JPH10123642A - Silver halide photographic emulsion, its manufacture, silver halide photographic material using it, its processing method, and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly sensitive photographic material improved in pressure resistance and silver color tone and excellent in quick processing adaptability low replenishment processing adaptability by containing a flat silver halide grain containing thallium ion and spectrally sensitized. SOLUTION: Fifty percents of the whole projection area of silver halide grains in an emulsion is formed of flat silver halide grains, and the flat silver halide grain contains thallium ion. The content is 10<-9> -10<-1> per mole of the silver halide, preferably 10<-8> -10<-2> mole. In the formation of the silver halide grain under the presence of thallium ion, grain formation is performed under the presence of thallium ion in at least either one process when the grain forming process is formed of nucleus forming process, Ostwald aging process and crystal growing process. The flat silver halide grain is spectrally sensitized with a methine pigment or others. The pigment used herein include cyanine pigment, merocyanine pigment, and composite cyanine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic emulsion containing tabular silver halide grains, a method for producing the same, and a silver halide photographic material using the same and a processing method therefor.

[0002]

2. Description of the Related Art In recent years, with regard to the development processing of a silver halide photographic light-sensitive material, it has been increasingly desired to shorten the processing time.

For example, in the medical field, the number of X-ray films taken has increased due to the spread of periodic medical examinations, medical checkups, etc., and the increase in examinations including diagnosis in general medical care. Need to be notified. In recent years, angiographic imaging, intraoperative imaging, and the like have been increasing, but these essentially require the photograph to be viewed in a short time. To meet these demands, it is necessary to promote the automation of diagnosis (imaging, transportation, etc.) and to process X-ray films more quickly.

[0004] Low replenishment of the developing solution is also strongly demanded. From the viewpoint of environmental protection, there has been a demand for a reduction in the amount of development processing waste liquid. However, since the ban on the dumping of industrial waste into the ocean at the end of 1995 has been increasingly demanded.

It is necessary to address these demands for rapid processing and low replenishment processing as a whole system including a photosensitive material, a processing solution, and a processor. Particularly, the development of a photosensitive material to be processed is important. Many studies have been made so far.

In order to increase the developing speed and the fixing speed,
It is preferable to reduce the silver iodide content of the silver halide grains. However, it is known that lowering the average silver iodide content lowers the intrinsic sensitivity of silver halide. Further, when the silver iodide content of the silver halide surface is reduced,
It is known that the absorption of a spectral sensitizing dye is deteriorated and the spectral sensitivity is reduced, and that pressure fog may be increased. It is known that when the silver iodide content in silver halide is further reduced, pressure fog may increase.

It is also advantageous from the viewpoint of low replenishment processing to reduce the amount of silver coated on the light-sensitive material. Preferably, particles are used. Further, tabular silver halide grains are preferred from the viewpoint of color sensitization efficiency, that is, from the viewpoint of sensitivity.

In recent years, many techniques for improving sensitivity and image quality using such tabular silver halide grains have been disclosed. Examples of such techniques are described in JP-A-58-111935 and JP-A-58-111936. No. 58-111937, No. 5
Nos. 8-113927 and 59-99433.

JP-A-63-92942 discloses a technique of providing a core having a high silver iodide content in tabular silver halide grains, and JP-A-63-151618 discloses a hexagonal tabular silver halide grain. Are disclosed, and the effect of increasing the sensitivity is shown.

In addition to this, Japanese Patent Application Laid-Open No. 63-106746 discloses
JP-A-1-183644, JP-A-1-27923
No. 7 discloses a technique relating to the composition distribution of tabular silver halide grains.

However, tabular silver halide grains have the disadvantage that the pressure characteristics deteriorate. In general, silver halide grains are sensitive to pressure, and as the sensitivity increases,
Increasingly, they become more sensitive to pressure,
In the case of tabular silver halide grains, the degree is remarkable. This is because, when compared at the same volume, even if the materials have the same mechanical strength, the tabular grains are thinner than the spherical grains, so that a large moment is likely to be applied, and the mechanical strength of the whole grains is weak. Is interpreted as

The pressure characteristics vary depending on the conditions of chemical sensitization of the silver halide grains in addition to the shape of the silver halide grains. In general, it is known that when the degree of chemical sensitization is insufficient (insufficient chemical ripening), pressure desensitization is large, and when the degree of chemical sensitization is excessive, pressure desensitization is small but pressure fog increases. . In the case of tabular grains subjected to appropriate chemical sensitization, an increase in pressure fog often becomes a problem. When a spectral sensitizing dye is adsorbed, pressure fog due to chemical sensitization tends to be remarkable. Selenium and / or for higher sensitivity
Also, many studies on tellurium sensitization have been made, but these sensitization methods also tend to increase pressure fog.

Therefore, it is desired that the tabular silver halide grains have improved pressure characteristics, particularly reduced pressure fog.

Many studies have been made to improve the pressure characteristics.

For example, US Pat. No. 2,628,167 discloses that an emulsion containing a thallium salt improves pressure desensitization and achieves high sensitivity and high γ. Although pressure fog is not described, it is presumed that the technique for reducing pressure fog generally increases pressure fog because it has a trade-off relationship of increasing pressure desensitization.

In addition, JP-A-59-99433, 6
Nos. 0-35726, 60-147727, 63-
No. 301937, No. 63-149641, No. 63-1
No. 06746, No. 63-151618, No. 63-22
0238, JP-A-1-131541, JP-A2-1
No. 93138, No. 3-172836, No. 3-2317
39, JP-A-6-266032, JP-A-6-324
No. 418 discloses means for improving pressure characteristics.
These measures have not been able to achieve a sufficient improvement effect.

In particular, no effective means for reducing pressure fog has been found for tabular silver halide grains subjected to spectral sensitization or tabular silver halide grains sensitized to selenium and / or tellurium. is the current situation.

Moreover, the technology for reducing pressure fog has a trade-off relationship of increasing pressure desensitization.
It was difficult to develop a technology that satisfies both.

Recently, silver halide grains containing silver chloride have attracted attention from the viewpoint of rapid processing and low replenishment processing.

As described above, it is preferable to use tabular silver halide grains having a large projected area also in silver halide grains containing silver chloride.

Therefore, development of tabular silver halide grains containing silver chloride is desired in order to obtain a high-sensitivity silver halide photographic material having rapid processing and low replenishment processing suitability.

However, when an emulsion containing silver halide grains containing silver chloride is used, significant desensitization and fog increase are caused, and the sensitivity and gradation change in the development processing are large, so that practical use is extremely difficult. there were.

Further, many studies have been made on tabular grains containing silver chloride having a (111) plane as a main plane.
In addition, there is a significant problem that the additive has a large adverse effect on the photographic performance and the formed (111) plane is unstable. It was expected that practical use would be difficult.

On the other hand, many studies have been made on tabular grains containing silver chloride and having the (100) plane as a main plane.

JP-A-5-204073 discloses an emulsion comprising high silver chloride tabular grains whose main plane is (100), using silver iodide during nucleation. JP-A-7-234470 discloses an emulsion comprising silver halide tabular grains having a halogen composition gap plane in the center of the grains and having a (100) main plane. However, these emulsions were not practical because of insufficient sensitivity and low γ.

In JP-A-7-128768, the main plane is the (100) plane, and the grains containing silver chloride are selenium and / or tellurium-sensitized to achieve high sensitivity by rapid processing and low replenishment processing. I can do it. Generally, tabular grains are said to have low pressure resistance. However, when selenium and / or tellurium sensitization is applied to these (100) tabular grains, pressure fog may increase significantly. Do you get it.

As described above, conventionally, it has been known that when selenium and / or tellurium sensitization is performed on (100) tabular grains having (100) as a main plane, pressure fog is greatly increased. And therefore no solution was known.

Another disadvantage of the tabular grains is that silver tone is deteriorated. When the grain thickness of the silver halide grains is reduced, the light scattering of the blue light component by the filament silver formed in the development process increases, and as a result, the transmitted light becomes light with a strong yellow tint, so that the silver image has a yellow tint. I'm scared.
Although the color tone of the developed silver image is called a silver tone, a silver color tone with a yellow tint is not preferred in a medical light-sensitive material. Therefore, it has been necessary to develop silver halide grains having a good silver tone while being flat.

As described above, the tabular silver halide grains subjected to spectral sensitization and the tabular silver halide grains subjected to selenium and / or tellurium sensitization include silver iodobromide, silver bromide, silver chlorobromide, Pressure fog,
And silver tones were found to be a problem, but no effective solution has yet been found.

It has been known that thallium ions are contained in silver halide grains. "Th
e Influence of Thalous I
ons on the Properties of
Silver Halideemulations ",
(The Journal of Photograph
hic Science, Vol. 27, 37-41
(1979)) uses thallium ions when forming silver bromide and silver iodobromide tabular grains and silver chlorobromide and silver chloride grains. In the case of silver iodobromide tabular grains, thallium ions are used. It is shown that in the presence of, the particle size is reduced and the particle size distribution is narrowed. However, no mention is made of the pressure characteristics, and neither spectral sensitization nor selenium and / or tellurium sensitization has been performed, so that tabular silver halide grains which have been spectrally sensitized, selenium and / or The effect of thallium ions on tellurium sensitized tabular grains was not predictable.

[0031]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a silver halide photographic emulsion and a light-sensitive emulsion having high sensitivity, improved pressure resistance, improved silver tone, and excellent rapid processing suitability and low replenishment processing suitability. Is to provide the material.

A second object is to provide a method for producing a silver halide photographic emulsion having such performance.

A third object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material having such performance in a quick, safe and environmentally friendly manner.

[0034]

The object of the present invention has been attained by the following constitutions.

(1) A silver halide photographic emulsion containing thallium ions and containing spectrally sensitized tabular silver halide grains.

(2) A silver halide photographic emulsion containing tabular silver halide grains containing thallium ions and sensitized with selenium and / or tellurium.

(3) The silver halide photographic emulsion according to (2), wherein the tabular silver halide grains are spectrally sensitized.

(4) The silver halide photographic emulsion according to any one of (1) to (3), wherein thallium ions are contained inside the silver halide grains.

(5) The method for producing a silver halide photographic emulsion according to any one of (1) to (4), wherein silver halide grains are formed in the presence of thallium ions. A method for producing a silver halide photographic emulsion.

(6) A silver halide photograph comprising a support and a silver halide photographic emulsion layer containing the silver halide photographic emulsion according to any one of (1) to (4). Photosensitive material.

(7) A method for processing a silver halide photographic material, comprising subjecting the silver halide photographic material of (6) to photographic processing including development processing.

(8) The method for processing a silver halide photographic material according to (7), wherein the development processing time is 12 seconds or less.

(9) A method of processing while continuously replenishing a processing solution according to the photosensitive material to be processed, wherein the replenishment amount of the developing solution is 100 ml per 1 m ^{2 of the} photosensitive material to be processed.
(7) or (8), wherein the silver halide photographic light-sensitive material is processed.

(10) A developing solution and / or a replenishing solution containing substantially no dihydroxybenzene-based developing agent and containing a compound represented by the following formula (A): The method for processing a silver halide photographic light-sensitive material according to any one of (1) to (9).

[0045]

Embedded image

In the formula, R ₁ and R ₂ each represent a hydroxy group,
Represents an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P and Q represent a hydroxy group, a carboxy group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, a methylcapto group, an alkyl group or an aryl group; And Q represent an atom group forming a 5- to 8-membered ring together with the two vinyl carbon atoms substituted by R ₁ and R ₂ and the carbon atom substituted by Y. Y is = O,
Or = represents a N-R _3. R ₃ represents a hydrogen atom, a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group.

(11) The silver halide according to any one of (7) to (10), wherein the processing is performed by an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank of the automatic developing machine. Processing method of photographic photosensitive material.

(12) The silver halide photographic material described in (6) is sandwiched between high sensitivity intensifying screens, X-ray photographed, and processed by the processing method described in any one of (7) to (11). An image forming method comprising:

Hereinafter, the present invention will be described in more detail.

The silver halide photographic emulsion of the present invention is characterized in that tabular silver halide grains constitute 50% or more of the total projected area of the silver halide grains in the emulsion, but preferably 70% or more. , More preferably 80% or more and 100%
Below, more preferably, 90% or more and 100% or less consist of tabular silver halide grains.

Tabular silver halide grains are grains having two opposing parallel main planes, and the average value of the ratio of the grain size to the grain thickness (hereinafter referred to as aspect ratio) is 1.
It means something greater than 3. Here, the grain size means an average projected area diameter (hereinafter, referred to as a grain size), and is a circle equivalent diameter of a projected area of the tabular silver halide grains (of a circle having the same projected area as the silver halide grains). (Diameter), and thickness refers to the distance between two parallel major planes forming tabular silver halide grains.

The average aspect ratio of the tabular silver halide grains contained in the silver halide photographic emulsion of the present invention (hereinafter sometimes abbreviated to the tabular silver halide grains of the present invention) is preferably 2 or more and less than 20. But more preferably 2 or more and 1
Less than 5, more preferably 2 or more and less than 12,
Most preferably, it is 2 or more and less than 8.

The main plane of the tabular silver halide grains of the present invention may be either the (111) plane or the (100) plane.

When the main plane is a (111) plane, the tabular silver halide grains are preferably hexagonal.
Hexagonal tabular grains (hereinafter sometimes abbreviated as hexagonal tabular grains) are those whose main plane ((111) plane) is hexagonal and whose maximum adjacency ratio is 1.0 to 2.0. Say 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 grains preferably have rounded corners if the maximum adjacent side ratio is 1.0 to 2.0. The length of a side having a rounded corner is represented by the distance between the intersection of the extended straight line portion of the side and the extended straight line portion of the adjacent side. It is also preferred that the tabular grains are further rounded and are substantially circular.

In the present invention, it is preferable that at least one half of each side forming the hexagon of the hexagonal tabular grain is substantially a straight line. In the present invention, the adjacent side ratio is 1.0
More preferably, it is 1.5.

When the main plane is composed of (111) planes, the tabular silver halide grains of the present invention have 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 light-sensitive silver halide photographic emulsion is applied so that the main planes of the tabular silver halide grains contained are oriented substantially parallel to the support to prepare a sample. This is cut using a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

The distance between twin planes in the present invention indicates the distance between twin planes when there are two twin planes, and the distance between twin planes when there are three or more twin planes. This is the longest distance.

In the present invention, the distance between twin planes can be determined as follows. That is, the section was observed using the above-mentioned transmission electron microscope, and 100 or more tabular silver halide grains showing a cross section cut almost perpendicularly to the main plane were arbitrarily selected. The inter-plane distance can be measured, and the distance can be obtained by the averaging.

In the present invention, the average value of the distance between twin planes is preferably 0.008 μm or more, more preferably 0.010 μm or more, and still more preferably 0.012 μm or more.
It is not less than μm and not more than 0.05 μm.

When the main plane is a (100) plane, the shape of the main plane of the tabular silver halide grains is a right-angled parallelogram or a shape in which the corners of a right-angled parallelogram are rounded. The adjacent side ratio of the right-angled parallelogram is preferably less than 10, more preferably less than 5, further preferably less than 2. In addition, the length of the side when the corner is rounded is represented by the length up to the intersection with the line obtained by extending the straight part of the side of the right-angled parallelogram and extending the straight part of the adjacent side.

In the present invention, the method of measuring the crystal plane of tabular silver halide grains is described in Journal of
Imaging Science, vol. 29, N
o5, Sept. 1985, SPRINGFIELD
The method reported by Tani et al. In US, 165-171 can be used.

The silver halide grains of the present invention may have dislocations. Dislocations are described in F. Hamilton,
Photo. Sci. Eng., 57 (1967);
Shiozawa, J .; Soc. Photo. Sci. J
Apan, 35, 213 (1972), which can be observed by a direct method using a low-temperature transmission electron microscope. That is, silver halide grains taken out so as not to apply enough pressure to generate dislocations from the emulsion are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for the electron beam to pass through. Therefore, a high-pressure type (200 KV or more for a 0.25 μm-thick particle)
Can be observed more clearly using an electron microscope.

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

The average thickness of the tabular silver halide grains of the present invention is preferably from 0.01 to 1.0 μm, more preferably from 0.02 to 0.40 μm, even more preferably from 0.02 to 0.4 μm. 30 μm.

In the present invention, the tabular silver halide grains are preferably monodisperse grains having a narrow particle size distribution.

Specifically, when the width of the distribution is defined by (standard deviation of particle size / average particle size) × 100 = width (%) of particle size distribution, it is preferably 30% or less, and 25% or less. The following is more preferable, 20% or less is still more preferable, and 17% or less is the most preferable.

The tabular silver halide grains of the present invention preferably have a narrow thickness distribution. Specifically, when the width of distribution is defined by (standard deviation of thickness / average thickness) × 100 = width (%) of thickness distribution, it is preferably 30% or less, and more preferably 25%. The content is particularly preferably 20% or less.

The particle size and thickness can be optimized to optimize sensitivity and other photographic properties. Optimum particle size and optimum depending on other factors constituting the photosensitive material (sensitivity of hydrophilic colloid layer, hardness, chemical ripening conditions, sensitivity of photosensitive material, amount of silver coating, etc.) that affect sensitivity and other photographic characteristics The thickness is different.

In the silver halide photographic emulsion of the present invention, silver bromide, silver iodobromide, silver iodochloride, silver chloroiodobromide, silver chlorobromide, silver chloride and the like can be used as silver halide. In particular, silver bromide, silver iodobromide, silver chloroiodobromide and silver chlorobromide are preferred. When silver iodide is contained, the silver iodide content is preferably 0.8 mol% or less as the average silver iodide content in the whole silver halide grains, but is preferably 0.5 mol% or less. And more preferably 0.05 mol% or more and 0.4 or more.
It is preferably at most mol%. Silver iodobromide is preferred over pure silver bromide.

In the present invention, when the tabular silver halide grains have the (111) plane as the main plane, the silver bromide content is 5%.
It is preferably at least 0 mol%. Also, (100)
When the surface is a main plane, the silver chloride content is preferably 30 mol% or more.

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

The tabular silver halide grains contained in the silver halide photographic emulsion of the present invention preferably have a more uniform halogen composition between grains. When the distribution of the halogen composition between the grains was measured by the EPMA method, the relative standard deviation of the composition between the grains of iodine was particularly 35% or less, more preferably 20%
The following is preferred.

In the present invention, when the tabular silver halide grains contain silver iodide, the silver iodide is contained on the surface and / or inside, but is preferably contained at least on the surface. In the case of the surface, it is particularly preferable to contain it on the outermost surface as described later.

In the present invention, the tabular silver halide grains preferably have silver bromide and / or silver iodide on the outermost surface of the grains. Silver bromide content on the outermost surface is 20 mol%
Or more, more preferably 50 mol% or more. The silver iodide content is preferably at most 10 mol%, more preferably at most 5 mol%, most preferably at most 1.0 mol%.

Here, the halogen composition on the outermost surface of the tabular silver halide grains is defined by the XPS method (X-ray Photo).
Oletron Spectroscopy (X-ray Photoelectron Spectroscopy) refers to the halogen composition of a portion up to a depth of 50 °, which can be determined as follows.

The sample was cooled to −110 ° C. or less in an ultra-high vacuum of 1 × 10 ⁻⁸ torr or less, and irradiated with MgKα as an X-ray for a probe at an X-ray source voltage of 15 kv and an X-ray source current of 40 mA. 2, measured for Br3d and I3d3 / 2 electrons. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the halide composition on the outermost surface is determined from these intensity ratios.

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

In the present invention, the tabular silver halide grains preferably have a silver bromide and / or silver iodide localized phase near the surface and / or near the apex. The term "near the surface" as used in the present invention means that the particle size is 1 particle,
Within / 5, preferably within 1/7. Further, the vicinity of the vertex in the present invention means about ３ of the diameter of a circle having the same area as the area of the projected silver halide grain in the present invention.
Is defined as an area of a tabular grain having the length of one side as one side and the vertex of the grain as one corner.

The silver bromide content of the silver bromide localized phase near the surface and / or near the apex is preferably at least 20 mol%.
Mole% or more is more preferable. The silver iodide content of the localized silver iodide phase is preferably 5 mol% or less, more preferably 1 mol% or less.

In the present invention, the tabular silver halide grains preferably contain silver iodide inside, and more preferably exist at least at the center. In this case, the inner composition preferably contains silver iodide in an amount of 0.1 mol% to 5 mol%. Here, the halogen composition distribution inside the silver halide grains can be determined by pre-treating the grains into ultrathin sections, and then observing and analyzing them with a transmission electron microscope while cooling. Specifically, silver halide grains are taken out of the emulsion, embedded in a resin, and cut with a diamond knife to produce a 60-nm-thick section. This section can be obtained by observation and point analysis with a transmission electron microscope equipped with an energy dispersive X-ray analyzer while cooling the section with liquid nitrogen, and by quantitative calculation (Inoue, Nagasawa: Photographic Society of Japan, 1987) Conference Abstracts 62 pages).

The tabular silver halide grains of the present invention are characterized by containing thallium ions. In the present invention, the content of thallium ion is 10 ^-9 to 10 ^-1 mol, preferably 10 ^-8 to 1 ^-1 mol per mol of silver halide.
0 ^-2 mol. There are no particular restrictions on the location of the compound, but the compound is preferably contained inside. The inside indicates a position inside the outermost surface of the particle. Further, it is preferable that thallium ions be contained more uniformly.

It was not expected from the prior art that the inclusion of thallium ions could reduce so-called pressure fogging such as scratch resistance and roller marks. It is presumed that the thallium ions incorporated in the crystal increased the strength of the crystal. Therefore, other than thallium ions, the same effect can be expected for cations that are taken into silver halide crystals and increase the strength of the crystals.

Conventionally, a technique for improving pressure desensitization by containing thallium ions in the grains has been known. However, the present invention relates to a method for sensitizing tabular grains by spectral sensitization or selenium and / or tellurium sensitization. This is a technique for improving pressure fog, which is a problem due to significant deterioration, and is completely different from the prior art.

The method for producing a silver halide photographic emulsion of the present invention is characterized in that tabular silver halide grains are formed in the presence of thallium ions.

In the present invention, formation of silver halide grains in the presence of thallium ions means that, for example, when the grain formation process comprises a nucleation process, an Ostwald ripening process, and a crystal growth process, at least one of the processes. It is necessary that the particles be formed in the presence of thallium ions.

In the present invention, thallium ions are preferably added in the form of a water-soluble salt such as thallium nitrate or thallium sulfate.

In the present invention, the temperature at the time of adding thallium ions is preferably from 10 to 90 ° C., more preferably from 15 to 90 ° C.
80 ° C. , PH at the time of adding thallium ion is 1-1
0 is preferable, and 2 to 9 is more preferable. The preferred range of pAg upon addition of thallium ions varies depending on the shape, crystal face, halogen composition, addition process and the like of tabular silver halide grains, and cannot be determined unconditionally.
They can be freely selected as long as the desired particle formation is not hindered.

When thallium ions are present during the nucleation process, water, a halide, a dispersion medium and the like and a thallium compound are mixed in a reaction vessel in advance, and a silver salt solution and a halide solution are simultaneously or alternately added to the solution. Alternatively, a method of performing nucleation by adding only a silver salt solution, including a thallium compound in the silver salt solution and / or the halide solution, and simultaneously or alternately using the silver salt solution and the halide solution or the silver salt solution A method of performing nucleation by adding only the solution to the dispersion medium solution in the reaction vessel; a method of interrupting the addition of the silver salt and / or halide solution during the nucleation and adding a thallium compound solution; On the way, the method of adding the thallium compound solution while the addition of the silver salt and / or the halide solution is continued, and adding the solution containing the fine-grained thallium halide at any time during nucleation. How to, etc. are preferably used.

The above methods (1) to (5) may be used in combination.

The amount of thallium ion added in the nucleation process is 5 × 10 ^-9 to 1 mol, preferably 5 × 10 ^{-8 to} 5 × 10 ^-1 mol, per mol of silver used in the nucleation process. is there.

When thallium ions are present during the Ostwald ripening process, a method of adding a thallium compound solution at any stage from the start to the end of the ripening, and containing fine-grained thallium halide at any stage of the ripening. A method of adding a solution and the like are preferably used. The thallium compound solution may be a mixed solution with other additives.

The amount of thallium ion added during the Ostwald ripening process is 5 × 10 ^-9 to 1 mol per mol of silver, preferably 1 mol, based on the total amount of silver used before the ripening.
0 ^{-8 to} 5 × 10 ^-1 mol.

When thallium ions are present during the crystal growth process, a thallium compound is contained in a silver salt solution and / or a halide solution and / or a fine grain silver halide emulsion, and added to a dispersion medium solution in a reaction vessel. A method of performing crystal growth, a method of interrupting the addition of a silver salt and / or halide solution and / or a fine grain silver halide emulsion during crystal growth, and adding a thallium compound solution; And / or a method of adding a thallium compound solution while continuously adding a halide solution and / or a fine grain silver halide emulsion, a method of adding a solution containing a fine grain thallium halide at any time of crystal growth, and the like. Is preferably used.

The amount of thallium ion added during the crystal growth process is 10 ^-9 to 10 ^-1 mol, preferably 10 ^-8 to 10 ^-2 mol, per mol of silver used in the process.

In the present invention, a method for producing a silver halide photographic emulsion containing tabular silver halide grains other than the presence of thallium ions is not particularly limited, and any conventionally known method can be employed.

In the method for producing a silver halide photographic emulsion of the present invention containing tabular silver halide grains having a (111) plane as a main plane, the method comprises a nucleation step, a ripening step, and a crystal growing step. Preferably.

Further, after the nucleation step, the ripening step or after the crystallization step, the production is interrupted at any stage during the crystal growth step, and the formed silver halide grains are used as seed grains and newly added. It is preferable to grow the seed grains by a method of depositing silver halide on the surface of the seed grains.

For example, in order to obtain a silver halide photographic emulsion of the present invention containing tabular silver halide grains having a (111) plane as a main plane, a water-soluble silver salt solution and a halide solution are mixed with a dispersion medium solution. In the method for producing a silver halide photographic emulsion fed to the presence, (a) the pBr of the mother liquor is reduced by at least 1/2 period from the initial stage of the formation of a silver halide precipitate having a silver iodide content of 0 to 5 mol%. A nucleation step of maintaining the concentration at 2.5 to -0.7 is provided. (B) Following the nucleation step, the mother liquor contains a silver halide solvent in an amount of 10 ^{-5 to} 2.0 mol per mol of silver halide. A seed grain forming step for forming silver halide seed grains that are substantially monodisperse spherical twins is provided, or
Following the nucleation step, the temperature of the mother liquor is raised to 40 to 80 ° C. to provide a seed grain formation step for forming silver halide twin seed grains. (C) Then, a water-soluble silver salt solution and a halide A method of providing a crystal growth step for growing seed grains by adding a solution and / or a fine grain silver halide emulsion is preferably used.

Here, the mother liquor is a liquid (including a silver halide photographic emulsion) which is used for preparing a silver halide photographic emulsion up to a completed photographic emulsion.

The silver halide grains formed in the nucleation step are twin grains composed of 0 to 5 mol% of silver iodide.

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

The crystal growth process for growing the silver halide seed grains includes pAg during precipitation of silver halide, pH, temperature,
This can be achieved by controlling the concentration of the silver halide solvent and the composition of the silver halide, and the addition rate of the silver salt and the halide solution.

In the production of the emulsion of the present invention, ammonia, ammonia,
Known silver halide solvents such as thioether and thiourea can be present.

In order to obtain the tabular silver halide grains of the present invention, the conditions for crystal growth of the produced seed grains are described in JP-A-51-39027 and JP-A-55-142329.
Nos. 58-113928, 54-48521 and 58-49938, a water-soluble silver salt solution and a halide solution were added by the double jet method, and the addition rate was adjusted according to the grain growth. Therefore, the rate at which new nucleation does not occur and the size distribution does not spread due to Ostwald ripening, ie, the rate at which new nuclei are generated is 30 to 100
%. As another condition for growing seed particles, the Photographic Society of Japan, Showa 5
As can be seen in the 88th Annual Meeting Abstracts, Item 88, a method of growing by adding a fine grain silver halide emulsion, dissolving and recrystallizing is preferably used. Particularly, silver iodide fine grains, silver bromide fine grains, and silver iodobromide fine grains are preferably used.

In the method for producing a silver halide photographic emulsion of the present invention containing tabular silver halide grains having the (100) plane as a main plane, for example, iodine may be added under conditions that facilitate formation of the (100) plane. Nuclei can be formed at a low pCl in the presence of ions. After nucleation, Ostwald ripening and / or growth is performed to obtain tabular silver halide grains having a desired grain size and distribution.

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

In this case, the growth may be temporarily stopped in the middle, and the seed grains may be used as the seed grains to grow silver halide on the seed grains.

Specifically, an aqueous solution and a seed particle containing a protective colloid are previously present in a reaction vessel, and if necessary, silver ions, halide ions or silver halide fine particles are supplied to grow the seed particles. it can.

Further, as described in Japanese Patent Application No. 7-157670, at least 1) a step of adding a silver salt in the absence of iodide to start nucleation, and 2) a step of continuing the addition of iodide. A method for producing a silver halide photographic emulsion, which has two steps of adding a silver salt and causing nucleation and / or crystal growth, can also be used.

Specifically, (a) nucleation is started in the absence of iodide, and then nucleation is performed in the presence of iodide. (B) nucleation is started in the absence of iodide, (C) starting nucleation in the absence of iodide, and subsequently growing crystals simultaneously with nucleation in the presence of iodide. In any case, the feature is that iodide is not present at the start of nucleation and iodide is present immediately thereafter.

Further, in the production method of the present invention, a method in which iodide is not present at the time of nucleation and / or immediately thereafter can be advantageously used.

Hereinafter, each process will be described in detail.

(1) Nucleation Step A silver salt and / or halide salt solution is added to a dispersion medium solution containing at least a dispersion medium and water while stirring to form nuclei. The pCl at the start of nucleation is adjusted to a value that easily forms the (100) plane, that is, 0.5 to 3.5, preferably 1.0 to 3.0, and more preferably 1.5 to 2.5. When iodine is used, iodine can be introduced up to the solid solution limit of silver iodide and silver chloride, but the iodine ion concentration in the protective colloid solution at the start of nucleation is 10 mol%.
Or less, more preferably 0.001 mol% or more and 10 mol% or less, and most preferably 0.05 mol% or less.
Not less than 10 mol%. Further, bromine ions in the protective colloid solution during nucleation may be present as long as chloride ions are present in an amount of 20 mol% or more. The pH is 1.
It is preferably 0 or more, more preferably 1.5 or more, and still more preferably 2.0 to 8.0. Gelatin and gelatin derivatives are preferably used as the dispersion medium, and gelatin from which impurities have been removed is more preferable. In particular, it is preferable to use a so-called low methionine gelatin having a methionine content of less than 30 μmol / g of gelatin, preferably less than 15 μmol / g of gelatin. Further, the molecular weight is 1000 to 10 × 10 ⁴ , preferably 2000 to 6 ×
It is preferable to use a 10-called low molecular weight gelatin ^4. These gelatins may be used alone or as a mixture of two or more. Dispersion medium concentration is 0.1 ~
It is preferably 10% by weight, more preferably 0.3 to 5% by weight. The addition time of the silver salt solution during nucleation is preferably 5 seconds or more and less than 1 minute. During this time, other halide salts may or may not be added. That is, a so-called single jet method in which only a silver salt is added or a double jet method in which a silver salt and a halide salt solution is added may be used. The temperature is preferably from 30 to 90 ° C, more preferably from 35 to 70 ° C. The amount of silver added during nucleation is preferably from 0.1 mol% to 10 mol% of the total silver amount.

(2) Ripening Step The method for producing a silver halide photographic emulsion of the present invention preferably has a ripening step following the nucleation step. In the ripening process, tabular grains generated during nucleation by Ostwald ripening can be further grown and other grains can be eliminated. Aging temperature is 20 ~ 90 ℃
Is preferably 30 to 85 ° C, and most preferably 40 to 80 ° C. The temperature during ripening may be constant or changed, but a method of changing the ripening temperature is preferable, and it is more preferable to raise the ripening temperature. The pCl during aging is preferably 0.5 to 3.5, and 1.0 to 3.0.
Is more preferred. Further, the pH is preferably 1 to 12, more preferably 2 to 8, and most preferably 2 to 6. The ripening is preferably carried out in the absence of a so-called silver halide solvent such as ammonia.

(3) Crystal Growth Step The production method of the present invention may include a crystal growth step following the ripening step. The pCl during crystal growth is 0.5-
It is adjusted to a range of 3.5, preferably 1.0 to 3.5.
0, and more preferably 1.5 to 2.5. Also,
The pH is preferably from 1 to 12, more preferably from 2 to 8, and most preferably from 2 to 6. The temperature during crystal growth is 40 ~
90 ° C. is preferred, more preferably 45-80 ° C., and most preferably 50-75 ° C. The method of adding silver ions and halide ions during crystal growth is any of a double jet method in which a silver salt and a halide salt solution is added, a fine particle supply method in which a previously prepared AgX fine particle emulsion is added, and a combination of both methods. May be used.
Among these, the fine particle supply method is preferably used. When the fine particle supply method is used, the diameter of the fine particles is 0.15 μm.
Or less, more preferably 0.1 μm or less, and most preferably 0.06 μm or less.

It is also possible to preferably use a method in which the growth is temporarily stopped halfway, and the growth is stopped by using the seed grains as seed grains to precipitate silver halide on the seed grains.

Specifically, a dispersion medium solution and seed particles are preliminarily placed in a reaction vessel, and a silver salt solution, a halide salt solution, or silver halide fine particles are supplied as necessary to grow the seed particles. it can.

In the method for producing a silver halide photographic emulsion of the present invention, a known silver halide solvent such as ammonia, thioether, and thiourea can be present.

In the method for producing a silver halide photographic emulsion of the present invention, during growth, a silver salt solution and a halide solution are added by a double jet method. Particles having a desired particle size and distribution can be obtained by a method in which the size distribution is not spread due to Ostwald ripening, that is, a method in which the size is gradually changed within the range of 30 to 100% of the rate at which new nuclei are generated. As another condition for further growth, a method in which a fine grain silver halide emulsion is added, dissolved and recrystallized, as described in the Abstracts of the 88th Annual Meeting of the Photographic Society of Japan, 1983, is also preferably used. In particular, silver iodide fine grains, silver bromide fine grains, silver iodobromide fine grains, silver bromochloride fine grains,
Silver chloride fine particles are preferably used.

The tabular silver halide grains according to the present invention include:
So-called halogen conversion type (conversion type) particles may be used. The halogen conversion amount is 0.1 to silver amount.
The conversion is preferably 2 mol% to 0.5 mol%, and the conversion may be performed either during physical ripening or after completion of physical ripening. As a method of halogen conversion, an aqueous halogen solution or fine silver halide particles having a smaller solubility product with silver than the halogen composition of the grain surface before the halogen conversion is usually added. The particle size at this time is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm.

When silver iodide and / or silver bromide are contained on the outermost surface of the tabular silver halide grains of the present invention, a method of adding a silver nitrate solution and an iodine Ion and / or bromine ion-containing solution, silver iodide, silver bromide, silver iodobromide or silver chloroiodobromide, and the like, potassium iodide or iodide. A method of adding a mixture of potassium bromide and potassium bromide or the like can be applied. Of these, the method of adding fine silver halide grains is preferable.
Particularly preferred is a method of adding silver iodide fine grains, silver bromide fine grains, and silver iodobromide fine grains.

The above-mentioned silver iodide and / or silver bromide content on the outermost surface is adjusted from the final stage of the silver halide crystal production process to the chemical ripening process, and immediately before the application of the silver halide photographic emulsion. Can be selected until the completion of the liquid preparation step, but it is preferable to adjust the pH by the end of the chemical ripening step. The chemical ripening step referred to here is a point in time when physical ripening and desalting of the silver halide emulsion of the present invention are completed, when a chemical sensitizer is added, and thereafter, an operation for stopping chemical ripening is performed. Up to. The addition of silver halide fine grains may be carried out several times at intervals, 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 preferably in the range of 30 to 80 ° C., more preferably 40 to 65 ° C. Further, the present invention is preferably carried out under the condition that part or all of the silver halide fine grains to be added disappears immediately before coating immediately after the addition, more preferably 20% of the added silver halide fine grains. The above is the disappearance immediately before the application.

In producing the silver halide photographic emulsion of the present invention, stirring conditions during the production are extremely important. As a stirrer, disclosed in JP-A-62-160128,
An apparatus in which the additive liquid nozzle is installed in the liquid near the mother liquid inlet of the stirrer is particularly preferably used. In this case, the rotation speed of the stirring is preferably set to 100 to 1200 rpm.

The details of the above-mentioned supersaturation factor are as follows.
For example, JP-A-63-92942,
213637 and the like can be referred to.

In the silver halide grains of the present invention, silver nuclei may be formed during grain formation. Silver nucleation is carried out by adding a reducing agent to a silver halide photographic emulsion or a mixed solution for grain growth, or a silver halide photographic emulsion or a mixed solution for grain growth is reduced to a low pAg of pAg7 or less. It is carried out by ripening or growing the particles under high pH conditions of pH 7 or higher. A method performed by combining these methods is a preferred embodiment of the present invention.

As a technique for forming silver nuclei, reduction sensitization has been known for a long time. For example, Journal o
f Photographic Science No. 25
Vol. 19-27 (1977) and Photogra.
phic scienceand engineeri
ng, Vol. 32, pp. 113-117 (1979), the silver nuclei formed by reduction sensitization are Ph
autographfish Korrespndenz
Volume 1, 20 (1957) and Photograph
ic Science and Engineerine
g In the 19th volume, 49-55 (1975)
As described by icell and Lowe, it has been considered that the compound contributes to sensitization through a reaction represented by the following formula at the time of exposure.

AgX + hv → e ⁻ + h ⁺ (1) Ag ₂ + h ⁺ → Ag ⁺ + Ag (2) Ag → Ag ⁺ + e ⁻ (3) Here, h ⁺ and e ⁻ were generated by exposure. Free holes and free electrons, hv indicates a photon, and Ag ₂ indicates a silver nucleus formed by reduction sensitization.

Preferred reducing agents include, for example, thiourea dioxide, ascorbic acid and its derivatives,
And tin salts. Other suitable reducing agents include
Examples include borane compounds, hydrazine derivatives, formamidine sulfinic acid, silane compounds, amines and polyamines, and sulfites. The addition amount of these reducing agents is preferably from 10 ^-2 to 10 ^-8 mol per mol of silver halide.

For low pAg ripening, a silver salt can be added, but a water-soluble silver salt is preferable and silver nitrate is preferable as the water-soluble silver salt. The pAg at the time of aging is suitably 7 or less, preferably 6 or less, and more preferably 1 to 1.
3 (where pAg = -log [Ag ⁺ ]).

The high pH ripening is carried out, for example, by adding an alkaline compound to a silver halide photographic emulsion or a mixed solution for grain growth. As the alkaline compound, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like can be used. In the method of adding ammoniacal silver nitrate to silver halide formation, an alkaline compound other than ammonia is preferably used because the effect of ammonia is reduced.

As a method for adding a silver salt and an alkaline compound for forming silver nuclei, rush addition or addition over a certain period of time may be used. In this case, the addition may be performed at a constant flow rate, or may be performed while changing the flow rate with respect to time.

Also, the required amount may be added in several portions. Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, it may be present in the reaction vessel, or may be mixed in a soluble halide solution and added together with the halide. Furthermore,
The addition may be performed separately from the soluble silver salt and the soluble halide.

An oxidizing agent can be used in the silver halide photographic emulsion of the present invention. The following oxidizing agents can be used.

Hydrogen peroxide (water) and its adduct: H
₂ O ₂ , NaBO ₂ , H ₂ O ₂ -3H ₂ O ₂ , Na ₄ P ₂ O ₇ -2
Such as _{H 2 O 2, 2Na 2 SO} 4 -H 2 O 2 -2H 2 O. Peroxy acid salts: K ₂ S ₂ O ₃ , K ₂ C ₂ O ₃ , K ₄ P ₂ O ₃ , K ₂ [T
_{i (O 2) C 2 O} 4 ]-3H ₂ O and the like.

In addition, peracetic acid, ozone, iodine, bromine,
And thiosulfonic acid compounds.

The amount of the oxidizing agent used in the present invention is affected by the type of the reducing agent, the conditions for forming silver nuclei, the timing of adding the oxidizing agent, and the adding conditions. ^-2 to ^10-5 mol is preferred.

The oxidizing agent may be added at any time during the silver halide photographic emulsion production process. It can be added prior to the addition of the reducing agent. Further, after the oxidizing agent is added, a reducing substance may be newly added to neutralize the excess oxidizing agent. These reducing substances are substances capable of reducing the oxidizing agent, and include sulfinic acids, di- and trihydroxybenzenes, chromans, hydrazines and hydrazides, p-phenylenediamines, aldehydes, aminophenols, Examples include enediols, oximes, reducing sugars, phenidones, sulfites, and ascorbic acid derivatives. These reducing substances are added in an amount of 10 ^-3 per mole of the oxidizing agent used.
10 ³ mol is preferable.

In the silver halide photographic emulsion of the present invention, heavy metal ions can be used. As heavy metal ions,
Periodic table of iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, etc.
Group VIII metal, cadmium, zinc, mercury, etc.
Group II transition metals, and various ions such as lead, rhenium, molybdenum, tungsten, and chromium, among which iron,
Transition metal ions of iridium, platinum, ruthenium and osmium are preferred.

These heavy metal ions can be added to a silver halide photographic emulsion in the form of a salt or a complex salt. Among them, those added to the emulsion in the form of a complex salt are preferred because they can be easily incorporated into a silver halide photographic emulsion.

When a heavy metal ion forms a complex,
Examples of the ligand include cyanide, thiocyanic acid, isothiocyanic acid, cyanic acid, chloride, bromide, iodide, carbonyl, and ammonia.
Among them, thiocyanic acid, isothiocyanic acid and cyanate ion are preferred.

The heavy metal compounds preferably used in the present invention are shown below, but are not limited thereto.

(1) FeCl ₂ , (2) FeCl ₃ ,
(3) (NH ₄ ) Fe (SO ₄ ) ₂ , (4) K ₃ [Fe (C
N) ₆ ], (5) K ₄ [Fe (CN) ₆ ], (6) K ₂ [I
rCl ₆ ], (7) K ₃ [IrCl ₆ ], (8) K ₂ [Pt
Cl ₆ ], (9) K ₂ [Pt (SCN) ₄ ], (10) K ₂
[Pt (CN) ₄ ], (11) K ₂ [PdCl ₆ ], (1
2) K ₃ [PdCl ₆ ], (13) CdCl ₂ , (14)
ZnCl ₂ , (15) K ₂ [Mo (CO) ₄ (CN
O) ₂ ], (16) K ₃ [Re (CNO) ₆ ], (17)
K ₃ [Mo (CNO) ₆ ], (18) K ₄ [Fe (CN
O) ₆ ], (19) K ₂ [W (CO) ₄ (CNO) ₂ ],
(20) K ₂ [Cr (CO) ₄ (CNO) ₂ ], (21)
K ₄ [Ru (CNO) ₆ ], (22) K ₂ [Ni (C
N) ₄ ], (23) PbCl ₂ , (24) K ₃ [Co (N
H ₃ ) ₆ ], (25) K ₅ [Co ₂ (CNO) ₁₁ ], (2
6) K ₃ [Re (CNO) ₆ ], (27) K ₄ [Os (C
NO) ₆ ], (28) K ₂ [Cd (CNO) ₄ ], (2
9) K ₂ [Pt (CNO) ₄ ], (30) K ₃ [IrB
r ₆ ] In order to incorporate a heavy metal ion into a silver halide photographic emulsion, the heavy metal compound is added before forming silver halide grains.
During the formation of silver halide grains, it may be added at any place in each step during physical ripening after the formation of silver halide grains. For this purpose, for example, a heavy metal compound may be added as an aqueous solution at a desired timing. Alternatively, they may be dissolved together with the silver halide and added continuously during the grain formation step.

The amount of heavy metal ion added to the silver halide photographic emulsion is from 1 × 10 ^-9 to 1 / mol of silver halide.
× 10 ^-2 mol is preferred, and especially 1 × 10 ^-8 to 1 × 10 ^-3.
Molar is preferred.

In the present invention, it is preferable to add a silver halide solvent before the desalting step in order to accelerate the developing speed. For example, 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, gelatin is preferably used as a dispersion medium for the protective colloid of the silver halide grains. As the gelatin, alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 20,000 to 10%) is used.
And modified gelatin such as phthalated gelatin. Other hydrophilic colloids can also be used. Specifically, Research Disclosure Magazine (Resea
rch Disclosure, hereinafter abbreviated as RD. ) Volume 176, NO. 17643 (December 1978), section IX.

In the silver halide photographic emulsion of the present invention, unnecessary soluble salts may be removed during the growth of silver halide grains, or they may be kept contained. When removing the salts, see RD Vol. It can be carried out based on the method described in 17643, Section II. When seed particles are used, desalting is preferably performed once when the formation of the seed particles is completed.

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

As these dyes, any of the nuclei usually used can be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc. A renin nucleus, a benzindolenin nucleus, an indole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may have a substituent on a carbon atom.

The merocyanine dye or the complex merocyanine dye includes pyrazoline- as a nucleus having a ketomethine structure.
5-6 nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. In addition, the emulsion layer may contain, in addition to the sensitizing dye, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect. For example, a substituted aminostilbene compound which is a nitrogen-containing heterocyclic nucleus group (for example, US Pat.
33,390 and 3,635,721), formaldehyde condensates of aromatic organic acids (for example, also described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like. Good.

US Pat. Nos. 3,615,613 and 3,6
No. 15,641, No. 3,617,295, No. 3,63
The combinations described in US Pat. No. 5,721 and the like are particularly useful. The sensitizing dye may be added during or during each step of nucleation, growth, desalting, and chemical sensitization, or after chemical sensitization.

In the tabular silver halide grains according to the present invention, the following cyanine or carbocyanine dyes can be used alone or in combination.

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The tabular silver halide grains of the present invention are preferably selenium and / or tellurium sensitized.

In the case of selenium sensitization, a wide variety of selenium compounds can be used as the selenium sensitizer. For example, US Pat. Nos. 1,574,944, 1,602,5
Nos. 92 and 1,623,499, JP-A-60-150
No. 046, JP-A-4-25832 and JP-A-4-10924.
Compounds described in Nos. 0 and 4-147250 can be used. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg,
Allyl isoselenocyanate, etc.), selenoureas (e.g., N, N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-)
Heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (for example, , Selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate) And the like, selenophosphates (eg, tri-p-triselenophosphate, etc.), and selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenoketones, selenides.

Specific examples of techniques for using these selenium sensitizers are described, for example, in US Pat. Nos. 1,574,944 and 1,60.
2,592, 1,623,499, 3,29
7,446, 3,297,447, 3,32
0,069, 3,408,196, 3,40
8,197, 3,442,653, 3,42
0,670, 3,591,385, French Patent 2,693,038, 2,093,209, JP-B-52-34491, JP-B-52-34492, and 53.
-295, 57-22090, JP-A-59-18
Nos. 0536, 59-185330, 59-181
No. 337, No. 59-187338, No. 59-1922
No. 41, No. 60-150046, No. 60-15163
7, JP-A-61-246738, JP-A-3-4221
No. 3-24537, No. 3-11838, No. 3
-116132, 3-148648, 3-23
No. 7450, No. 4-16838, No. 4-25832
Nos. 4-32831, 4-96059, 4-
No. 109240, 4-140738, 4-140
No. 739, No. 4-147250, No. 4-149439
Nos. 4-184331, 4-190225, 4-191729, 4-195,035, British Patents 255,846 and 861,984. In addition, H. E. FIG.
Spencer et al. Journal of Photo
graphic Science, Vol. 31, 158-
It is also disclosed in scientific literature such as page 169 (1983).

The amount of the selenium sensitizer used depends 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. Depending on the properties of the selenium compound to be used, the addition may be carried out by dissolving in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent. A method of premixing with a gelatin solution and adding,
Alternatively, a method of adding the compound in the form of an emulsified dispersion of a mixed solution with a polymer soluble in an organic solvent according to the method disclosed in JP-A-4-140739 may be used.

The temperature of chemical ripening using a selenium sensitizer is 4
The range is preferably from 0 to 90 ° C, more preferably from 45 ° C to 80 ° C. The pH is 4-9 and the pAg is 6
The range of -9.5 is preferred.

Regarding tellurium sensitizers and sensitization methods, see, for example, US Pat. Nos. 1,623,499 and 3,320,069.
Nos. 3,772,031 and 3,531,289
No. 3,655,394, British Patent 235,211
Nos. 1,121,496 and 1,295,462
No. 1,396,696, Canadian Patent 800,95
No. 8, JP-A-4-204640, JP-A-4-33304
No. 3 and the like. Examples of useful tellurium sensitizers include telluroureas (e.g., N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea, N, N'-dimethyl). -N'-phenyltellurourea), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluramides ( For example, telluroacetamide, N, N-dimethyltellurobenzamide), telluro ketones, telluro esters, isotellurocyanates, and the like.

The technique for using the tellurium sensitizer is the same as the technique for using the selenium sensitizer.

The tabular silver halide grains of the present invention are preferably used in combination with chemical sensitization other than selenium and / or tellurium sensitization. Chemical sensitization process conditions such as pH, pA
There are no particular restrictions on g, temperature, time, and the like, and the reaction can be performed under conditions generally performed in the art. As a preferable chemical sensitization method when used in combination, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin,
Examples thereof include a reduction sensitization method using a reducing substance, gold and other noble metal sensitization methods using a noble metal. Above all,
Sulfur sensitization, gold sensitization, reduction sensitization and the like are preferred.

Examples of the sulfur sensitizer applicable in the present invention include US Pat. Nos. 1,574,944 and 2,410,
No. 689, No. 2,278,947, No. 2,728,6
No. 68, No. 3, 501, 313, No. 3, 656, 95
No. 5, West German Application Publication (OLS) 142228, JP-A-56-24937, and JP-A-55-45016. Specific examples include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl, 3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, and sulfur alone. And the like are preferred examples. In addition, as the elemental sulfur, α-sulfur belonging to the orthorhombic system is preferable.

Examples of the gold sensitizer include chloroauric acid, gold thiosulfate, gold thiocyanate, and gold complexes of thioureas, rhodanines, and other various compounds.

The amounts of the sulfur sensitizer and the gold sensitizer to be used are not uniform depending on the type of silver halide grains, the type of compound used and the ripening conditions.
It is preferably from 1 × 10 ^-4 mol to 1 × 10 ^-9 mol per mol. Further, preferably 1 × 10 ⁻⁵ mol to 1 ×
10 ^-8 mol.

In the present invention, the sulfur sensitizer and the gold sensitizer may be added by dissolving them in water or alcohols or other inorganic or organic solvents and adding them in the form of a solution. Alternatively, it may be added in the form of a dispersion obtained by emulsifying and dispersing using a medium such as gelatin.

In the present invention, selenium and / or tellurium sensitization, sulfur sensitization and gold sensitization may be performed simultaneously, or separately and stepwise.

It is also preferable to perform so-called reduction sensitization on the surface of the grains by placing the grains in an appropriate reducing atmosphere.

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

The amount of the reducing agent added depends on the type of reduction sensitizer, the particle size of silver halide grains, the composition and crystal habit, the temperature of the reaction system,
It is preferable to change the pH depending on environmental conditions such as pH and pAg. For example, in the case of thiourea dioxide, approximately 0.01 to 2 mg per mole of silver halide is used as a rough guide.
Is preferable. In the case of ascorbic acid, the range is preferably about 50 mg to 2 g per mol of silver halide.

The conditions for reduction sensitization are as follows:
0 ° C., time is about 10 to 200 minutes, pH is about 5 to 11, p
Ag is preferably in the range of about 1 to 10 (here, pAg
The value is 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 from 1 to 6, and preferably from 2 to 4. Conditions such as temperature, pH, and time are preferably in the above-described reduction sensitization condition range. As a stabilizer for a silver halide photographic emulsion containing silver halide grains subjected to reduction sensitization, the following general stabilizers can be used, but the antioxidant disclosed in JP-A-57-82831 can be used. Agent and / or V.I. S. Gahler's paper [Zeithshift fur wissensc]
haftliche Photographie B
d. 63, 133 (1969)] and JP-A-54-1
Good results are often obtained when thiosulfonic acids described in No. 019 are used in combination. These compounds may be added at any stage of the emulsion production process from the crystal growth to the preparation process immediately before coating.

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

In the present invention, the dye is substantially insoluble in water at a pH of 7 or less and substantially water-soluble at a pH of 8 or more, and specifically, represented by the following general formulas [1] to [6]. Selected from the dyes represented.

[0181]

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[Wherein A and A 'may be the same or different and each represents an acidic nucleus, B represents a basic nucleus, Q represents an aryl group or a heterocyclic group, and Q' represents a heterocyclic ring. X and Y may be the same or different and each represents an electron-withdrawing group; L ₁ , L ₂ and L ₃
Each represents a methine group. m represents 0 or 1, and n
Represents 0, 1 or 2, and p represents 0 or 1. However, the dyes represented by the general formulas [1] to [6] have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule. The acidic nucleus represented by A and A 'in the general formulas [1], [2] and [3] is preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, Oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, pyrazolopyridone.

The basic nucleus represented by B in the general formulas [3] and [5] is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole, thiazole, benzothiazole, naphthothiazole, indolenine, pyrrole , Indole.

Examples of the aryl group represented by Q in the general formulas [1] and [4] include a phenyl group, a naphthyl group,
And a julolidyl group. In addition, the general formula [1],
Examples of the heterocyclic groups represented by Q and Q 'in [4] and [6] include pyridyl, quinolyl, isoquinolyl, pyrrolyl, pyrazolyl, imidazolyl, indolyl, furyl, thienyl and the like. Is mentioned. The aryl group and the heterocyclic group include those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, and a carboxy group. Group, cyano group, hydroxy group, mercapto group,
Examples include an amino group, an alkoxy group, an aryloxy group, an acyl group, a carbamoyl group, an acylamino group, a ureido group, a sulfonamide group, a sulfamoyl group, and the like. These substituents may be used in combination of two or more. Preferred substituents include an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a t-butyl group, an n-octyl group,
-Hydroxyethyl group, 2-methoxyethyl group, etc.), hydroxy group, cyano group, halogen atom (eg, fluorine atom, chlorine atom, etc.), alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, 2-hydroxy group) Ethoxy group, methylenedioxy group, n-butoxy group, etc., substituted amino group (for example, dimethylamino group, diethylamino group,
Di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-ethyl-N-methanesulfonamidoethylamino group, morpholino group, piperidino group, pyrrolidino group, etc.), carboxy group, sulfonamide group (Eg, methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (eg, sulfamoyl group,
Methylsulfamoyl group, phenylsulfamoyl group, etc.), and these substituents may be combined.

The electron-withdrawing groups represented by X and Y in the general formulas [4] and [5] may be the same or different, and the σp value of the substituent constant Hammett (edited by Toshio Fujita,
“Chemical domain special issue No. 122 Structure-activity relationship of drugs”, 9
Pages 6 to 103 (1979), Nankodo and the like. ) Is preferably 0.3 or more, for example, a cyano group,
Alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenoxycarbonyl group, 4-hydroxyphenoxycarbonyl group), carbamoyl group (for example, carbamoyl group, methyl Carbamoyl, ethylcarbamoyl, butylcarbamoyl, dimethylcarbamoyl, phenylcarbamoyl, 4-carboxyphenylcarbamoyl, etc.), acyl (eg, methylcarbonyl, ethylcarbonyl, butylcarbonyl, phenylcarbonyl, 4-phenyl) Ethylsulfonamidophenylcarbonyl group, etc., alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, octyls) Honiru group), an arylsulfonyl group (e.g., phenylsulfonyl group, 4-chlorosulfonyl group, etc.).

L ₁ , L ₂ and L in the general formulas [1] to [5]
_The methine group represented by ₃ includes those having a substituent,
Examples of the substituent include an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, a hexyl group, etc.), an aryl group (eg, a phenyl group, a tolyl group, a 4-hydroxyphenyl group), and an aralkyl group (eg, Benzyl group, phenethyl group, etc.), heterocyclic group (eg, pyridyl group, furyl group, thienyl group, etc.), substituted amino group (eg, dimethylamino group, diethylamino group, anilino group, etc.), and alkylthio group (eg, methylthio group, etc.). No.

In the present invention, among the dyes represented by the general formulas [1] to [6], a dye having at least one carboxy group in the molecule is preferably used, and more preferably a dye represented by the general formula [1] And particularly preferably a dye in which Q in the general formula [1] is a furyl group.

Next, specific examples of the dye preferably used in the present invention will be described.

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[0190]

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[0193]

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In the present invention, specific examples of the dye to be used are further described in JP-A Nos. 52-92716 and 55-120.
No. 030, No. 55-155350, No. 55-1553
No. 51, No. 56-12639, No. 63-197943
, JP-A-2-1838, JP-A-2-1839, World Patent No. 88/04794, U.S. Pat.
No. 4,950,586, European Patent 489,973
And can be synthesized according to the methods described in these patents.

In the present invention, the dye dispersed in the form of solid fine particles is preferably dispersed so that the average particle diameter becomes 0.01 μm to 5 μm, and more preferably 0.09 μm.
1 μm to 1 μm, particularly preferably 0.01 μm to
0.5 μm. The dispersion coefficient of the particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. Here, the variation coefficient of the particle size distribution is a value represented by the following equation.

(Standard deviation of particle size) / (average value of particle size) × 100 In the present invention, the constituent layer to which the dye is added and contained is a silver halide emulsion layer or a layer closer to the support than the silver halide emulsion layer or both. Preferably, it is more effective to add it in the coating layer adjacent to the transparent support. The concentration of the dye is preferably high on the side close to the support.

In the present invention, the amount of the dye to be added can be changed according to the sharpness target. Preferably, 0.2 to 20 / m ^2, more preferably, 0.8
１５15 mg / m ² .

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

In the surface layer of the silver halide photographic light-sensitive material of the present invention, a silicon compound described in US Pat. Nos. 3,489,576 and 4,047,958 as a slipping agent, described in JP-B-56-23139. In addition to colloidal silica, paraffin wax, higher fatty acid ester, starch derivative and the like can be used.

To the constituent layers of the silver halide photographic light-sensitive material of the present invention, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be added as plasticizers.

Further, in the present invention, a polymer latex can be contained in any one of the silver halide emulsion layers and the constituent layers other than the emulsion layers for the purpose of improving pressure resistance. As the polymer latex, a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid or styrene, a styrene-butadiene copolymer, an active methylene group, a polymer or copolymer comprising a monomer having a water-soluble group or a crosslinkable group with gelatin may be used. It can be preferably used.

Particularly, in order to increase the affinity with gelatin as a binder, a copolymer with a water-soluble group mainly composed of a hydrophobic monomer such as an alkyl ester of acrylic acid or styrene or a monomer having a crosslinkable group with gelatin is most preferable. It is preferably used. Desirable examples of the monomer having a water-soluble group include acrylic acid, methacrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, and styrenesulfonic acid. Desirable examples of the monomer having a crosslinking property with gelatin are provided. Examples thereof include glycidyl acrylate, glycidyl methacrylate, N-methylol acrylamide, and the like.

In the present invention, as a matting agent, for example, US Pat. Nos. 2,992,101 and 2,701,245
Nos. 4,142,894, 4,396,706 and the like, homopolymers of polymethyl methacrylate or polymers of methyl methacrylate and methacrylic acid, organic compounds such as starch, silica, titanium dioxide, Fine particles of an inorganic compound such as strontium sulfate and barium sulfate can be used in combination. The particle size is preferably from 0.6 to 10 μm, particularly preferably from 1 to 5 μm.

In the present invention, organic matter aggregated particles can be used as the matting agent. The term “organic matter aggregated particles” refers to a substance having a particle diameter of 0.1 mm.
It refers to aggregated particles having a particle diameter of 1.0 to 20 μm in which a plurality of temporary particles having a small particle diameter of 0.5 to 0.50 μm are aggregated. The shape of the aggregated particles may be spherical or amorphous. The component as an organic substance is arbitrarily selected from alkyl methacrylate, alkyl acrylate, methacrylate in which an alkyl group is substituted with fluorine or silicon, acrylate and styrene, and may be a homopolymer or a copolymer, but polymethyl methacrylate is preferred. Specific examples include GR-5 and GR-5P manufactured by Soken Chemical Co., Ltd. A preferable addition amount for obtaining the effect without deteriorating the haze is 10 to 200 mg / m ² .

In the present invention, for the purpose of improving the pressure resistance, it is preferable that the silver halide emulsion layer contains inorganic fine particles and / or a composite latex.

As the inorganic fine particles, the main components are silicon, aluminum, titanium, indium, yttrium, tin,
Oxide selected from antimony, zinc, nickel, copper, iron, cobalt, manganese, molybdenum, niobium, zirconium, vanadium, alkali metals, alkaline earth metals, etc. Among them, silicon oxide in terms of transparency and hardness (Colloidal silica), aluminum oxide, tin oxide,
Vanadium oxide and yttrium oxide are preferred. When these inorganic oxides are dispersed in water to form a sol,
The surface may be treated with alumina, yttrium, cerium, or the like in order to enhance the stability of its own water dispersion. In order to increase the affinity with gelatin, shelling may be performed with gelatin which has been crosslinked in advance. The preferred use amount of the inorganic fine particles used in the present invention is 0.05 to 1.0 in terms of a dry weight ratio to gelatin used as a binder of a layer to be added, preferably 0.1 to 0.1.
~ 0.7. The above-mentioned inorganic fine particles may be used in combination. The preferred particle size of the inorganic fine particles is 1 to 300 nm.

[0214] The hydrophilic colloid layer of the present invention contains a composite latex. The composite latex is contained in a weight ratio of 0.3 to 1.1 based on gelatin.

In the present invention, the composite latex is a dispersion of composite polymer fine particles composed of inorganic fine particles and a hydrophobic polymer, or a composite latex formed by polymerizing a composition having a hydrophobic monomer in the presence of inorganic fine particles. Refers to a dispersion of molecular fine particles.

Examples of the inorganic fine particles used in the composite latex according to the present invention include inorganic oxides, nitrides, and sulfides, and are preferably oxides. In particular,
Si, Na, K, Ca, Ba, Al, Zn, Fe, C
u, Sn, In, W, Y, Sb, Mn, Ga, V, N
b, Tu, Ag, Bi, B, Mo, Ce, Cd, Mg,
Single or composite oxides such as Be and Pb are preferable, and in particular, Si, Y, Sn, Ti, Al, V, Sb, In, Mn,
Single or multiple oxides of Ce and B are preferred from the viewpoint of miscibility with the emulsion.

These may be crystalline or amorphous, but are preferably amorphous. The average particle diameter of the inorganic fine particles is about 0.5 to 3000 nm, preferably 3 to 500 nm. The inorganic fine particles are preferably used by dispersing in water and / or a solvent soluble in water. The addition amount of the inorganic fine particles is 1 to 200 with respect to the hydrophobic polymer compound.
It is about 0% by weight, preferably 30 to 1000% by weight.

Examples of preferred oxides are shown below.

SO-1 SiO ₂ SO-11 ZrSiO ₄ SO-2 TiO ₂ SO-12 CaWO ₄ SO-3 ZnO SO-13 CaSiO ₃ SO-4 SnO ₂ SO-14 InO ₂ SO-5 MnO ₂ SO-15 SnSbO ₂ SO-6 Fe ₂ O ₃ SO-16 Sb ₂ O ₅ SO-7 ZnSiO ₄ SO-17 Nb ₂ O ₅ SO-8 Al ₂ O ₃ SO-18 Y ₂ O ₃ SO-9 BeSiO ₄ SO-19 CeO ₂ SO-10 Al ₂ SiO ₅ SO-20 Sb ₂ O ₃ Among these, particularly preferred are oxides of Si, and furthermore, colloidal silica.

In the present invention, the hydrophobic polymer means a polymer which does not substantially elute in an aqueous solution such as a developing solution.
As the hydrophobic monomer forming the hydrophobic polymer compound,
Vinyl esters, acrylic esters, methacrylic esters, olefins, styrenes, crotonic esters, itaconic diesters, maleic diesters, fumaric diesters, allyl compounds, vinyl ethers, vinyl ketones, vinyl Heterocyclic compounds,
Glycidyl esters, unsaturated nitriles, various unsaturated acids and the like can be mentioned, but those forming the composite latex used in the present invention are preferably selected from vinyl esters, acrylic esters and methacrylic esters. At least one kind or styrenes,
As the former, it is particularly preferred that the ester group has 6 or more carbon atoms. It is preferable to use a hydrophobic monomer having a glycidyl group in combination with these hydrophobic monomers, and to use at least 1% by weight, more preferably 20% by weight or more.

The polymerization method of the composite latex includes an emulsion polymerization method, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, a radiation polymerization method and the like.

(Example of Production of Composite Latex L-1) 100
A stirrer, a thermometer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser were attached to a 0 ml four-necked flask, and 360 cc of distilled water, 30% by weight of colloidal silica dispersion was introduced while introducing nitrogen gas for deoxygenation. After adding 126 g, the mixture was heated until the internal temperature reached 80 ° C., and 4.5 g of hydroxypropylcellulose and 1 g of dodecylbenzenesulfonic acid were added. 0.023 g of ammonium persulfate as initiator
Is added, and then 12.6 g of vinyl acetate is added.
Allowed to react for hours. After cooling, the pH was adjusted to 6 with a sodium hydroxide solution to obtain a composite latex L-1.

The silver halide photographic light-sensitive material of the present invention preferably contains a water-soluble polymer. As the water-soluble polymer, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone and the like described in US Pat. No. 3,271,158 can be effectively used. Polysaccharides such as dextrin, dextran, saccharose and pullulan are also effective. Among them, polyacrylamide, dextran and dextrin are preferable, and dextrin is particularly preferable. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less.

In the present invention, the amount of the hydrophilic binder in the silver halide emulsion layer is preferably 3.0 g / m ² or less, more preferably 1.0 g or more per one side of the support when the emulsion layer is on both sides of the support. 2.0 g / m ² or less. When it is on one side of the support, the weight is preferably 6.0 g / m ² or less, more preferably 4.0 g / m ² or less.

The silver halide photographic light-sensitive material of the present invention may be a black-and-white silver halide photographic light-sensitive material (for example, a light-sensitive material for medical use, a light-sensitive material for printing, a negative light-sensitive material for general photography), a color photographic light-sensitive material (for example, a color negative). Photographic materials, color reversal photographic materials, color printing photographic materials), diffusion transfer photographic materials, heat-developable photographic materials, etc., preferably black-and-white silver halide photographic materials, and particularly preferably medical photographic materials. It is.

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 an emulsion layer or a layer having another layer.
And / or a precursor thereof.

The silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer of the light-sensitive material of the present invention preferably contain an inorganic or organic hardener. For example, chromium salts (chrome alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea,
Methylol dimethylhydantoin), dioxane derivatives (such as 2,3-dihydroxydioxane), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'- Active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine) such as methylenebis (β- (vinylsulfonyl) propionamide), mucohalic acids (such as mucochloric acid and mucophenoxycyclolic acid), isoxazoles , 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination, and among them, JP-A-53-41221, JP-A-53-57257 and JP-A-53-57257.
Active vinyl compounds described in JP-A-162456 and JP-A-60-80846 and active halogen compounds described in U.S. Pat. No. 3,325,287 are preferred.

As the hardener of the present invention, a polymer hardener can also be effectively used. For example, dialdehyde starch, polyacrolein, a polymer having an aldehyde group such as an acrolein copolymer described in US Pat. No. 3,396,029, a polymer having an epoxy group described in US Pat. No. 3,623,878, US Pat. , 362, 827, RD-17
No. 333 (1978), a polymer having a dichlorotriazine group, a polymer having an active ester group described in JP-A-56-66841, a polymer having an active ester group described in JP-A-56-142524, U.S. Pat. 40
7, JP-A-54-65033, RD-16725
(1978), a polymer having an active vinyl group or a group that is a precursor thereof is preferable. Among them, an active vinyl group or a polymer having a long spacer as described in JP-A-56-124524 is preferable. Polymers in which the precursor groups are attached to the polymer backbone are particularly preferred.

In the photographic light-sensitive material of the present invention, an appropriate amount of a hardening agent is added in advance in the coating step of the photographic material to adjust the water swelling ratio in the development-fixing-rinsing step so as to be suitable for rapid processing. By doing so, it is preferable to reduce the water content in the photosensitive material before the start of drying.

The silver halide light-sensitive material of the present invention preferably has a swelling ratio of 150 to 250% during the development process, and a film thickness after expansion of 70 μm or less. 250% water swelling
If the temperature exceeds the limit, drying failure occurs, and for example, conveyance failure also occurs in automatic developing machine processing, particularly in rapid processing.

When the water swelling ratio is less than 150%, development unevenness and residual color tend to increase during development. The water swelling ratio as referred to herein means the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, and this is divided by the film thickness before processing and multiplied by 100. .

The support which can be used in the silver halide photographic light-sensitive material of the present invention includes, for example, the aforementioned RD-1
7643 and RD-308119, page 1009.

As a suitable support, a plastic film or the like may be used. The surface of the support may be provided with an undercoat layer for improving the adhesion of the coating layer, or may be subjected to corona discharge, ultraviolet irradiation or the like.

In the silver halide photographic light-sensitive material of the present invention, various additives can be further added to the silver halide emulsion depending on the purpose. Examples of additives and others used are RD-17643 (December 1978), 1871
6 (November 1979) and 308119 (1989)
December, December). The locations of those descriptions 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 Fogging inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 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, preferred silver halide copying of the present invention Photographic processing method of the photographic material (hereinafter, sometimes referred to as processing method) will be described.

In the method for processing a silver halide photographic light-sensitive material of the present invention, the silver halide photographic light-sensitive material of the present invention is preferably processed in a development processing time of 12 seconds or less. here,
The development processing time refers to the time during which the photosensitive material is immersed in the developer. More specifically, for example, when processing is performed by an automatic developing machine of a roller transport type, the photosensitive material starts to come out from the moment when the tip of the photosensitive material enters the developer. Time to the moment. The development processing time is more preferably from 1 second to 10 seconds, still more preferably from 2 seconds to 7 seconds. The development temperature is preferably 25
-50 ° C, more preferably 30-40 ° C. The fixing processing time is preferably from 1 second to 10 seconds, and more preferably from 2 seconds to 7 seconds. The fixing processing temperature is preferably from 20C to 50C, more preferably from 30C to 40C. The temperature and time of the water washing treatment are 0-50 ° C for 2 seconds-15.
Seconds are preferable, and 2 seconds to 8 seconds at 15 ° C to 40 ° C are more preferable.

The light-sensitive material which has been developed, fixed and washed (or stabilized) is dried through a squeeze roller for squeezing the washing water. Drying is performed at 40 ° C. to 100 ° C., and the drying time can be appropriately changed depending on the environmental temperature.
It may be 12 seconds, particularly preferably at 40 ° C to 80 ° C for 3 seconds to
8 seconds. More preferably, a far infrared heater is used. Furthermore, the total processing time (DRY TO
DRY) is preferably from 10 seconds to 30 seconds, more preferably from 10 seconds to 25 seconds.

As a developing solution for developing the silver halide photographic light-sensitive material of the present invention, as a developing agent, for example, dihydroxybenzene, for example, hydroquinone described in JP-A-4-15641, JP-A-4-16841, etc.
Examples of 3-pyrazolidones such as para-aminophenols such as p-aminophenol, N-methyl-p-aminophenol, and 2,4-diaminophenol include 1-phenyl-3-pyrazolidones and 1-phenyl-3- Pyrazolidone, 1-phenyl-4-methyl-4-
Hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone and the like, and further, ascorbic acids, which are used alone or in combination as necessary.

The above paraaminophenols and 3-aminopyrazolidones are preferably used in an amount of 0.004 mol / l, more preferably 0.04 to 0.12 mol / l.

The dihydroxybenzenes, para-aminophenols, 3
The total molar number of pyrazolidones and ascorbic acids is 0.
It is preferably at most 1 mol / liter.

In particular, in the method for processing a silver halide photographic light-sensitive material of the present invention, a developer containing substantially no dihydroxybenzene-based developing agent and containing the compound represented by the formula (A) It is preferable that the silver halide photographic light-sensitive material of the present invention is processed by an automatic processor using a development replenisher.

In the compound represented by formula (A) according to the present invention, R ₁ and R _{2 in} the formula each represent a hydroxy group or an amino group (substituents are alkyl groups having 1 to 10 carbon atoms, for example, methyl , Ethyl, hydroxyethyl, etc. as substituents), acylamino group (acetylamino, benzoylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino, p-toluenesulfonylamino group, etc.), alkoxysulfonyl Amino (methoxycarbonylamino group, etc.), mercapto group, alkylthio group (methylthio, ethylthio group, etc.)
Represents Preferred examples of R ₁ and R ₂ include a hydroxy group,
Examples include an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group. P and Q in the formula represent an alkyl group, an alkoxy group, a hydroxy group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, and a mercapto group. Combine to form R ₁ ,
R ₂ represents a group of atoms necessary for forming a 5- to 8-membered ring together with two vinyl carbon atoms substituted with Y and a carbon atom substituted with Y.

Specific examples of the ring structure include -O- and -C (R
₃ ), R ₄ )-, C (R ₅ ) =, -C (= O)-, -N
(R ₆ )-and -N =. Where R ₃
To R ₆ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (as a substituent, a hydroxy group, a carboxy group or a sulfo group), an optionally substituted allyl group having 6 to 15 carbon atoms Examples of the group include an alkyl group, a halogen atom, a hydroxy group, a carboxy group, and a sulfo group), a hydroxy group, and a carboxyl group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 8-membered ring. These 5
Examples of 8-membered rings include dihydrofuranone, dihydropyrone, pyranone, cyclopentenone, cyclohexenone,
Pyrolinone, pyrazolinone, pyridone, azacyclohexenone, uracil ring and the like can be mentioned, and preferable examples thereof include dihydrofuranone, cyclopentenone, cyclohexenone, pyrrolinone, azacyclohexenone and uracil ring.

In the method for processing a silver halide photographic light-sensitive material of the present invention, the compound represented by the above general formula (A) is preferably used in an amount of 0.005 to 0.5 mol per liter of developer. , More preferably 0.02 to 0.4 mol.

Specific examples of the compound represented by formula (A) are shown below, but the invention is not limited thereto.

[0246]

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[0247]

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[0248]

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[0249]

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The above compounds are typically ascorbic acid or erythorbic acid or a derivative thereof, and are commercially available or can be synthesized by a known synthesis method.

The developer preferably contains a 1-phenyl-3-pyrazolidone-based or p-aminophenol-based developing agent as an auxiliary developing agent of the above compound.

Preservatives may include sulfites, such as potassium sulfite, sodium sulfite, and reductones, such as piperidinohexose reductone, which are preferably 0.2-1 mol / l, more preferably Is preferably 0.3 to 0.6 mol / liter.
Also, the addition of a large amount of ascorbic acids leads to processing stability.

The alkaline agent includes a pH adjuster such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate and potassium tertiary phosphate.

Further, borate described in JP-A-61-28708, saccharose described in JP-A-60-93439,
Buffers such as acetoxime, 5-sulfosalicylic acid, phosphates and carbonates may be used. The content of these chemicals increases the pH of the developer from 9.0 to 13, preferably from pH 10 to 10.
Choose to be 12.5.

As a solubilizer, polyethylene glycols and esters thereof can be contained, and as a sensitizer, for example, a development accelerator, a surfactant, and the like can be contained.

As the silver sludge inhibitor, for example, those described in
A silver stain inhibitor described in JP-A-6-106244;
The sulfide and disulfide compounds described in No. 1844, and the cysteine derivatives and triazine compounds described in Japanese Patent Application No. 4-92947 are preferably used.

As organic inhibitors, azole organic antifoggants such as indazole, imidazole, benzimidazole, triazole, benzotriazo, tetrazole and thiadiazole compounds are used.

The inorganic inhibitors include sodium bromide, potassium bromide, potassium iodide and the like. In addition,
L. F. A. Menson, "Photographic Processing Chemistry," Focal Press (19
66), pages 226-229, U.S. Pat.
No. 15,2,592,364, JP-A-48-649
No. 33 may be used.

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

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

In the present invention, the replenishment of the developer replenishes the amount corresponding to the processing agent fatigue and oxidative fatigue. Examples of the replenishment method include replenishment by width and feed speed described in JP-A-55-126243, area replenishment described in JP-A-60-104946, and area replenishment controlled by the number of continuously processed sheets described in JP-A-1-149156. May be.

In the method for processing a silver halide photographic light-sensitive material of the present invention, when the processing is performed while continuously replenishing a processing solution according to the light-sensitive material to be processed, the replenishment amount of the developing solution is processed. It is preferable that the replenisher is replenished at 15 to 250 cc per 1 m ^{2 of the} photosensitive material, and more preferably 15 to 100 cc.

Preferred fixing solutions may include fixing materials commonly used in the art. pH is 3.
8 or more, preferably 4.2 to 5.5.

Examples of the fixing agent include thiosulfates such as ammonium thiosulfate and sodium thiosulfate. Ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The concentration of the ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / l, more preferably in the range of 0.8 to 3 mol / l. The fixing solution may be one that forms an acidic hardening. In this case, aluminum ions are preferably used as the hardener. For example, it is preferable to add in the form of aluminum sulfate, aluminum chloride, potassium alum and the like. Other fixatives include 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.), and hydrochloric acid, if desired. PH adjusting agents such as various acids, metal hydroxides (potassium hydroxide and sodium hydroxide), and chelating agents having water softening ability. Examples of the fixing accelerator include JP-B-45-35754 and 58-122535.
And thioethers described in U.S. Pat. No. 4,126,459.

Further, a method of supplying a developer and / or a fixing agent as a solid processing agent to a processing tank of an automatic developing machine is also preferably used.

Here, the solid processing agents are powder processing agents, solid processing agents such as tablets, pills and granules, etc., which have been subjected to moisture proof processing as required.

The powder means an aggregate of fine crystals. Granules are obtained by adding a granulation process to powder, and have a particle size of 5
It refers to a granular material of 0 to 5000 μm. Tablets are obtained by compressing powder or granules into a certain shape.

To solidify the photographic processing agent, a concentrated solution or a fine or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is added to the surface of the temporarily molded photographic processing agent. Any means can be adopted, such as forming a coating layer by spraying (Japanese Patent Application Nos. 2-135887 and 2-13987).
No. 203165, No. 2-203166, No. 2-203
No. 167, 2-203168 and 2-34009
No.).

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

As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, and spray drying granulation are used. Can be done.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Furthermore, the particle size distribution is
Preferably, 0% or more is within a deviation of ± 100 to 150 μm. Next, when the obtained granules are compressed under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, and a briquetting machine can be used. The solid processing agent obtained by pressurization and compression can take any shape, but from the viewpoint of productivity, handling properties or dust when used on the user side, cylindrical, so-called tablets are used. preferable.

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

The method for producing a tablet processing agent is described in, for example, JP-A-51-61837, JP-A-54-155038, and JP-A-52-55038.
No. 88025, British Patent No. 1213808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-10942 and 2-109.
It can be produced by a general method described in the specification of JP-A Nos. 043, 3-39735 and 3-39939. Furthermore, powder processing agents are described, for example, in JP-A-54-13333.
No. 2, British Patent Nos. 725,892 and 729,862, and German Patent No. 3,733,861.

The solid processing agent has a bulk density of 1.0 g /
Preferably ^{cm 3 ~2.5g / cm 3, 1.0g} / cm 3
If it is larger, the strength of the obtained solid is 2.5 g /
When the diameter is smaller than ³ cm3, the solubility of the obtained solid is more preferable. When the solid processing agent is granules or powder, the bulk density is preferably 0.40 to 0.95 g / cm ³ .

Solid processing agents are used in photographic processing agents such as a developer, a fixing agent, and a rinsing agent, but the developer has a great effect of stabilizing photographic performance.

The solid processing agent may be solidified as only one part of a certain processing agent, but preferably all the components of the processing agent are solidified. It is desirable that each component is molded as a separate solid processing agent and is mounted in the same unit.
It is also desirable that the separate components are packaged in the order in which they are periodically and repeatedly placed in a package.

It is preferable that all the processing agents to be replenished into each processing tank according to the processing amount information are charged as solid processing agents.
When replenishing water is required, replenishing water is replenished based on the processing amount information or other replenishing water control information. In this case, the liquid to be replenished to the treatment tank can be only replenishing water. That is, when two or more types of processing tanks need replenishment, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the size of the automatic developing machine can be reduced. The replenishing water tank may be provided outside or externally, or may be built in an automatic developing machine, and the built-in water tank is preferable in terms of space saving and the like.

In the case where the developer is solidified, it is preferable that all of the alkali agent and the reducing agent are solidified, and in the case of tablets, at least three or less, most preferably one agent is used. It is. When the solid processing agent is divided into two or more agents, it is preferable that these tablets and granules are packaged in the same manner.

It is preferable to take an image using the photosensitive material of the present invention and a radiographic intensifying screen. The filling rate of the phosphor in the phosphor layer of the radiation intensifying screen is preferably 68% or more, more preferably 70% or more, and most preferably 72% or more.

The phosphor layer has a thickness of 150 μm or more,
250 μm or less is preferred. The thickness of the phosphor layer is 150μ
This is because if it is less than m, sharpness rapidly deteriorates.

It is preferable that the radiographic intensifying screen is filled with a phosphor in a gradient particle size structure. In particular, it is preferable to apply large-sized phosphor particles to the surface protective layer side and to apply small-sized phosphor particles to the support side.
In the case of 0 μm and those having a large particle size, the range is preferably 10 to 30 μm.

In the fluorescent intensifying screen used in the combination, the filling rate of the phosphor particles is increased so that the X-ray absorption of each intensifying screen is 3 x 100 μm in thickness of the phosphor layer.
It is preferably 0% or more. The amount of X-ray absorption was determined as follows. That is, with a three-phase power supply, the inherent filtration is 80K from an X-ray generator equivalent to 2.2 mm of aluminum.
X-rays generated from a tungsten target operated by the VP are transmitted through a 3 mm-thick aluminum plate having a purity of 99% or more, and are passed through a tungsten anode of the target tube.
The X-rays arrived at the radiographic intensifying screen fixed at the position of 00 cm, and then measured at 50 cm after the phosphor layer of the radiographic intensifying screen using an ionizing dosimeter to determine the amount of X-ray absorption. As a reference, the X-ray dose at the above measurement position measured without passing through the intensifying screen was used.

Preferred binders used for the radiographic intensifying screen include thermoplastic elastomers. Specifically, it is selected from the group consisting of polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, ethylene vinyl acetate, polyvinyl chloride, natural rubber, fluorine rubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber and silicone rubber. At least one thermoplastic elastomer is included.

The filling rate of the phosphor can be determined from the porosity of the phosphor layer formed on the support by the following equation.

[0284]

(Equation 1)

Preferred phosphors for use in the radiographic intensifying screen include the following.

A tungstate-based phosphor (CaWO ₄ ,
MgWO ₄ , CaWO ₄ : Pb, etc.), terbium-activated rare earth oxysulfide-based phosphor [Y ₂ O ₂ S: Tb, Gd ₂ O ₂ S:
Tb, La ₂ O ₂ S: Tb, (Y, Gd) ₂ O ₂ S: Tb,
Tm etc.), terbium-activated rare earth phosphate-based phosphor (YP
O ₄ : Tb, GdPO ₄ : Tb, LaPO ₄ : Tb, etc.),
Terbium-activated rare earth oxyhalide phosphor La
OBr: Tb, LaOBr: Tb. Tm, LaOCl:
Tb, LaOCl: Tb. TmGdOBr: Tb, Gd
OCr: Tb, etc.), thulium-activated rare earth oxyhalide phosphor (LaOBr: Tm, LaOCl: Tm)
Etc.), barium sulfate-based phosphor [BaSO ₄ : Pb, Ba
SO ₄ : Eu ²⁺ , (Ba.Sr) SO ₄ : Eu ²⁺ etc.], 2
Eurobium-activated alkaline earth metal phosphate-based phosphor [Ba3 (PO ₄ ) ₂ : Eu ²⁺ , (Ba, Sr) ₃ , (P
O ₄ ) ₂ : Eu ₂ etc.] divalent eurobium-activated alkaline earth metal fluorohalide-based phosphor [BaFCl: Eu
²⁺ , BaFBr: Eu ²⁺ , BaFCl: Eu ²⁺ . Tb,
BaFBr: Eu ²⁺ . Tb, BaF ₂ . BaCl ₂ . XB
aSO ₄ . KCl: Eu ²⁺ , (Ba.Mg) F ₂ . BaC
l ₂ . KCl: Eu ²⁺ etc.], iodide-based phosphor (CSI:
Na, CSI: Tl, NaI. KI: Tl, etc.) Sulfide-based phosphor [ZnS: Ag, (Zn.Cd) S: Ag, (Z
n. Cd) S: Cu, (Zn. Cd) S: Cu. Al
Etc.), a hafnium phosphate-based phosphor (HfP ₂ O ₇ : Cu
Etc.) However, the phosphor used is not limited to these, and any phosphor that emits light in the visible or near ultraviolet region upon irradiation with radiation can be used.

[0287]

EXAMPLES Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto. Example 1 <Preparation of hexagonal tabular silver iodobromide> Preparation of Em-1 A1 ossein Gelatin 75.5 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous ethanol) 6.78 ml Potassium bromide 64.7 g Make up to 10800 ml with water.

B1 0.7N silver nitrate aqueous solution 1340ml C1 2.0N silver nitrate aqueous solution 1500ml D1 1.3N potassium bromide aqueous solution 410ml E1 2.0N potassium bromide aqueous solution The following silver potential control amount F1 ossein gelatin 125g water 4000ml G1 KSCN aqueous solution ( 2N) 60 cc H1 Fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μ) (*) Equivalent to 0.008 mol * 5.0 weight containing 0.06 mol of potassium iodide 2 liters of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added to 6.64 liters of a 6% aqueous gelatin solution over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are formed, p is added using an aqueous sodium carbonate solution.
H was adjusted to 6.0.

At 55 ° C., JP-B-58-58288, 5
Solution A using a mixing stirrer described in JP-A-8-58289.
400 ml of the solution B1 and the entire amount of the solution D1 were added to 1 by a simultaneous mixing method over 40 seconds to form nuclei.

After the addition of the solution B1 and the solution D1, the solution F1 is added, and the mixture is heated to 70 ° C. for ripening. After the remaining amount of the solution B1 was further added over 25 minutes, the mixture was aged for 10 minutes using a 28% aqueous ammonia solution, and the pH was adjusted with acetic acid.
To neutral. Simultaneous addition and mixing of solutions C1 and E1 at a rate commensurate with the critical growth rate while maintaining pAg = 7.8,
After the total amount of C1 was added, G1 and H1 were added. After stirring for 5 minutes, soluble salts were desalted and removed by sedimentation.

Subsequently, the emulsion was heated to 47 ° C. and subjected to spectral sensitization and chemical sensitization by the following method [sensitization-1].

[Sensitization-1] A predetermined amount of each of the spectral sensitizing dyes A and B was added as a dispersion in the form of fine solid particles, and then a mixed aqueous solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate and triphenylphosphine selenide were added. And aged for 2 hours and 30 minutes in total. At the end of ripening, 4-hydroxy-6-methyl-1,3,3 is used as a stabilizer.
An appropriate amount of 3a, 7-tetrazaindene (TAI) was added.

The spectral sensitizing dyes and other additives and the amounts thereof (per mole of silver halide) are shown below.

Spectral Sensitizing Dye (A) 5,5′-Dichloro-9-ethyl-3,3′-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride 390 mg Spectral sensitizing dye (B ) 5,5'-Di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di (4-sulfobutyl) benzimidazolocarbocyanine sodium anhydride 4 mg adenine 10 mg sodium thiosulfate (sulfur sensitized) 3.3 mg ammonium thiocyanate 50 mg chloroauric acid (gold sensitizer) 2.0 mg silver iodide fine particles 5 mmol triphenylphosphine selenide (selenium sensitizer) 4.0 mg stabilizer (TAI) 1000 mg The silver iodide fine particles are 3% by weight of gelatin used during the emulsion growth, and silver iodide particles (average particle size of 0.05 μm).
Is a fine grain emulsion composed of

A solid fine particle dispersion of the spectral sensitizing dye was prepared by a method according to the method described in Japanese Patent Application No. 4-99437.

That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature had been previously adjusted to 27 ° C., and the mixture was subjected to 3.5 with a high-speed stirrer (dissolver).
Obtained by stirring at 00 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., stirred and completely dissolved. 3.8 kg of photographic gelatin on the other hand
Was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at 50 ° C. at a peripheral speed of the dispersion blade of 40 m / sec for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was reduced to 0.3.
Ethyl acetate was removed while stirring until the amount became less than wt%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. A part of the dispersion thus obtained was fractionated and used for experiments.

Emulsion Em-1 thus prepared was composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0 for 90% or more of the total projected area of silver halide grains. It was confirmed with an electron microscope that the average thickness was 0.20 μm and the average particle size (in terms of circular diameter) was 0.80 μm. The distribution of the circle equivalent diameter was 15%.

Preparation of Em-2 Em-2 was prepared in the same manner as Em-1, except that the solution C1 was changed to the solution C2.

C2 2.0 N silver nitrate aqueous solution 1500 ml Thallium nitrate 1.05 g Preparation of Em-3 In the preparation of Em-1, except that the solution B1 was changed to the solution B3 and the solution C1 was changed to the solution C3, in the same manner as in Em-1. Thus, Em-3 was prepared.

B3 0.7N silver nitrate solution 1340ml thallium nitrate 0.25g C3 2.0N silver nitrate aqueous solution 1500ml thallium nitrate 0.80g Preparation of Em-4 In the same manner as Em-1, it was added up to TAI to prepare an emulsion. The following solution I-4 was added, and stirring was stopped for 5 minutes.
m-4 was obtained.

I-4 1.05 g of thallium nitrate 20 ml of distilled water Next, an additive described in the second layer (emulsion layer) described below was added to the obtained emulsion to prepare an emulsion layer coating solution. At the same time, a coating solution for the dye layer and a coating solution for the protective layer were prepared using the additives described in the first layer (dye layer) and the third layer (protective layer), and the coating amount was determined using these three coating solutions. Has a silver content of 1.6 g / m per side
^2. Simultaneous double-sided coating on the support at a speed of 80 m / min using two slide hopper coaters so that the amount of gelatin applied is 2.5 g / m ^2, and drying for 2 min 20 sec. . 1-4 were obtained. As a support, glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%
% And butyl methacrylate, an aqueous dispersion of a copolymer obtained by diluting the copolymer composed of three monomers of 40 wt% to 10 wt% and a colloidal tin oxide dispersion (Japanese Patent Application No. 7-231445). Using a mixture of (1) and (2) as a subbing liquid, a polyethylene terephthalate film base colored blue with a concentration of 0.15 for an X-ray film of 175 μm was used.

The additives used for each layer are as follows.
The amount of addition is shown in an amount per 1 m ² .

First Layer (Dye Layer) Solid Fine Particle Dispersion Dye (AH) 20 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2,4- Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² latex (L) 0.2 g / m ² Potassium polystyrene sulfonate 50 mg / m ² Second layer (emulsion layer) Potassium tetrachloropalladium (2) 100 mg / m ² Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5- triazine 5 mg / m ² t-butylcatechol 5 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 20mg / m ² styrene - anhydrous Sodium maleic acid copolymer 80 mg / m ² of polystyrene sulphonic acid 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl - triphenyl - phosphonium chloride 1 mg / m ² 1,3-dihydroxybenzene-4- Ammonium sulfonate 50 mg / m ² 2-mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² Compound (H) 0.5 mg / m ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 20 mg / m ² Compound (M) 5 mg / m ² Compound (N) 5 mg / m ² Composite latex (L-1) 1.0 g / m ² dextrin (average molecular weight about 1000) 0.2 g / m ² dextran (average molecular weight of about 40000) 0.2g / m ² styrenesulfonic acid isocyanatomethyl Um (molecular weight: about 500,000) 7 mg / m ² However, gelatin coating amount was adjusted to be 0.8 g / m ^2.

Third Layer (Lower Layer of Protective Layer) Gelatin 0.2 g / m ² Tricresyl phosphate 0.2 g / m ² Latex (L) 0.2 g / m ² Sodium polyacrylate (average molecular weight 50,000) 30 mg / m ² sodium styrene sulfonate (molecular weight: about 500,000) 7 mg / m ² 4th layer (upper protective layer) matting agent 27 mg / m ² consisting of gelatin 0.28 g / m ² polymethyl methacrylate (area average particle diameter 7.0μm ) 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² latex (L) 0.2 g / m ² colloidal silica (average particle size 0.014 μm) 50 mg / m ² poly Acrylamide (average molecular weight 10,000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (SI) 50 mg / m ² Compound (I) 30 mg / m ² Compound (J) 2 mg / m ² Compound (S-1) 7 mg / m ² Compound (K) 15 mg / m ² Compound (O) 50 mg / m ² Compound (S-2) 5 mg / M ² compound (F-1) 3 mg / m ² compound (F-2) 2 mg / m ² compound (F-3) 1 mg / m ² compound (F-4) 10 mg / m ² compound (P) 50 mg / m ²

[0306]

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[0307]

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[0308]

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<Sensitometry Evaluation> Sample N obtained
o. Photographic characteristics were evaluated using the samples Nos. 1 to 4. First, sample 2
The film was sandwiched between two screens (KO-250, manufactured by Konica Corporation), exposed to X-rays at a tube voltage of 80 kvp and a tube current of 100 mA for 0.05 seconds through an aluminum wedge, and exposed to light. went.

[0310] After the treatment, fog and sensitivity were measured. The fog is represented by the lowest density, the sensitivity is represented by the reciprocal of the exposure amount that gives a density of fog + 1.0, and the sample No. The relative sensitivities when the sensitivities in the processing of No. 1 were set to 100 were shown. Table 1 shows the obtained results.

<Evaluation of Pressure Resistance> Evaluation of Scratch Resistance A load of 5 g was applied to each of Nos. 1 to 4 using a 0.3 mm needle-head scratch hardness tester, and then the photographic processing of Process 1 was performed, and the pressure fogging density was measured with a microdensitometer. The degree of fogging was determined for Sample No. The fog rise of 1 is shown as a relative value when 100 is taken. Table 1 shows the obtained results.

Evaluation of Roller Marks The pressure characteristics during development (pressure marks by rollers of an automatic developing machine, ie, the degree of generation of roller marks) were evaluated as follows. That is, the sample No. 1-4 for 10cm
The sheet was cut to a size of × 30 cm, and white light exposure was applied so that the density became 1.0. In processing-1, the roller in the developing step of the automatic developing machine was changed to a special facing roller having a strong unevenness, the sample was subjected to photographic processing, and roller marks generated at that time were observed. And was classified into 5 stages.

5: No roller mark occurred 4: Very slight occurrence 3: Slight occurrence (within practical tolerance) 2: Many occurrence (out of practical tolerance) 1: Extremely large occurrence

<Evaluation of Silver Tone> Sample No. 35 cm × 43 cm. After uniformly exposing 1 to 6 with tungsten light so that the transmitted light blackening density becomes 1.0, the photographic processing of the following processing -1 is performed, and the processed film sample is yellowed according to the following five-step evaluation. The degree of taste was visually evaluated.

Evaluation Rank 1: Yellowish color is strong and clearly does not endure practical use 2: Some yellowishness is recognized, and there is a concern that it becomes a problem in practical use 3: Yellowishness is slightly recognized, but under normal conditions It can be used in practical use 4: Yellow color is hardly recognized and there is no problem in practical use. 5: Yellow color is not recognized at all and it has a cool black tone.

Table 1 shows the obtained results.

[Treatment-1] (Development using solid processing agent containing hydroquinone) A tablet for replenishment of development was prepared according to the following operation (A, B).

Operation (A) 3000 g of hydroquinone as a developing agent is pulverized in a commercially available bandam mill until the average particle size becomes 10 μm. 3000 g of sodium sulfite and 2 parts of potassium sulfite were added to the fine powder.
000 g and 1000 g of Dimaison S were added and mixed in a mill for 30 minutes, and then at room temperature for about 10 minutes in a commercially available stirring granulator.
After granulating by adding 30 ml of water, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the moisture of the granulated material. 100 g of polyethylene glycol 6000 was added to the granules thus prepared in 2 parts.
After uniformly mixing the mixture in a room conditioned at 5 ° C. and 40% RH or less for 10 minutes using a mixer, the obtained mixture was mixed with a tableting machine obtained by modifying a Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. The tablet was compressed and compressed at a filling amount of 3.84 g per tablet to prepare 2500 tablets A for development replenishment.

Procedure (B) DTPA 100 g, potassium carbonate 4000 g, 5-methylbenzotriazole 10 g, 1-phenyl-5-mercaptotetrazole 7 g, 2-mercaptohypoxanthine 5 g, KOH 200 g, N-acetyl-D, L-penicillamine Pulverization and granulation are performed as in (A). The amount of water to be added is 30.0 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. The mixture obtained in this manner was compressed into tablets using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with the filling amount per tablet being 1.73 g, and subjected to compression tableting.
Zero tablets B for replenishment for development were prepared.

Next, replenishing tablets for fixing were prepared by the following operations (C, D).

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is ground in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), the amount of water added was 500 m
and perform granulation. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules. 4 g of sodium N-lauroylalanine is added to the granules thus prepared, and mixed for 3 minutes in a room conditioned at 25 ° C. and 40% RH or less using a mixer. Next, the obtained mixture was subjected to compression tableting using a tableting machine obtained by modifying a Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. to make the filling amount per tablet 6.202 g, and 2500 fixing tablets C for replenishment were used. A preparation was made.

Operation (D) Boric acid 1000 g, aluminum sulfate / 18-hydrate 150
0 g, sodium hydrogen acetate (equimolar mixture of glacial acetic acid and sodium acetate and dried) 3000 g, tartaric acid 200
g is ground and granulated in the same manner as in the operation (A). The amount of water to be added is 100 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. 4 g of sodium N-lauroylalanine was added to the thus-prepared product, and the mixture was mixed for 3 minutes. The obtained mixture was converted into tablets per tablet using a tableting machine modified from Tuff Presto Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Was compression-compressed at 4.562 g to prepare 1250 fixing replenishing tablets D.

Developer Starter Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make 1 L.

At the start of the processing of the developing solution (running start), the developing tank was filled with 16.5 liters of the developing solution diluted with diluting water and 330 ml of a starter was added as a starting solution to fill the developing tank to start the processing. did. still,
The pH of the developer to which the starter was added was 10.45.

The sample prepared above was exposed to light so that the optical density after development processing was 1.0, and the sample was run. For the running, an automatic developing machine SRX-502 equipped with a charging member of a solid processing agent and modified so as to be able to process at a processing speed of 25 seconds was used.

During the running, the photosensitive material contains 0.6 photosensitive material.
The above-mentioned ^two agents A and B and 2 ml of water were added per 2 m ² . When each of A and B was dissolved in 38 ml of water, the pH was 10.70. ^Two fixing agents, one D agent and 74 ml of water were added to the fixing solution per 0.62 m ² of the photosensitive material. The rate of addition of water to each processing agent was started almost simultaneously with the addition of the processing agent, and was added at a constant speed for 10 minutes in approximately proportion to the dissolution rate of the processing agent.

(Processing Conditions) Development 35 ° C. 8.2 seconds Fixing 33 ° C. 5 seconds Rinse at room temperature 4.5 seconds Squeeze 1.6 seconds Drying 40 ° C. 5.7 seconds 25 seconds in total

[0328]

[Table 1]

According to the sample No. of the present invention, 2-No. No. 4 is sample No. 4. Compared to No. 1, it is found that the toner has low fog and high sensitivity, has significantly improved scratch resistance, roller marks and the like, and has a good silver tone. In particular, Sample No. to which thallium ion was more uniformly added. 3 is excellent.

Example 2 <Preparation of silver chloroiodide perpendicular parallelogram tabular grains> Preparation of Em-5 A5 Ossein gelatin 75.0 g KI 1.25 g NaCl 33.0 g Make up to 15000 ml with distilled water B5 Silver nitrate 410 g Distillation Make 684 ml with water 11590 g C5 silver nitrate Make 19316 ml with distilled water D5 KI 4.0 g NaCl 140 g Make 684 ml with distilled water E5 NaCl 2272 g KBr 3277 g Make 19274 ml with distilled water At 40 ° C., Japanese Patent Publication No. 58-58888; 58-
Solution A5 in a mixing stirrer as described in US Pat.
, The total amount of solution B5 and solution D5 was added over 1 minute. The EAg was adjusted to 149 mV, and after Ostwald ripening for 20 minutes, the total amount of Solution C5 and Solution E5 was added over 320 minutes. Meanwhile, EAg was controlled at 100 mV.

Immediately after the addition was completed, desalting and washing were performed.

Subsequently, the above emulsion was heated to 55 ° C., and subjected to spectral sensitization and chemical sensitization by the following method [Sensitization-2].

[Sensitization-2] As a compound adsorbed on silver halide, 4-hydroxy-6-methyl-1,3,3a,
After addition of 7-tetrazaindene (TAI), predetermined amounts of the following spectral sensitizing dyes, a mixed aqueous solution of ammonium thiocyanate and chloroauric acid, 1-ethyl-3- (2-thiazolyl) thiourea, triphenyl A solid fine particle dispersion of phosphine selenide and butyl-diisopropylphosphine telluride was added, and the mixture was stirred for 20 minutes. Thereafter, 0.1 mol% of a silver bromide fine particle emulsion was added, and ripening was performed for a total of 2 hours. At the end of ripening, 1-phenyl-5-
Mercaptotetrazole (PMT) and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) were added.

The spectral sensitizing dyes and other additives and their amounts (per mole of silver halide) are shown below.

Spectral sensitizing dye (D-31) 350 mg Spectral sensitizing dye (D-32) 25 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 50 mg Ammonium thiocyanate 145 mg Chloroauric acid (gold sensitizer) 25.5 mg 1-ethyl-3- (2-thiazolyl) thiourea (sulfur sensitizer) 5.0 mg triphenylphosphine selenide (selenium sensitizer) 3.0 mg butyl- Diisopropylphosphine telluride (tellurium sensitizer) 0.5 mg Silver bromide fine particles 0.1 mol% PMT (as a stabilizer at the end of chemical ripening) 10 mg TAI (as a stabilizer at the end of chemical ripening) 100 mg A solid fine particle dispersion is prepared by adding a predetermined amount of a spectral sensitizing dye to water whose temperature has been previously adjusted to 27 ° C., and using a high-speed stirrer (dissolver). At 3,500rpm 30~120
Obtained by stirring for minutes.

Emulsion Em-5 thus prepared was
65% of the total projected area of the silver halide grains is a right-angled parallelogram tabular grain having a (100) plane as a main plane,
Electron microscopy revealed that the average thickness was 0.14 μm, the average particle size was 1.0 μm, and the coefficient of variation was 25%.

Preparation of Em-6 Em-6 was prepared in the same manner as Em-5, except that solution C5 was changed to solution C6.

C6 Silver nitrate 11590 g Thallium nitrate 18.8 g Make up to 19316 ml with distilled water Preparation of Em-7 Except for changing the solution B5 to the solution B7 and the solution C5 to the solution C7 in the preparation of Em-5, Similarly, Em-7 was prepared.

B7 Silver nitrate 410 g Tallium nitrate 0.64 g Make up to 684 ml with distilled water C7 Silver nitrate 11590 g 18.2 g with thallium nitrate Make up 19316 ml with distilled water Preparation of Em-8 In the same manner as in Em-5, the emulsion was added up to TAI, and the emulsion was added. After preparation, the following solution I-8 was added, and the mixture was stirred for 5 minutes and stopped.
m-8 was obtained.

I-8 18.8 g of thallium nitrate Distilled water 376 ml Next, using the emulsion thus prepared, in the same manner as in Example 1, Sample No. 5-No. 8 was obtained.

Except that the intensifying screen was changed to the following high-sensitivity intensifying screen S1 and that the photographic processing was changed from processing-1 to processing-2, the sensitometric evaluation and pressure were performed in the same manner as in Example 1. Evaluation of resistance and evaluation of silver tone were performed. Table 2 shows the results. In addition, the evaluation of the sensitivity, the scratch resistance, and the silver tone was performed using Sample No. The relative value when 5 is set to 100 is shown.

[Production of high-sensitivity intensifying screen S1] Phosphor Gd ₂ O ₂ S: Tb (average particle size: 1.8 μm) 200 g Binder Polyurethane-based thermoplastic elastomer Demolac TPKL-5-26 25 <solid content 40 %> (Manufactured by Sumitomo Bayer Urethane Co., Ltd.) 20 g Nitrocellulose (digestibility: 11.5%) 2 g was added to a methyl ethyl ketone solvent and dispersed with a propeller mixer to give a coating solution for forming a phosphor layer having a viscosity of 25 PS (25 ° C.). Was prepared. (Binder / phosphor ratio = 1/22) Separately, 90 g of a soft acrylic resin solid content and 50 g of nitrocellulose were added to methyl ethyl ketone as a coating liquid for forming an undercoat layer, and dispersed and mixed to obtain a viscosity of 3 to 6 PS (25
C).

A thickness of 250 μm into which titanium dioxide has been kneaded.
Of polyethylene terephthalate (support) is placed horizontally on a glass plate, and the above-mentioned coating solution for forming an undercoat layer is uniformly applied on the support using a doctor blade, and then gradually raised from 25 ° C to 100 ° C. The coating film was dried by drying to form an undercoat layer on the support. (The thickness of the coating film was 15 μm) The coating solution for forming the phosphor layer was uniformly coated on the coating solution with a doctor blade to a thickness of 240 μm and dried, followed by compression. Compression is performed using a calendar roll.
The test was performed at a thickness of 0 kgw / cm ² and a temperature of 80 ° C. After this compression, a transparent protective film having a thickness of 3 μm was formed by the method described in Example 1 of JP-A-6-75097.

The characteristics of the obtained screen are as follows.
60 μm, phosphor filling rate 68%, sharpness (CTF) 48
%Met.

[Processing-2] (Development using a solid processing agent not containing hydroquinone) Procedure (A) 13,000 g of sodium erythorbate as a developing agent is ground in a commercially available bandam mill until the average particle size becomes 10 μm. To this fine powder, 4877 g of sodium sulfite, 975 g of phenidone, and 1635 g of DTPA were added, mixed in a mill for 30 minutes, and mixed at room temperature in a commercial stirring granulator at room temperature.
After granulating for 30 minutes by adding 30 ml of water,
The granulated product is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the moisture of the granulated product.

To the prepared granules, 2167 g of polyethylene glycol 6000 was uniformly mixed for 10 minutes using a mixer in a room humidified at 25 ° C. and 40% RH or less, and the mixture was tough by Kikusui Seisakusho. Presto Collect 15
The tableting machine modified from 27HU was used for compression and tableting at a filling amount of 8.715 g per tablet to prepare 2500 tablets E for development replenishment.

DTPA: diethylenetriaminepentaacetic acid
5. Sodium operation (B) 19,500 g of potassium carbonate, 8.15 g of 1-phenyl-5-mercaptotetrazole, sodium hydrogen carbonate
25 g, glutaraldehyde sulfite adduct 650 g, and polyethylene glycol 6000 1354 g are pulverized and granulated in the same manner as in the operation (A). The amount of water added is 3
After granulation, the mixture is dried at 50 ° C. for 30 minutes to remove the water content of the granules almost completely. The resulting mixture was compressed and tableted using a tableting machine modified from Tough Press Collect 1527HU (described above) with a filling amount per tablet of 9.90 g, and 2,500 tablets F for development replenishment were prepared. Created.

Next, a fixing tablet was prepared in the following manner.

Operation (C) 18560 g of ammonium thiosulfate, 1392 g of sodium sulfite, 580 g of sodium hydroxide, and 2.32 g of disodium ethylenediaminetetraacetate were pulverized and granulated in the same manner as in the operation (A). The amount of water to be added is 500 ml, and after granulation, it is dried at 60 ° C. for 30 minutes to almost completely remove water from the granulated material. The obtained mixture was subjected to a tableting machine modified from Tough Presto Collect 1527HU (described above),
Compression and tableting were performed at a filling amount of 8.214 g per tablet to prepare 2500 fixing supplement replenishing tablets G.

Operation (D) 1860 g of boric acid, aluminum sulfate / 18-hydrate 6500
g, glacial acetic acid 1860 g, sulfuric acid (50 wt%) 928 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water to be added is 100 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. The obtained mixture was filled with 4.459 g of tablet per tablet using a tableting machine modified from Tough Press Collect 1527HU (described above).
Then, compression and tableting were performed to prepare 2500 fixing replenishing tablets H.

Developer Starter Glacial acetic acid 2.98 g Potassium bromide 4.00 g Water was added to make up to 1 liter.

At the start of the processing of the developer (start of running), the developer 16.5 prepared by diluting the developing tablet with dilution water.
The processing was started by filling the developing tank with a liquid obtained by adding 330 ml of a starter per liter as a starting liquid.
The pH of the developer to which the starter was added was 10.45.

The sample prepared above was exposed to light so that the optical density after the development processing became 1.0, and the sample was run. For running, Konica's SRX-50 automatic processor
2 was equipped with a solid processing agent charging member, and was modified so that the processing speed could be reduced to 15 seconds.

During running, the photosensitive material 1.
1 ² per the A agent 00m, two and water B agent 20
ml. When each of A and B was dissolved in 20 ml of water, the pH was 10.70.

To the fixing solution were added four of the above agent C, ^{two of the} above agent D and 50 ml of water per 1.00 m ² of the light-sensitive material.
For each treatment agent, the rate of water addition starts at about the same time as the addition of the treatment agent and is approximately 10 in proportion to the dissolution rate of the treatment agent.
Minutes at a constant speed.

(Processing conditions) Current image 39 ° C. 5.0 seconds Fixing 36 ° C. 3.5 seconds Rinse with water Normal temperature 2.5 seconds Squeeze 1.5 seconds Drying 50 ° C. 2.5 seconds (total 15 seconds) Processing The liquid composition is as follows.

Developer composition (per liter of water) Potassium carbonate 120.0 g Sodium erythorbate 40.0 g DTPA 5.0 g 1-phenyl-5-mercaptotetrazole 0.05 g Sodium hydrogen carbonate 20.0 g 1-phenyl-3- Pyrazolidone 3.0 g Sodium sulfite 15.0 g Polyethylene glycol 15.0 g Glutaraldehyde sulfite adduct 4.0 g Fixer composition (per liter of water) Ammonium thiosulfate 160.0 g Sodium sulfite 12.0 g Boric acid 10.0 g Sodium hydroxide 5. 0 g Glacial acetic acid 10.0 g Aluminum sulfate · 18 hydrate 35.0 g Sulfuric acid (50 wt%) 5.0 g Ethylenediaminetetraacetic acid disodium dihydrate 0.02 g

[0358]

[Table 2]

According to the sample No. of the present invention, 6-No. Sample No. 8 is Sample No. As compared with No. 5, it was found that the film had low fog and high sensitivity, was significantly improved in scratch resistance, roller marks, and the like, and had a good silver tone. In particular, Sample No. to which thallium ion was more uniformly added. 7 is excellent.

[0360]

According to the present invention, the silver halide emulsion and the method for producing the same, the silver halide photographic light-sensitive material, the processing method therefor and the image forming method have low fog, high sensitivity, and improved pressure resistance such as scratch resistance and roller marks. And the silver tone is improved. The effect is remarkable in rapid processing and low replenishment photographic processing.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/14 G03C 1/14 5/17 5/17 5/26 5/26 520 520 5/30 5/30 5/31 5 / 31 G21K 4/00 G21K 4/00 A

Claims (12)

[Claims] 1. A silver halide photographic emulsion comprising tabular silver halide grains containing thallium ions and spectrally sensitized. 2. A selenium and / or selenium containing thallium ion.
Or a silver halide photographic emulsion containing tellurium-sensitized tabular silver halide grains. 3. The silver halide photographic emulsion according to claim 2, wherein the tabular silver halide grains are spectrally sensitized. 4. The silver halide photographic emulsion according to claim 1, wherein thallium ions are contained inside the silver halide grains. 5. A method for producing a silver halide photographic emulsion according to claim 1, wherein silver halide grains are formed in the presence of thallium ions. Emulsion manufacturing method. 6. A silver halide photographic light-sensitive material comprising a support and a silver halide photographic emulsion layer containing the silver halide photographic emulsion according to claim 1. 7. A method for processing a silver halide photographic light-sensitive material, comprising subjecting the silver halide photographic light-sensitive material according to claim 6 to photographic processing including development processing. 8. The processing method for a silver halide photographic material according to claim 7, wherein the development processing time is 12 seconds or less. 9. A method for processing while continuously replenishing a processing solution according to a photosensitive material to be processed, wherein a replenishment amount of a developing solution is less than 100 ml per m ^{2 of the} photosensitive material to be processed. 9. A method for processing a silver halide photographic light-sensitive material according to claim 7 or 8. 10. A developing solution and / or a replenishing solution containing substantially no dihydroxybenzene-based developing agent and containing a compound represented by the following general formula (A): 10. The method for processing a silver halide photographic light-sensitive material according to any one of claims 1 to 9. Embedded image [Wherein, R ₁ and R ₂ each represent a hydroxy group, an amino group,
Represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P, Q
Represents a hydroxy group, a carboxy group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, a methylcapto group, an alkyl group or an aryl group, or P and Q are And 5 to 5 carbon atoms together with the two vinyl carbon atoms substituted by R ₁ and R ₂ and the carbon atom substituted by Y
Represents an atom group forming an 8-membered ring. Y is = O or = N
It represents the -R _3. R ₃ represents a hydrogen atom, a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group. ] 11. A silver halide photographic light-sensitive material according to claim 7, wherein the processing is performed by an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank of the automatic developing machine. Processing method. 12. The method according to claim 7, wherein the silver halide photographic light-sensitive material according to claim 6 is sandwiched between high-sensitivity intensifying screens, X-ray photographed, and processed by the processing method according to any one of claims 7 to 11. Image forming method.