JP3401696B2 - Silver halide photographic material and processing method thereof - Google Patents

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 containing tabular silver halide grains, more specifically a medical silver halide photographic light-sensitive material containing tabular silver halide grains and a processing method thereof. Regarding

[0002]

2. Description of the Related Art In recent years, with regard to the development processing of silver halide photographic light-sensitive materials, it has been increasingly desired to reduce the processing time and the processing waste liquid. For example, in the medical field, regular health checkups,
The spread of medical checkups and the number of examinations including diagnosis in general medical care have increased rapidly, which has led to an increase in the number of X-ray photographs taken, and there is an ever-increasing demand for further rapid development processing and reduction of processing waste liquid. It is rising.

However, in order to speed up the processing, it is necessary to shorten the processing time of each processing step such as developing, fixing, washing with water, and drying, and the load on each step increases.

For example, if the developing time is simply shortened, the image density of the conventional photosensitive material is lowered, that is, the sensitivity is lowered and the gradation is deteriorated. Further, if the fixing time is shortened, the fixing of silver halide becomes incomplete, which causes deterioration of image quality. Therefore,
In order to solve such a problem, it is necessary to accelerate the developing speed and the fixing speed.

In order to accelerate the developing speed and fixing speed,
It is preferable to reduce the silver iodide content of the silver halide grains. However, it is generally known that when the average silver iodide content is lowered, the intrinsic sensitivity of silver halide is lowered and the storability of a raw film under high humidity is deteriorated. Further, when the silver iodide content on the surface of the silver halide grain is lowered, the adsorption property of the spectral sensitizing dye is deteriorated and, as a result, the spectral sensitivity is lowered, or the silver iodide content inside the silver halide grain is decreased. It is also known that when the value is decreased, the pressure resistance deteriorates and scratches easily occur.

On the other hand, regarding the processing of silver halide photographic light-sensitive materials, it is essential to reduce the replenishment amount of the processing solution from the viewpoint of environmental protection and cost, and it is particularly desirable that there is no pollution due to the processing waste solution.

There has been a demand for the development of a new technique which provides high sensitivity, low fog photographic performance by rapid processing with a low replenishing amount, and has improved pressure resistance and storability over time.

[0008]

SUMMARY OF THE INVENTION Therefore, a first object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity and low fog photographic performance by rapid processing with a low replenishing amount. . In addition to the above, a second object of the present invention is to provide a silver halide photographic light-sensitive material excellent in pressure resistance (scratch resistance) of the film and excellent in storability under high humidity, and a processing method thereof. Is.

[0009]

As a result of intensive studies, the present inventor has found that the object of the present invention can be achieved by the following constitution.

(1) In a silver halide photographic light-sensitive material having a photosensitive silver halide emulsion layer on a support, 50% or more of the total projected area of silver halide grains contained in the silver halide emulsion layer is 50% or more. A silver halide photographic light-sensitive material characterized by satisfying the following conditions 1 to 3 and containing a palladium compound in the silver halide emulsion layer. 1. 1. A silver halide grain having a silver chloride content of 50 mol% or more and 100 mol% or less. Main plane is (100) plane and aspect ratio is 2 or more, 15
The following tabular grains 3. The edge ratio (long-side edge length / short-side edge length) of silver halide grains is 1 to 2 (2) The above silver halide grains are chemically sensitized in the presence of selenium and / or tellurium compounds. The silver halide photographic light-sensitive material as described in (1) above. (3) Total processing time (Dry to Dry) is 10 seconds to
The silver halide according to the item (1) or (2), which is processed in 45 seconds and the replenishment amounts of the developing solution and the fixing solution are 30 ml / m ² or more and 200 ml / m ² or less, respectively. Processing method of photographic light-sensitive material.

The present invention will be described in detail below.

The silver halide photographic light-sensitive material of the present invention may have a silver halide emulsion layer on both sides of the support, or may have a silver halide emulsion layer on only one side.

In the present invention, the silver halide grains contained in the emulsion layer have a total projected area of 50% or more and 100% or more and a silver chloride content of 50 mol% or more and 100 mol% or less. And the main plane is (100)
It is composed of tabular grains having an aspect ratio of 2 or more and 15 or less. (Hereinafter, it may be abbreviated as the tabular silver halide grain of the present invention). Here, the tabular silver halide grain means a grain having two parallel main planes facing each other, and one having an average ratio of grain size to grain thickness (hereinafter referred to as aspect ratio) of more than 2. Say. Here, the grain size means an average projected area diameter (hereinafter referred to as a grain size), and a diameter corresponding to a circle of a projected area of the tabular silver halide grains (a diameter of a circle having the same projected area as the silver halide grains). ), And the thickness means the distance between two parallel principal planes forming a tabular silver halide grain.

The aspect ratio of the tabular silver halide grains of the present invention is 2 or more, preferably 2 or more and 15 or less, and particularly preferably 5 or more and 10 or less.

In the present invention, 50% or more, preferably 70% or more of the total projected area of silver halide grains contained in the emulsion layer.
% Or more, more preferably 90% or more is composed of tabular silver halide grains having a (100) plane as a main plane, and the grains have a silver chloride content of 50 mol% or more, preferably 70 mol% or more, and further preferably Is 90 to 100 mol% of silver halide grains.

In the present invention, the main plane of the tabular silver halide grain is a right-angled parallelogram or a right-angled parallelogram with rounded corners. The edge ratio (long side edge length / short side edge length) of the right-angled parallelogram is 1 to 2, preferably 1 to 1.5, and more preferably 1 to 1.
It is 2. When the corner is rounded, the length of the side is represented by the distance between the straight line portion of the side and the intersection with a line obtained by extending the straight line portion of the adjacent side.

The average grain size of the tabular silver halide grains of the present invention is preferably 0.15 to 5.0 μm,
The thickness is more preferably 4 to 3.0 μm, most preferably 0.4 to 2.0 μm.

The average thickness of the tabular silver halide grains of the present invention is preferably 0.01 to 1.0 μm, more preferably 0.02 to 0.40 μm, still more preferably 0.02 to 0. It is 30 μm.

Particle size and thickness can be optimized to optimize sensitivity and other photographic properties. Optimum particle size, optimum depending on sensitivity and other factors that make up the photosensitive material (thickness of hydrophilic colloid layer, hardness, chemical ripening condition, set sensitivity of photosensitive material, silver coating amount, etc.) The thickness is 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 = width of grain size 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.

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

The content of silver iodide in the tabular silver halide grains of the present invention is preferably 3.0 mol% or less as an average silver iodide content in the whole silver halide grains, but 1.0 mol%
The following are more preferable.

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 (E
electron Probe Micro Analysis
(Zer 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, an X-ray analysis is performed by irradiating with an electron beam, and electron beam excitation is performed. Elemental analysis of extremely minute portions can be performed. By this method, the silver halide composition of each grain can be determined by obtaining the characteristic X-ray intensity of silver and iodide emitted from each grain. 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 contained in the silver halide emulsion of the present invention preferably have a more uniform iodide content between grains. When the distribution of the iodide content between grains was measured by the EPMA method, the relative standard deviation was 35.
% Or less, and more preferably 20% or less.

In the present invention, the tabular silver halide grains contain silver iodide, but it is preferable that the tabular silver halide grains are contained at least inside. In the case of the inside, it is more preferable that it exists at least in the center. Further, it is also preferable that it exists on the outermost surface.

In the present invention, the halogen composition distribution inside the silver halide grain is obtained by pretreating the grain into an ultrathin section 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. It is determined by observing and spot analysis with a transmission electron microscope equipped with an energy dispersive X-ray analyzer while cooling this section with liquid nitrogen, and performing quantitative calculation.
(Inoue, Nagasawa: Proceedings of the 62nd Annual Meeting of the Photographic Society of Japan, p62) In the present invention, the silver iodide content on the outermost surface of the tabular silver halide grains means the XPS method (X-ray Pho).
toelectron Spectroscopy: X
It refers to the silver iodide content of a portion up to a depth of 50Å analyzed by line photoelectron spectroscopy, and can be determined as follows.

The sample was cooled to -110 ° C. or lower in an ultrahigh vacuum of 1 × 10 ^-8 torr or less, and MgKα was irradiated as an X-ray for a probe with an X-ray source voltage of 15 kV and an X-ray source current of 40 mA to obtain Ag3d5 /. 2, Br3d, I3d 3/2 electrons are measured. The integrated intensity of the measured peak is corrected by a sensitivity factor (Sensitivity Factor), and the halide composition of the outermost surface is determined from the intensity ratio of these.

The purpose of cooling the sample is to eliminate the measurement error caused by the destruction of the sample (decomposition of silver halide and diffusion of halide [especially iodine]) due to X-ray irradiation at room temperature and to enhance the measurement accuracy. By cooling to -110 ° C, sample destruction can be suppressed to a level that does not hinder measurement.

The tabular silver halide grains of the present invention may have dislocations. The dislocation is described in, for example, J. F. Hamilt
on, Photo. Sci. Eng, 57 (1967)
, T. Shiozawa, J .; Soc. Photo. S
ci. It can be observed by a direct method using a transmission electron microscope at low temperature described in Japan, 35, 213 (1972). That is, the silver halide grains, which were taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion, were placed on a mesh for electron microscope observation, and the sample was taken 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 an electron beam to pass therethrough. Therefore, a high voltage type (200 kV or more for particles having a thickness of 0.25 μ)
It can be observed more clearly by using the electron microscope.

The tabular silver halide grains of the present invention can be prepared by the method described in US Pat. No. 5,320,938. That is, it is preferable to nucleate with low pCl in the presence of iodide ions under the condition that the (100) plane is easily formed. After nucleation, Ostwald ripening and / or growth can be performed to obtain tabular silver halide grains having a desired grain size and distribution. For example, first, a silver salt solution, a halide solution containing iodine ions, and a protective colloid solution are added to the first container to form nuclei, and after the nucleation, the mixed solution is transferred to the second container and grown there. The method is preferably used.

At that time, the growth may be temporarily stopped on the way, and the seed grains may be used to grow silver halide on the seed grains.

Specifically, an aqueous solution containing a protective colloid and seed particles may be preliminarily present in a reaction vessel, and silver ions, halogen ions, or silver halide fine particles may be supplied as necessary to grow the seed particles. .

To prepare the tabular silver halide grains of the present invention, pCl of the protective colloid solution is preferably in the range of 0.5 to 3.5, more preferably 1.0 to 3.0, Most preferred is 1.5 to 2.5.

In the preparation of the tabular silver halide grains of the present invention, nucleation is started at the time when the silver salt solution is added to the protective colloid solution, and iodide ions are added simultaneously with the silver salt solution or the silver salt solution. It is preferable to add it prior to the solution, most preferably when it is added prior to the silver salt solution.

In the preparation of tabular silver halide grains of the present invention, iodine can be introduced up to the solid solution limit of silver iodide and silver chloride, but iodine ions in the protective colloid solution at the start of nucleation are contained. The concentration is preferably 10 mol% or less,
It is more preferably 0.01 mol% or more and 10 mol% or less, and most preferably 0.05 mol% or more and 10 mol% or less. In the production of tabular silver halide grains of the present invention, the addition time of the silver salt solution during nucleation is 5 seconds or more 1
Less than a minute is preferred. Further, it is preferable that both the silver salt solution and the halide solution be added at the time of nucleation. It is particularly preferable to add iodine ions.

The bromine ion in the protective colloid solution at the time of nucleation may be present as long as chlorine ion is present in an amount of 50 mol% or more.

In the present invention, the silver chloride content of the nucleus is 50.
It is at least mol%, preferably at least 70 mol%, more preferably at least 90 mol%.

The pH during nucleation is preferably 2-8. The temperature is preferably 30 to 90 ° C, more preferably 35 to 70 ° C. The amount of silver added during nucleation is preferably 0.1 mol% to 10 mol% of the total silver amount. Further, in the preparation of the tabular silver halide grains of the present invention, a known silver halide solvent such as ammonia, thioether or thiourea can be present.

In the preparation of the tabular silver halide grains of the present invention, a silver salt solution and a halide solution are added at the time of growth by the double jet method, and the rate of addition is such that new nucleation does not occur depending on the growth of grains, Further, particles having a desired particle size and distribution can be obtained by a method in which the size distribution is not broadened due to Ostwald ripening, that is, a method of gradually changing it within a range of 30 to 100% of the speed at which new nuclei are generated. Another condition for further growth is the Photographic Society of Japan Showa 5
A method of growing by adding silver halide fine particles, dissolving and recrystallizing is also preferably used, as described in 88th Annual Meeting Summary. Particularly, silver iodide fine particles, silver bromide fine particles, silver iodobromide fine particles, and silver chloride fine particles are preferably used.

The tabular silver halide grains of the present invention may be so-called halogen conversion type grains. The amount of halogen conversion is preferably 0.2 mol% to 0.5 mol% with respect to the amount of silver, and the conversion time may be physical ripening or after physical ripening. As a method for halogen conversion, 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 halogen conversion is usually added. At this time, the fine particle size is preferably 0.2 μm or less, more preferably 0.1 μm or less.
It is 02 to 0.1 μm.

When the outermost surface of the tabular silver halide grain of the present invention contains silver iodide and / or silver bromide, the method is as follows: a silver nitrate solution and iodine are added to an emulsion containing the tabular grain as a base. Method of simultaneously adding a solution containing ions and / or bromide ions, a method of adding fine silver halide grains such as silver iodide, silver bromide, silver iodobromide or silver chloroiodobromide, potassium iodide or iodide A method of adding a mixture of potassium bromide and potassium bromide or the like can be applied. Among these, the method of adding fine silver halide grains is preferable.
Particularly preferable is a method of adding fine silver iodide grains, fine silver bromide grains, and fine silver iodobromide grains.

The time for adjusting the content of silver iodide and / or silver bromide on the outermost surface is from the final step of the production step of the silver halide crystal to the chemical ripening step, and immediately before the coating of the silver halide emulsion. It can be selected before the completion of the liquid preparation step, but it is preferable to adjust it before 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 solution of the present invention when the silver halide fine grains are added is preferably in the range of 30 to 80 ° C.
Furthermore, 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 grains to be added are partially or wholly disappeared after the addition and immediately before coating. More preferable condition is 20% of the added silver halide fine grains. The above is the disappearance just before coating.

When silver bromide is added to the outermost surface of the tabular silver halide grains of the present invention, the method is to add a silver nitrate solution and a bromide ion-containing solution to the base tabular grain-containing emulsion. A method of simultaneously adding, a method of adding fine silver halide grains of silver bromide and the like can be applied. Among these, the method of adding fine silver halide grains is preferable. Particularly preferred is the addition of fine silver bromide particles.
At this time, iodine and / or chlorine may be contained if necessary. Particularly in the case of iodine, an organic compound that releases iodine ions may be used.

The vicinity of the surface in the present invention means a position within 1/5 of the particle size measured from the outermost surface of the particle. It is more preferably within 1/7.

As the halogen composition, the silver bromide content localized near the surface is preferably 20 mol% or more, more preferably 50 mol% or more. The silver iodide content localized near the surface is preferably 5 mol% or less, more preferably 1.0 mol% or less.

The term "vicinity near the apex" as used in the present invention means that one side has a length of about 1/3 of the diameter of a circle having the same area as the projected area of the silver halide grain in the present invention, and the apex of the grain is one. This is within the area of tabular grains that form one corner. As a method of forming a desired localized phase in the vicinity of the apex, a method of adsorbing a compound that selectively adsorbs on the (100) plane on the surface of the grain to suppress or prevent the initiation of halogen substitution can be preferably used. Examples of such compounds include cyanine dyes, merocyanine dyes, mercaptoazoles, and purines.

When a localized phase is formed near the apex, pressure desensitization is likely to occur, but this is not recognized in the present invention. (1
00) is considered to be peculiar to tabular grains having a main plane, but this could not be expected easily at first.

In producing the tabular silver halide grains of the present invention, the stirring conditions during production are extremely important. As the stirring device, the device shown in JP-A-62-160128, in which the additive liquid nozzle is installed in the liquid near the mother liquor suction port of the stirrer, is particularly preferably used. At this time, the stirring rotation speed is preferably 100 to 1200 rpm.

The tabular silver halide grain of the present invention contains a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium salt (a complex salt) in the step of forming and / or growing the grain. It is preferable to add a metal ion by using at least one selected from the group consisting of the above) and an iron salt (including a complex salt) so that these metal elements are contained 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, a thiocyanate compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) is added in an amount of 1 × 10 ⁻³ mol or more and 3 × 10 ³ mol / mol of silver.
It is preferable to add ^-2 mol or less.

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 (having a molecular weight of 20,000 to 10).
10,000), modified gelatin such as phthalated gelatin is used. Other hydrophilic colloids can also be used. Specifically, Research Disclosure (Resea)
rch Disclosure, hereinafter abbreviated as RD. ) Volume 176 No. 17643 (December 1978).

In the preparation of the tabular silver halide grains of the present invention, unnecessary soluble salts may be removed during the growth of the silver halide grains, or may be contained therein. When removing the salts, RD Vol. 176 No.
It can be performed based on the method described in 17643.

The tabular silver halide grains of the present invention can be chemically sensitized. There are no particular restrictions on the conditions of the chemical ripening, that is, the steps of chemical sensitization, such as pH, pAg, temperature, time, etc., and the conditions generally used in the art can be used.

The silver halide emulsion layer containing tabular silver halide grains of the present invention contains a palladium compound. Examples of the palladium compound used in the present invention include a divalent palladium salt or a tetravalent salt.

Preferred palladium compounds are (R)
_{It is represented by 2} Pd (X) ₂ or (R) ₂ Pd (X) ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents chlorine, bromine or iodine.

Specific examples of the palladium compound used in the present invention are shown below.

In the present invention, K ₂ PdCl ₄ , (N
H ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdB
r ₄ is preferred. As another palladium compound, for example, P
dCl ₂ , PdBr ₂ , PdI ₂ , Pd (NO ₃ ) ₂ , Pd
SO ₄ , Pd (OH) ₂ , PdO, Pd (NH ₃ ) ₄ C
l ₂ , Pd (NH ₃ ) ₄ (NO ₃ ) ₂ , PdCl ₂ (NH ₃ )
₂ , Pd (NO ₂ ) ₂ (NH ₃ ) ₂ , Na ₂ Pd (NO ₂ ) ₄ ,
K ₂ Pd (CN) ₄ , K ₂ Pd (NO ₂ ) ₂ SO ₄ , Pd (C
H ₃ COO) ₂ , Pd (C ₂ H ₅ COO) ₂ , PdCl ₂ (C
₆ H ₅ CN) ₂ , PdCl ₂ (C ₇ H ₈ ), PdCl ₂ (C ₇ H
₈ ), PdCl ₂ (pph ₃ ) ₂ , PdCl ₂ (C ₃ H ₆ ) ₂ ,
Pd (acac) ₂ , Pd (C ₁₇ H ₃₄ O) ₂ , Pd (CH
₂ COO) (PPh) ₂ or Pd (PPh) can also be used.

These palladium compounds are preferably water-soluble palladium compounds.

The position of addition of the palladium compound to the emulsion may be any of the steps for producing the silver halide emulsion of the present invention, but it is preferably after the grain forming step has been completed, particularly between the chemical sensitization step and the coating step. It is preferable to add it. After completion of the grain formation step means completion of addition of the silver salt solution in grain formation.

The palladium compound may be added all at once, or may be added in several portions. Moreover, you may add continuously within a predetermined time.

The silver halide emulsion may be ripened after addition of the palladium compound, or may be left at high temperature for a long time.

The silver halide emulsion of the present invention may be gold-sensitized with a gold compound.

As the gold sensitizer, a commonly used gold compound can be used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate and pyridyl trichlorogol.

The amount of the gold sensitizer used is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but usually it is 1 × 10 1 per mol of silver halide.
It is preferably ⁻⁴ mol to 1 × 10 ⁻⁹ mol. More preferably, it may be 1 × 10 ^-8 mol to 5 × 10 ^-4 mol.

[0065] The palladium compounds that can be used in combination with a gold compound in the present invention, per mol of silver halide 1 × 10 well ^-2 mol to 1 × 10 ^-7 mol, preferably 1 × 10 ^{- It is 2} mol to 1 × 10 ⁻⁵ mol.

In the present invention, the molar ratio of the gold compound to the palladium compound is preferably 1/5 or less, more preferably 1/12 to 1/1000 in order to exert the effect of the present invention. More preferable.

These palladium compounds are preferably used in combination with thiocyanate ions in an amount 5 times or more the molar amount of the palladium compound.

In the present invention, a selenium sensitization method using a selenium compound and a tellurium sensitization method using a tellurium compound can be used.

In the case of selenium sensitization, the selenium sensitizer used includes a wide variety of selenium compounds, and useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate), 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 selenourea, etc.), selenoketones (eg, selenacetone, selenacetophenone, etc.), selenamides ( For example selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.) ), And selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). A particularly preferred selenium sensitizer is
Selenoureas, selenoamides, and selenoketones,
It is a selenide.

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

The temperature of the chemical ripening using the selenium sensitizer is 4
The range of 0 to 90 ° C is preferable. More preferably 45 ° C
It is above 80 ° C. The pH is 4-9 and the pAg is 6
The range of -9.5 is preferable.

With respect to tellurium sensitizers and sensitization methods, a wide range of tellurium compounds are included. 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 (for example, 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 in accordance with the technique for using the selenium sensitizer.

In the present invention, the reduction sensitization method using a reducing substance may be used alone or in combination with other methods.
Preferred examples of reduction sensitizers include thiourea dioxide and ascorbic acid and their derivatives.
Other preferred reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

By adding a water-soluble silver salt, so-called silver ripening, which is a kind of reduction sensitization technique, is performed. PA during silver aging
1-6 is suitable for g, Preferably it is 2-4. The conditions such as temperature, pH and time are preferably within the above-mentioned reduction sensitization condition range.

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

The sensitizing dye is used during or during the steps of nucleation, growth, desalting and chemical sensitization of silver halide grains.
Alternatively, it may be added after any chemical sensitization.

The silver halide photographic light-sensitive material of the present invention is processed as described in RD-17643, XX to XXI, pages 29 to 30 or 308119, XX to XXI, pages 1011 to 1012. Treatment with the liquid may be performed.

Developers for black and white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-P-aminophenol). Etc. can be used alone or in combination. For the developer, known agents such as preservatives, alkaline agents, pH buffers, antifoggants, hardeners, development accelerators, surfactants, defoamers, toning agents, water softeners, and solubilizers are known. You may use an agent, a viscosity imparting agent, etc. as needed. A fixing agent such as thiosulfate or thiocyanate is used as the fixing solution, and a water-soluble aluminum salt such as aluminum sulfate or potassium alum may be contained as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener, and the like.

The silver halide photographic light-sensitive material of the present invention is processed by an automatic developing machine, and the steps from development to drying, that is, from the time when the tip of the light-sensitive material begins to be dipped in the developing solution, the tip is dried through the processing step. The time to exit the zone (so-called Dry to Dry time) is 10 seconds to 45
It is within seconds, preferably within 30 seconds.

The developing temperature is preferably 25 ° C to 50 ° C and 3
0 degreeC-40 degreeC is more preferable. Fixing temperature and time is about 2
6 seconds to 20 seconds is preferable at 0 ° C to 50 ° C, and 30 ° C to 40 ° C.
More preferably, the temperature is 6 seconds to 15 seconds. Drying time is usually 35
The drying zone provided with a hot air of -100 ° C, preferably 40-80 ° C, or a heating means by far infrared rays may be installed in the automatic processor.

The automatic developing machine is equipped with a mechanism for applying water or a rinse solution of an acidic solution having no fixing ability to the light-sensitive material during the steps of development, fixing and washing with water (Japanese Patent Laid-Open No. HEI 3).
No. 264953) may be used. Furthermore, a device capable of preparing a developing solution and a fixing solution may be incorporated.

In the processing method of the present invention, the replenishment amount of the developing solution and the fixing solution is 200 ml or less per 1 m ^{2 of} the film to be processed, and preferably 30 ml to 15 ml.
It is processed in the range of 0 ml. According to the present invention, deterioration of photographic performance was not observed even when the replenishment amount was low.

[0084]

EXAMPLES The present invention will be described below with reference to examples.

Example 1 <Preparation of Emulsion Em-1> Aqueous gelatin solution 12 was placed in a reaction vessel.
00 ml (pH 4.3 including 18 g of deionized alkali-treated gelatin having a methionine content of about 40 μmol / g)
Add the solution and keep the temperature at 43 ℃.
AgNO During l ₃ 20 g, the gelatin 0.8 g, HNO ₃
1N solution (containing 0.2 ml) and solution X-1 (in 100 ml, NaCl 6.9 g, the gelatin 0.8 g, NaOH 1)
N solution (containing 0.3 ml) was co-mixed at 12 ml at 24 ml / min.

After stirring for 2 minutes, Ag-2 solution (100 ml
2g of AgNO ₃ , 0.8g of the gelatin, 1 of HNO ₃
N solution (containing 0.2 ml) and solution X-2 (containing 1.4 g of KBr, 0.8 g of the gelatin, and 0.2 ml of 1N NaOH solution in 100 ml) were simultaneously mixed and added at a rate of 31 ml / min in an amount of 19 ml.

After stirring for 2 minutes, Ag-1 solution and X-1 solution were simultaneously mixed and added at 36 ml at 48 ml / min. NaC
20 ml of liquid 1 (100 ml contains 10 g of NaCl)
In addition, the pH was adjusted to 4.8 and the temperature was raised to 75 ° C. Two
After aging for 0 minutes, the temperature is lowered to 60 ° C and the pH is adjusted to 5.0.
Then, the silver potential is 100 mV and Ag-3 solution (100 m
AgNO _3, including the 10g) and X-3 solution in l (100m
(containing 3.6 g of NaCl in 1) was added by the controlled-double jet method. The flow rate at the start of addition is 7 ml
The flow rate of 0.1 ml / minute is accelerated and added at 1 minute / minute,
400 ml of Ag-3 solution was added.

Next, AgI grains having an average equivalent spherical diameter of 0.03 μm were added in an amount of 0.2% per mol of silver halide, and the amount was about 5.
It was aged for minutes to complete the halogen conversion.

Next, a precipitating agent was added, the temperature was lowered to 30 ° C., washing with settling water was performed, an aqueous gelatin solution was added, and the pH was adjusted to 6 at 38 ° C.
2, PCl was adjusted to 3.0. <Step (1)> A part of the emulsion was sampled and a transmission electron micrograph image (hereinafter abbreviated as TEM image) of a grain replica was observed. The shape characteristic values of the grain were as follows. .
(Total projected area of (100) plane tabular grains having an aspect ratio of 2 or more / sum of projected areas of all AgX grains) = a1 = 0.9
1.

(Average aspect ratio (average diameter / average thickness) of (100) plane tabular grains having an aspect ratio of 2 or more = a
2 = 4.5.

(Aspect ratio of 2 or more, edge ratio of 1-2.
0 (100) plane tabular grain total projected area / total AgX grain projected area) = a3 = 0.97.

The silver chloride content of Em-1 is 99 mol%.
Met.

<Preparation of Emulsion Em-2, 3> Emulsion Em-1
And the silver chloride content was 60 mol% (Em-2).
NaCl in solution X-3 to be 0 mol% (Em-3)
Em- except that KBr was replaced with KBr to change the silver potential.
Adjustment was made in the same manner as 1. The shape and characteristic values of the obtained silver halide grains of Em-2 and 3 were the same as those of Em-1.

<Preparation of Emulsion Em-4> In the preparation of Emulsion Em-1, grains having different shapes were prepared by appropriately changing the potential, pH and the addition flow rate. The shape and characteristic values of the obtained Em-4 silver halide grains are as follows.

A ₁ = 0.95 a ₂ = 9.5 a ₃ = 0.90 Next, the emulsions of Em-1 to 4 were optimally chemically sensitized with stirring at 56 ° C. First, a thiosulfonic acid compound (C ₂ H ₅ SO ₂ SNa) was added, thiourea dioxide was further added, and the mixture was held for 22 minutes to carry out reduction sensitization.

Next, 4-hydroxy-6-methyl-1,
An appropriate amount of 3,3a, 7-tetrazaindene and the following spectral sensitizing dye was added. In addition, calcium chloride was also added.
Subsequently, sodium thiosulfate and triphenylphosphine selenide were added, chloroauric acid and potassium thiocyanate were further added <step (2)>, and the mixture was cooled 40 minutes later. The amount of the additive added during the chemical sensitization was adjusted so as to be optimum.

The following additives were added to the obtained emulsion to prepare an emulsion coating solution. <Step (3)> At the same time, a protective layer coating solution described later was also prepared. PdCl ₂ .2NaCl was used as the palladium compound according to the present invention, and an appropriate amount was added to steps (1) to (3) as shown in Table 1.

Using both coating solutions, the amount of silver was 1.6 g and the amount of gelatin was 2.2 g per 1 m ^{2 on} one side using two slide hopper type coaters at a speed of 80 m / min on the support. Simultaneous coating on both sides, drying in 2 minutes 20 seconds, and sample No. 1 to 11 were obtained. The support used was glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%, and butyl methacrylate 40 wt%.
An aqueous dispersion obtained by diluting a copolymer latex composed of one kind of monomer with pure water to a concentration of 10 wt% was applied as an undercoating liquid to give a thickness of 175 μm (concentration: 0.
Polyethylene terephthalate base (for X-ray film colored blue in 15) was used.

(A) 5,5'-dichloro-9-ethyl-
3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt (B) 5,5'-di- (butoxycarbonyl) -1,
1'-Di-ethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt The following additives were added to each emulsion obtained. The addition amount is indicated by the amount per mol of silver halide.

1,1-Dimethylol-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 , 3-ammonium dihydroxybenzene-4-sulfonic acid _{2g C 4 H 9 OCH 2 CH} (OH) CH 2 n (CH 2 COOH) 2 1g 1- phenyl-5-mercaptotetrazole _{15mg n-C 4 H 9 OCH} 2 CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g Dextran (average molecular weight 39,000) 20.0 g

[0101]

[Chemical 1]

The protective layer liquid used was as follows. 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 μ) 1.1 g Silicon dioxide (area average particle size) Matting agent of 1.2μ) 0.5 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ O 7 mg C ₄ F ₉ SO ₃ K 2 mg C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0104]

[Chemical 2]

The treating agent and the treating process used in the present invention are as follows.

(Developer composition) Part A (for 12l finish) 450 g potassium hydroxide Potassium sulfite (50% solution) 2280g Diethylenetriamine pentaacetic acid 120g Sodium bicarbonate 132g 5-methylbenzotriazole 120mg 1-phenyl-5-mercapto Tetrazole 200mg Hydroquinone 340g Add water to make 5000 ml.

Part B (for 12l finish) Glacial acetic acid 170g Triethylene glycol 185g 1-phenyl-3-pyrazolidone 22 g 5-nitroindazole 0.4g starter Glacial acetic acid 120g 225 g of KBr Add water to make 1 liter.

(Fixing solution composition) Part A (for 18 l finishing) Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-dimethyl) Amino) -1-ethyl-5-mercaptotetrazole 18g Part B Aluminum acid 800g To prepare a developing solution, add parts A and B to about 5 liters of water at the same time, add water while stirring and dissolve to make 12 liters, and add glacial acetic acid. The pH was adjusted to 10.40 with. This is used as a development replenisher. 20 ml of the above starter was added to 1 liter of this developer replenisher to adjust the pH to 10.26 to prepare a working solution.

The fixing solution was prepared by adding parts A and B to approximately 5 liters of water at the same time, adding water while stirring and dissolving to make 18 liters, and adjusting the pH to 4.4 with sulfuric acid and NaOH, and fixing this. Use the liquid replenisher.

Processing Steps Processing Temperature (° C.) Processing Time (sec) Development + Crossover 35 7.8 Fixing + Crossover 33 5.4 Washing + Crossover 18 4.3 (Rinsing water 7 l / min. Supply) Squeeze 40 3. 1 Dry 50 4.4 Total 25.0 (sensitometric evaluation) The obtained sample was sandwiched between X-ray fluorescent intensifying screens KO-250 (manufactured by Konica Corporation), and a tube voltage of 90 was applied.
An X-ray was irradiated at kVp20mA for 0.05 seconds, and a sensitivity curve was created by the distance method, which was used as the sensitivity of a fresh sample. The sensitivities in the table are obtained as the reciprocal of the X-ray required to obtain the density of fog +1.0, and the sample No. 1 sensitivity is 10
The relative sensitivity is shown when 0 is set.

For the development, the automatic developing machine SRX503 (manufactured by Konica Corporation) was remodeled, and the dry to dry process was performed in the above steps.
ry (all treatment steps) was treated in 25 sec mode. However, each sample was run from a new solution so that the activity of the solution was in equilibrium. The amount of replenishment to the developing solution and the fixing solution during the running process was 100 ml / m ² .

<Evaluation of Scratch Resistance> Temperature 23 for each sample
It was left to stand for 1 hour at 42 ° C. and RH. Then, under this condition, using a commercially available nylon scrubbing brush, 100 g / cm ²
After rubbing under a load of, the undeveloped product was developed with the above-mentioned automatic processor and visually evaluated according to the following criteria. A: Almost no scratches B: No problem in practical use, but some scratches C: Scratches are noticeable and practically problematic D: Very many scratches, wide scratches, density Darker <Film storability under high humidity> Temperature 2 for each sample
The sensitivity was determined by the same method as above after leaving it for 1 hour under high humidity at 3 ° C. and 80% RH. The sensitivity difference (ΔS) between the obtained sensitivity and the above sensitometric sample was determined. That is, the smaller the value of ΔS, the better the storage stability under high humidity. The above results are shown in Table 1 below.

[0113]

[Table 1]

As is apparent from the table, the samples of the present invention had low fog, high sensitivity, and were comparable in terms of storability.
Furthermore, the scratch resistance was remarkably superior to that of the comparative sample.

[0115]

EFFECTS OF THE INVENTION According to the present invention, halogenation which provides high sensitivity, low fog photographic performance by rapid processing with low replenishment, and is excellent in pressure resistance (scratch resistance) and storage stability under high humidity over time. A silver photographic light-sensitive material and a processing method thereof were obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI G03C 5/26 G03C 5/26 5/31 5/31 5/395 5/395 (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/035 G03C 1/00 G03C 1/09 G03C 5/26 G03C 5/31 G03C 5/395

Claims (3)

(57) [Claims] 1. In a silver halide photographic light-sensitive material having a photosensitive silver halide emulsion layer on a support, 50% or more of the total projected area of silver halide grains contained in the silver halide emulsion layer is as follows. 1. A silver halide photographic light-sensitive material which satisfies the conditions 1 to 3 above and contains a palladium compound in the silver halide emulsion layer. 1. 1. A silver halide grain having a silver chloride content of 50 mol% or more and 100 mol% or less. Main plane is (100) plane and aspect ratio is 2 or more, 15
The following tabular grains 3. The edge ratio (long side edge length / short side edge length) of silver halide grains is 1 to 2 2. The silver halide grains are selenium and / or
Alternatively, the silver halide photographic light-sensitive material according to claim 1, which is chemically sensitized in the presence of a tellurium compound. 3. The total processing time (Dry to Dry) is 10 seconds to 45 seconds, and the replenishment amounts of the developing solution and the fixing solution are 30 ml / m ² or more and 200 ml / m ² or less, respectively. The method for processing a silver halide photographic light-sensitive material according to claim 1 or 2.