratio) of the ratio of grain diameter / thickness (aspect ratio) of 3 or more. The tabular silver halide grains used in the present invention have an average aspect ratio of 3 or more, preferably 5 to 8.

The outer wall of the crystal of the tabular silver halide grain according to the present invention may be substantially composed of {111} planes or {100} planes. Further, it may have both a {111} plane and a {100} plane. In this case, 50% or more of the grain surface is a {111} plane, more preferably 60% to 90% is a {111} plane, and particularly preferably 70 to 95% is a {111} plane. It is preferable that the planes other than the {111} plane are mainly the {100} plane. This plane ratio is {111} plane and {100} plane in the adsorption of sensitizing dye.
Utilizing the difference in adsorption dependence with the surface [T. Tani, J. Imaging
Sci. 29,165 (1985)].

The tabular silver halide grains according to the present invention are
It may be polydisperse or monodisperse, but is preferably monodisperse. Specifically, (standard deviation of particle size / average particle size) x 100 = width of particle size distribution
When the width of the distribution is defined by the relative standard deviation (coefficient of variation) that can be represented 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 = width of thickness distribution
When the breadth of distribution is defined by (%), it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

Further, it is preferable that the distribution of the halogen content of individual grains in the tabular silver halide grain emulsion of the present invention is also small. Specifically, (standard deviation of halogen content / average halogen content) x 10
0 = 25% or less is preferable when the breadth of the halogen content is defined by the breadth (%) of the halogen content, more preferably 20% or less, and particularly preferably 15% or less.

In the present invention, the tabular silver halide grains are preferably hexagonal. Hexagonal tabular grains (hereinafter also referred to as hexagonal tabular grains) are the main planes ({11
The shape of (1} surface) is hexagonal, and the maximum adjacency ratio is 1.0
Say it is ~ 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, it is also preferable that the hexagonal tabular grains have rounded corners if the maximum adjacent side ratio is 1.0 to 2.0. 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. Further, it is also preferable that the tabular grains are more rounded and have a substantially circular shape.

In the present invention, each side forming the hexagon of the hexagonal tabular grain preferably has a half or more of a substantially straight line. In the present invention, the ratio of adjacent sides is 1.0 to
It is more preferably 1.5.

The halogenated grains according to the present invention may have dislocations. The rearrangement is, for example, JF Hamilton, Phot.Sc
i.Eng, 57 (1967), T.Shiozawa, J.Soc.Phot.Sci.Japa
n, 35, 213 (1972), and can be observed by a direct method using a transmission electron microscope at low temperature. That is, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on the mesh for electron microscope observation, and the sample to prevent damage (printout etc.) due to electron beam In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to pass through. Therefore, it is possible to observe more clearly using a high-voltage electron microscope (200 KV or more for particles having a thickness of 0.25 μm). .

The position and number of dislocations for each grain can be determined from the photograph of the grain obtained by such a method. The position of dislocation of the silver halide grain according to the present invention is 0.58 L from the center of the halide grain toward the outer surface.
It is desirable that it occurs in a region of up to 1.0 L, but more preferably it occurs in a region of 0.80 L to 0.98 L. The direction of the dislocation line is approximately from the center to the outer surface, but it often meanders.

In the present invention, the center of a silver halide grain means that silver halide microcrystals are dispersed in a methacrylic resin in the same manner as the method described in the summary of Inoue et al. When solidified and made into an ultrathin section with a microtome, and focusing on the section sample with the maximum cross-sectional area and the cross-sectional area of 90% or more than that, when drawing the minimum circumscribed circle to the cross section Is the center of the circle. In the present invention, the distance L from the center to the outer surface is defined as the distance between the center of the circle and the point intersecting the outer circumference of the particle when a straight line is drawn outward from the center of the circle.

Regarding the number of dislocations in the silver halide grains according to the present invention, 50% (number) of grains containing one or more dislocations
The presence of the above is desirable, and the higher the ratio (number) of the number of tabular grains having dislocation lines, the more preferable.

In the present invention, the particle size is the diameter when a projected image of particles is converted into a circular image having the same area. The projected area of a grain can be calculated from the sum of the grain areas. All of them can be obtained by observing, with an electron microscope, a silver halide crystal sample distributed on the sample stage to the extent that grains do not overlap.

The average projected area diameter of the tabular silver halide grains in the present invention is represented by the diameter corresponding to the circle of the projected area of the grains, and is preferably 0.30 μm or more, more preferably
It is 0.30 μm to 5 μm, more preferably 0.40 μm to 2 μm.

The particle size can be obtained by magnifying and projecting the particles with an electron microscope at a magnification of 10,000 to 70,000 and measuring the area of the projected image on the print.

The average particle diameter (φi) can be calculated by the following equation, where n is the number of measured particle diameters and ni is the frequency of particles having a particle diameter φi.

Average particle diameter (φi) = Σnidi / n (The number of measured particles is indiscriminately 1.000 or more.) The particle thickness can be obtained by observing the sample obliquely with an electron microscope. . The preferred thickness of the tabular grains of the present invention is 0.03-1.0 μm, more preferably
It is 0.05 to 0.5 μm.

The longest distance (a) between two or more parallel twin planes of the silver halide grain of the present invention and the grain thickness (b).
The ratio (b / a) is preferably 5 or more, and the ratio is preferably 50% (number) or more.

The twin plane distance (a) can be obtained as follows. That is, observation of the section using the above transmission electron microscope, with respect to the main plane, arbitrarily select 100 or more tabular silver halide grains showing a cross section cut substantially perpendicularly, for each grain ( It can be obtained by measuring a) and averaging them.

In the present invention, the average value of (a) is 0.008 μm.
Or more, but more preferably 0.010 μm or more,
It is 0.05 μm or less.

Further, in the present invention, it is necessary that (a) is within the above value range, and at the same time, its coefficient of variation is 35% or less, preferably 30% or less.

Further, in the present invention, the tabularity expressed by the following equation: A in consideration of factors of aspect ratio and grain thickness: A
= ECD / b ² is preferably 20 or more.

Here, ECD is the average projected diameter of tabular grains.
(b) is the thickness of the particles. Here, the average projected diameter represents the number average of diameters of circles having an area equal to the projected area of tabular grains.

The tabular silver halide grains used in the present invention are silver chlorobromide grains, and the average silver chloride content is 10 mol% or more, preferably 30 mol% or more and 60 mol% or less. The tabular silver halide grain used in the present invention may have a core / shell type structure having at least two layer structures having substantially different halogen compositions in the silver halide grain. The silver halide grains of the present invention are preferably grown by a method of precipitating silver halide on a seed crystal such as the method described in Examples of JP-A-60-138538.

Further, the silver halide grains of the present invention are cadmium, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt), and iron during the grain formation process and / or growth process. Add at least one metal ion selected from the group consisting of salt (including complex salt),
These metal elements can be contained in the inside of the grain and / or in the surface layer of the grain, and reduction sensitized nuclei can be imparted to the inside of the grain and / or the surface of the grain by placing in a suitable reducing atmosphere.

Further, the action of the reducing agent added at a desired time of particle formation can be improved by adding an oxidizing agent such as hydrogen peroxide (water) and its adduct, peroxo acid salt, ozone and I ₂ at a desired time. It is preferable to deactivate and suppress or stop the reducing property. The oxidizing agent may be added at any time from when the silver halide grains are formed to before the addition of the gold sensitizer in the chemical sensitization step (the chemical sensitizer when the gold sensitizer is used).

In the silver halide emulsion of the present invention, unnecessary water-soluble salts may be removed after the growth of silver halide grains,
It may be contained as it is. When removing salts, Research Disclosure (hereinafter abbreviated as RD) No.17643
It can be performed based on the method described in Section II.

The silver halide emulsion layer containing the group of grains in the present invention may contain other grains as long as the effects of the present invention are not impaired. The other particles referred to herein may be normal crystal particles such as cubes, tetradecahedrons and octahedra, and may be spherical particles or twin crystal particles. The higher the monodisperse claim of the twin crystal grains, the more preferable. The mixing ratio of the silver halide grains in the present invention to the above grains to be mixed is 90: 10 to 10: 10 by weight of silver.
It may be 90, more preferably 75:25 to 25:75.

Spectral sensitizing dyes are contained in the obtained silver halide grains in an amount of 90% or less of the grain surface area, preferably 70% to 70% of the surface area.
Silver halide grains adsorbed in the range of 80% are preferred.

In the present invention, 90% or less of the spectral sensitizing dye is adsorbed on the surface of the grain means that the amount of the dye adsorbing is relative to the saturated adsorption amount of the spectral sensitizing dye on the silver halide grain.
It means 90% or less, and practically means that the amount of the spectral sensitizing dye added to the saturated adsorption amount is 90% or less. It is preferably 70 to 80%. The amount of dye adsorbed can be determined by a method of centrifuging an emulsion adsorbing a dye to precipitate silver halide grains and colorimetrically determining the dye concentration of the solution.

Examples of the spectral sensitizing dye that can be adsorbed on the silver halide grains of the present invention include cyanine, carbocyanine, dicarbocyanine, complex cyanine, hemicyanine, styryl dye, merocyanine, complex merocyanine, and holopolar dye. The spectral sensitizing dyes used in 1. can be used alone or in combination.

Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these dyes, any of the nuclei normally used for cyanine dyes can be used as the basic heterocyclic nucleus. 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, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus. , Quinoline nucleus and so on. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye includes a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus as a nucleus having a ketomethylene structure. , 5 to 6-membered heterocyclic nuclei such as Rhodanine nucleus and thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used especially for the purpose of supersensitization.

To incorporate these sensitizing dyes in a silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, propanol, methyl cellosolve, 2,2,3,3. -It may be dissolved in a solvent such as tetrafluoropropanol or a mixed solvent and added to the emulsion. In addition, Japanese Patent Publication No. 44-23389, Japanese Patent Publication No. 44-27555,
As described in JP-B-57-22089 or the like, an acid or a base is allowed to coexist to form an aqueous solution, or a surfactant such as sodium dodecylbenzene sulfonate is allowed to coexist as described in U.S. Pat. An aqueous solution or colloidal dispersion may be added to the emulsion. Alternatively, the emulsion may be dissolved in a substantially water-immiscible solvent such as phenoxyethanol and then dispersed in water or a hydrophilic colloid to add to the emulsion. JP-A-53-102733,
As described in JP-A-58-105141, it may be directly dispersed in a hydrophilic colloid and the dispersion may be added to the emulsion.

When these compounds are added to the emulsion, a mixture thereof may be added or they may be added separately.

The silver halide emulsion used in the present invention is
Mixing conditions such as forward mixing method, back mixing method, double jet method, control double jet method, conversion method, particle preparation conditions such as core / shell method, etc. under solution conditions such as acidic method, ammonia method, neutral method, etc. It can be manufactured using these combination methods.

In order to remove soluble salts, the emulsion may be subjected to a Nudel washing method, a flocculation sedimentation method or the like, and a preferable washing method is, for example, an aromatic hydrocarbon containing a sulfo group described in JP-B-35-16086. Examples thereof include a method using a system aldehyde resin, and a desalting method using a polymer flocculant such as exemplified G-3 and G-8 described in JP-A-2-7037.

In the silver halide emulsion according to the present invention, various synthetic polymer compounds such as gelatin can be used as a binder.

As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin or gelatin derivative may be used. Examples of synthetic high molecular substances other than gelatin include cellulose derivatives such as hydroxyethyl cellulose,
A single or copolymer of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide and the like can be used.

The silver halide emulsion according to the present invention can be chemically sensitized. As the chemical sensitization method, sulfur sensitization, reduction sensitization, noble metal sensitization and combination sensitization methods thereof may be used. Specifically, allyl thiocarbamide, thiourea,
Sulfur sensitizers such as thiosulfate, thioether and cystine, precious metal sensitizers such as potassium chlorosulphate, aura thiosulfate and potassium chloroparadate, reduction sensitizers such as tin chloride, phenylhydrazide and redatactone. it can.

The emulsion according to the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research
Disclosure (RD) No.17643 (December 1978), N
o.18716 (November 1979) and No.308119 (December 1989)
Month). Examples of the support that can be used in the light-sensitive material of the present invention include those described in (RD) No. 117643, page 28 and (RD) No. 18716, page 647, left column. A suitable support is a plastic film or the like, and the surface of these supports may generally be provided with an undercoat layer, corona discharge, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer.
Then, the emulsion according to the present invention can be coated on one side or both sides of the support thus treated. The silver halide photographic light-sensitive material of the present invention may be optionally provided with an antihalation layer, an intermediate layer, a filter layer and the like.

The present invention is applicable to all silver halide photographic light-sensitive materials, but is particularly suitable for high-sensitivity black-and-white light-sensitive materials.

When the present invention is applied to medical X-ray radiography, for example, a fluorescent intensifying screen containing a phosphor that emits near-ultraviolet light or visible light by exposure to penetrating radiation as a main component is used. It is desirable that the emulsion is adhered to both sides of a light-sensitive material prepared by coating the emulsion of the present invention on both sides and exposed.

The penetrating radiation as used herein is an electromagnetic wave of high energy and means X-rays and gamma rays. Further, the fluorescent intensifying screen refers to, for example, an intensifying screen mainly containing tungsten calcium as a fluorescent component or a fluorescent intensifying screen mainly containing a rare earth compound activated by terbium. As the fluorescent intensifying screen, it is possible to use one in which the fluorescent component is uniformly coated on the support, or one coated in a cylindrical or conical shape.

When using a light-sensitive material having particularly low sensitivity, `9
2 Like the German Karman Karlsruhe Nuclear resarch microstructure intensifying screen presented at RSNA session 868C, the fluorescent component is increased in thickness and applied in a conical shape to simultaneously increase the sensitivity of the intensifying screen. It is preferable to use a fluorescent intensifying screen with reduced quantum mottle and improved graininess.

The processing of the light-sensitive material of the present invention is carried out, for example, in the above (R
D) No.17643 XX to XXI, pages 29 to 30 or 308119 XX
~ XXI, treatment with a treatment solution as described on pages 1011-1010 may be performed.

Dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-aminophenol) and the like are used alone as a developer in black and white photographic processing. Alternatively, they can be used in combination.
Known additives such as preservatives, alkaline agents, pH buffers, antifoggants, hardeners, development accelerators,
Surfactant, antifoaming agent, color tone agent, water softener, dissolution aid,
A viscosity imparting agent or the like can be used as necessary.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. Other preservatives, pH adjusters,
It may contain a water softener and the like.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, a slide hopper coating method, or the like can be used. For details, see (RD) No.17643, Volume 176, pp. 27-28, `` Coa
The method described in the section "Ting procedure" can be used.

[0075]

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

Example 1 (Preparation of Emulsion Em-1) Distilled water containing 90 g of high methionine gelatin (containing 59.7 micromoles of methionine per 1 g of gelatin) in a reactor equipped with a stirrer, 6000 g, 0.5M
CaCl ₂ .2H ₂ O and 9.3 g of NaBr were charged. PH at 40 ℃
Adjusted to 5.1 and kept the value of the whole precipitation intact by addition of NaOH or HNO ₃ . It was added AgNO ₃ solution of 0.5M over 4 minutes at a rate consuming 1.6% of the total amount of Ag used. The 0.5M AgNO ₃ solution was then added over an additional 55 minutes.

Next, the addition rate was linearly accelerated over another 55 minutes (9.32 times from the start to the end), during which Ag was added.
Consumed the remaining 98.4%. 4 minutes, 16 minutes, and
At 36 minutes, 30 cc of 37 mM adenine solution was added. At 10 minutes, 3.78 g of 3M CaCl ₂ solution was added to the precipitate. Adenine and CaCl
During the addition of the _two solutions, the AgNO ₃ inflow was stopped for 1 minute and the additives were mixed uniformly. A total of 1.44M Ag was precipitated. By this method, a tabular silver chlorobromide emulsion (Em-1) having an average silver chloride content of 50 mol% and a grain size of 0.4 μm, a projected area diameter of 1.2 μm and a coefficient of variation of 0.25 and an aspect ratio of 4 was prepared.

(Preparation of emulsion Em-2) Em-2 was obtained in the same manner as Em-1, except that the surface iodide was adjusted to the values shown in Table 1.

(Preparation of Emulsion Em-3) Em-3 was obtained in the same manner as Em-1, except that the surface iodide was adjusted to the values shown in Table 1.

(Preparation of emulsion Em-4) Em-4 was obtained in the same manner as Em-3 except that the average silver chloride content was adjusted to 30 mol%.

Next, after the above emulsions Em-1 to Em-4 were heated to 60 ° C., a spectral sensitizing dye was added as a dispersion in the form of solid fine particles so that the adsorption amount shown in Table 1 was obtained, and then adenine and ammonium thiocyanate were added. A mixed aqueous solution of salt, chloroauric acid and sodium thiosulfate and a dispersion liquid of triphenylphosphine selenide were added, and the mixture was aged for a total of 2 hours. At the end of aging, a predetermined amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

Sensitizing dye (A) 5,5'-dichloro-9-ethyl-3,
Anhydrous 3'-di- (3-sulfopropyl) -oxacarbocyanine sodium salt Sensitizing dye (B) 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'- Anhydrous Di- (4-sulfobutyl) -benzimidazolocarbocyanine-sodium salt The above additives and their addition amounts (per mol of AgX) are shown below.

Sensitizing dye (A) 430 mg Sensitizing dye (B) 4.3 mg Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.4 mg 4-Hydroxy-6-methyl-1 A solid dispersion of 3,3,3a, 7-tetrazaindene (TAI) 500 mg sensitizing dye was prepared by a method similar to the method described in Japanese Patent Application No. 4-99437. That is, a predetermined amount of dye is added to water whose temperature has been adjusted to 27 ° C in advance, and a high-speed stirrer (dissolver) is added.
Obtained by stirring at 3.500 rpm for 30-120 minutes.

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 completely dissolved by stirring. On the other hand, 3.8 kg of photographic gelatin is used with 38 kg of pure water.
Was dissolved in the solution, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Then, these two liquids were mixed and dispersed at 50 ° C. for 30 minutes at a peripheral speed of the dispersing blade of 40 m / sec by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm. After that, rapidly stirring under reduced pressure until the residual concentration of ethyl acetate becomes 0.3 wt% or less,
The ethyl acetate was removed. Then, this dispersion was diluted with pure water to obtain 80 kg. A part of the thus obtained dispersion was collected and used in the above experiment.

(Preparation of Sample) The following coating solutions were prepared. The addition amount is indicated by the addition amount per 1 m ^{2 on} one side of the silver halide photographic light-sensitive material.

First layer (transverse light shielding layer) Solid fine particle dispersion dye (AH) 180 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 5 mg Compound (I) 5 mg 2,4-dichloro-6-hydroxy-1,3,5 -Triazine sodium salt 5 mg Colloidal silica (average particle size 0.014 μm) 10 mg Second layer (emulsion layer) The following various additives were added to each emulsion obtained above.

Compound (G) 0.5 mg 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg t-butyl-catechol 130 mg polyvinylpyrrolidone (molecular weight 10,000) 35 mg styrene-maleic anhydride Polymer 80 mg Sodium polystyrene sulfonate 80 mg Trimethylolpropane 350 mg Diethylene glycol 50 mg Nitrophenyl-triphenyl-phosphonium chloride 20 mg 1,3-Dihydroxybenzene-4-ammonium ammonium 500 mg 2-Mercaptobenzimidazole-5-sodium sulfonate 5 mg Compound ( H) 0.5 mg nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg Compound (M) 5 mg Compound (N) 5 mg Colloidal silica 0.5 g Latex (L) 0.2 g Dextrin (average molecular weight 1000) 0.2 g (where the second layer volume with gelatin was coated was adjusted to 1.0 g / m ^2.) the third layer (protective layer) gelatin 0.8g polymerase Matte agent consisting of lumethacrylate 50 mg (area average particle size 7.0 μm) Formaldehyde 20 mg 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg Bis-vinylsulfonylmethyl ether 36 mg Latex (L) 0.2 g Polyacrylamide (average molecular weight 10000) 0.1 g Sodium polyacrylate 30 mg Compound (SI) 20 mg Compound (I) 12 mg Compound (J) 2 mg Compound (S-1) 7 mg Compound (K) 15 mg Compound (O) 50 mg Compound (S- 2) 5mg C ₉ F ₁₉ O (CH ₂ CH ₂ O) ₁₁ H 3mg C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₁₅ H 2mg C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ SO ₃ Na 1 mg

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Simultaneous multilayer coating of the above coating solution on both sides of a blue-colored undercoated polyethylene terephthalate support having a thickness of 175 μm in the order of a transverse light-shielding layer, an emulsion layer and an emulsion protective layer from the support side, Samples dried and shown in Table 1
No. 1 to 10 were created. The coated silver amount is for one side
It was adjusted to be 1.6 g / m ² .

<Evaluation of Sensitivity> The obtained sample was sandwiched between X-ray intensifying screens KO-250, and X was passed through a penetrometer B type.
After irradiating with rays, using roller transfer type automatic processor SRX-501, SR-DF treatment liquid (both manufactured by Konica Corporation) at 35 ° C for 4
It was treated for 5 seconds.

The reciprocal of the amount of exposure energy required to give a density of base density + fog density + 1.0 for the obtained sample was determined and expressed as a relative value when the sensitivity of Sample No. 1 was 100.

<Evaluation of Color Remaining> An unexposed sample was subjected to SRX-503.
Using an SR-DF processing solution with an automatic processor, the processing was carried out at 35 ° C. for 45 seconds, and the following 5-level visual evaluation was carried out for residual color contamination.

⊚: No residual color contamination ○: Slightly present Δ: Residual color contamination is acceptable for practical use ×: Residual color contamination is slightly high but the practical range is limited XX: Large amount of residual color contamination is not acceptable for practical use Is shown in Table 1 below.

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[Table 1]

As is clear from Table 1, the samples of the present invention are:
It can be seen that the photosensitive material has high sensitivity even in rapid processing and has little residual color contamination.

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As demonstrated by the examples, according to the present invention, it is possible to provide a silver halide photographic light-sensitive material which has high sensitivity even in rapid processing and has little residual color contamination.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one surface of a support, wherein the silver halide emulsion in at least one of the silver halide emulsion layers is A silver halide photographic light-sensitive material comprising silver halide grains satisfying the conditions 1), (2), (3) and (4). (1) The average silver chloride content is 10 mol% or more. (2) The silver halide grain surface contains 1 mol% or more and less than 13 mol% silver iodide. (3) The average aspect of silver halide grains. It contains tabular grains with a ratio of 3 or more. (4) The spectral sensitizing dye adsorbed on silver halide grains is 90% or less of the grain surface area.