JPH10115882A - Silver halide photographic emulsion and its manufacture, and silver halide photographic sensitive material using the same, and its processing, and x-ray image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain high sensitivity, low fog, high γ, and high covering power even in the case of an ultrahigh speed and low replenishing processing by incorporating a specified flat silver halide grains having cores comprising silver bromide and the like in the silver halide emulsion. SOLUTION: The silver halide photographic emulsion contains the silver halide grains having the cores made of silver bromide or iodobromide, and the flat silver halide grains having principal faces (100) and having a silver chloride content of 20-99mol.%. It is preferred to form the cores comprising silver bromide or iodobromide in the presence of bromine or iodine ions and for the flat silver halide grains to occupy >=50% of the projection areas of the total silver halide grains. Here, these flat silver halide grains means the grains having 2 opposite parallel principal and an average aspect ratio of >=1.3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly, to a silver halide photographic emulsion having ultra-rapid and low replenishment suitability, a photographic material using the same, a processing method therefor, and an X-ray image. It relates to a forming method.

[0002]

2. Description of the Related Art In recent years, with regard to the development processing of silver halide photographic light-sensitive materials, it has been increasingly desired to shorten the processing time. For example, in the medical field, the number of X-ray film shots has increased due to the spread of regular medical examinations, medical check-ups, etc., and the increase in examinations including diagnosis in general medical care, but it is necessary for the examinee to notify the results as soon as possible. There is. In recent years, angiographic photography, intraoperative photography, and the like have been steadily increasing, and it is necessary to view photographs in a short time.

In order to satisfy these demands, it is necessary to promote automation of diagnosis (photographing, 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.

[0005] To meet such demands for rapid processing and low replenishment processing, it is necessary to address the whole system including photosensitive materials, processing solutions and processors, but the development of photosensitive materials to be processed is particularly important. Yes, and much research has been done so far.

For the photosensitive material, for example, by changing the silver halide emulsion from silver iodobromide to silver bromide, silver chlorobromide and further to silver chloride emulsion, the processing time can be greatly reduced.
In addition, low replenishment suitability can be imparted. Also,
It is known that reducing the amount of silver applied to a light-sensitive material is also advantageous from the viewpoint of rapid processing and low replenishment processing.

However, when a silver chloride emulsion is used, a significant decrease in sensitivity and an increase in fog are likely to occur.
In addition, there is a disadvantage that the processing fluctuation is large.

In recent years, it has been known that tabular silver halide grains are preferable in terms of color sensitization efficiency, covering power and the like. Therefore, development of tabular silver halide grains containing silver chloride has been attempted as a high-sensitivity silver halide photographic material having rapid processing properties and low replenishment processing suitability.

Many studies have been made on tabular silver halide grains containing silver chloride having the (111) plane as the main plane, but all of them have been studied by adding additives to (11) planes.
1) The nature caused by the instability of the (111) plane of silver chloride, such as the fact that the additive has a large adverse effect on photographic performance due to the formation of the plane, or the formed (111) plane is unstable. Therefore, it was expected that practical application would be difficult.

On the other hand, many studies have been made on tabular grains containing silver chloride having a (100) plane as a main plane. For example, Japanese Patent Application Laid-Open No. H5-204073 discloses that silver iodide is used during nucleation. An emulsion comprising high silver chloride tabular grains having a (100) plane as the main plane is disclosed. JP-A-7-234470 discloses a tabular silver halide grain having a halogen composition gap plane at the center of the grain and having a (100) main plane. However, these emulsions were not practical because of insufficient sensitivity and low γ.

Further, Japanese Patent Application Laid-Open No. 8-76306 discloses that, in a core / shell type silver chlorobromide having a (100) major plane, the halogen composition in the shell portion is continuously changed to provide high sensitivity. It is said that low fog and high covering power can be obtained, and pressure blackening resistance has been improved.However, it is characterized by changing the halogen composition of the shell part, and the composition of the core part affects the above performance. States that it is small. The photographic performance achieved has been far from practical use.

In JP-A-8-122953, tabular silver halide grains having a (100) plane as a main plane are obtained by using a seed crystal containing silver chloride by a halogen gap or the like, and the monodispersion of the grains is obtained. It is said that the properties, sensitivity, granularity and the like have been improved, but are still insufficient for practical use.

As described above, the tabular silver halide grains containing silver chloride having the (100) plane as the main plane are still in a state where the basic photographic performances such as sensitivity, fog, γ and covering power are still satisfactory. No further improvement was required for practical use.

On the other hand, as for the developing solution, it is desired to make the processing solution non-polluting for environmental protection. In recent years, ascorbic acid and erythorbic acids have been disclosed as developing agents in place of, for example, hydroquinone. Accordingly, at present, there is a demand for a silver halide photographic light-sensitive material having a developability equal to or higher than that of the conventional silver halide photographic materials even in the development processing using these developing agents.

[0015]

Accordingly, a first object of the present invention is to provide a silver halide photographic emulsion capable of obtaining high sensitivity, low fog, high γ and high covering power even in ultra-rapid and low replenishment processing. An object of the present invention is to provide a silver halide photographic light-sensitive material using the same.

Further, a second object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material having such performance, which can be processed quickly and environmentally friendly. The object is to provide a sensitive X-ray imaging method.

[0017]

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

(1) Tabular silver halide grains having a nucleus portion of silver bromide or silver iodobromide and having a (100) major plane and a silver chloride content of 20 to 99 mol% are prepared. A silver halide photographic emulsion characterized by containing:

(2) The nucleus comprising silver bromide or silver iodobromide as described in the above (1) is formed in the presence of bromine ions or in the presence of bromine ions and iodine ions. A method for producing a silver halide photographic emulsion.

(3) A silver halide photographic light-sensitive material containing the silver halide photographic emulsion described in the above item (1).

(4) A method for processing a silver halide photographic light-sensitive material, comprising subjecting the silver halide photographic light-sensitive material described in the above item (3) to photographic processing including development processing.

(5) The method for processing a silver halide photographic material as described in (4), wherein the development time is 1 to 7 seconds.

(6) The method for processing a silver halide photographic light-sensitive material as described in the item (4) or (5), wherein the replenishing amount of the developing solution is 1 to 100 ml per m ^{2 of the} light-sensitive material to be processed.

(7) A developer and / or replenisher 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 the above items (1) to (6).

[0025]

Embedded image

Wherein R ₁ and R ₂ are each 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 mercapto group, an alkyl group or an aryl group; And Q represent an atom group necessary for bonding to form a 5- to 8-membered ring. Y represents ＝ O or ＮN—R ₃ , and 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.

(8) The halogenation according to any one of (4) to (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 of silver photographic photosensitive material.

(9) After sandwiching the silver halide photographic light-sensitive material described in the above item 3 with a high-sensitivity intensifying screen and taking X-rays,
(8) An X-ray image forming method, wherein the method is carried out by the method for processing a silver halide photographic light-sensitive material according to any one of (8).

Hereinafter, the present invention will be described in detail.

The silver halide photographic emulsion of the present invention is tabular silver halide grains in which the core of the silver halide grains is made of silver bromide or silver iodobromide. That is, the nucleus portion is characterized by not containing silver chloride. The nucleus portion referred to here is the central portion of the silver halide grains, and the first portion where the grains are precipitated as silver halide microcrystals from the liquid continuous phase, that is,
What is called a portion formed during nucleation.

The nucleus portion preferably contains silver iodide, that is, silver iodobromide. In the case of silver iodobromide, the silver iodide content of the core portion is preferably 0.1 mol% or more and 5 mol% or less.

The distribution of the halogen composition inside the silver halide grains can be determined by pretreating 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. While cooling this section with liquid nitrogen, observation and point analysis were performed with a transmission electron microscope equipped with an energy dispersive X-ray analyzer,
It can be obtained by quantitative calculation (Inoue, Nagasawa: Abstracts of the 62nd Annual Meeting of the Photographic Society of Japan, 1987 p62).

In the silver halide photographic emulsion of the present invention, 50% or more of the total projected area of the silver halide grains in the emulsion is composed of tabular silver halide grains, preferably 70% or more, more preferably 80% or more. % To 100%, more preferably 90% to 100%, of tabular silver halide grains.

Here, the 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 2-8.

In the present invention, tabular silver halide grains are characterized in that the main plane is a (100) plane. The shape of the main plane of the tabular silver halide grains of the present invention is a right-angled parallelogram or a shape in which the corners of the right-angled parallelogram are rounded. The adjacent side ratio of the right-angled parallelogram is preferably less than 10, more preferably less than 5, and further preferably 2
Is less than. 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 the 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 (P.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. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, 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 an electron beam to pass through. Therefore, a high-pressure type (200 kV or more for a particle having a thickness of 0.25 μm)
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 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 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.

The tabular silver halide grains of the present invention have a silver chloride content of 20 to 99 mol%, preferably 25 to 99 mol%.
Mol% or more and 99 mol% or less, more preferably 30 mol%
Or more and 99 mol% or less, more preferably 30 mol% or more and 9 or less.
0 mol% or less, most preferably 30 mol% or more and 80 mol% or less.

In the tabular silver halide grains of the present invention, silver iodobromochloride, silver bromochloride or the like can be used as silver halide. In the case of silver iodobromochloride, the content of silver iodide is preferably from 0.01 mol% to 1.0 mol% as an average silver iodide content in the whole silver halide grains, but 0.01 mol% or less.
It is more preferably at least 0.5 mol%.

In the case of silver bromochloride or silver iodobromochloride, the content of silver bromide is not particularly limited, and if the content of silver chloride and silver iodide is within the range of the present invention, the effect of the present invention is obtained. Can be presented.

In the present invention, the halogen composition and the average halogen composition of each silver halide grain 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 emulsion of the present invention preferably have a more uniform halogen composition between grains. When the distribution of the halogen composition between the grains is measured by the EPMA method, it is particularly preferable that the relative standard deviation of the composition between the grains of iodine is 35% or less, more preferably 20% or less.

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 silver halide composition on the outermost surface of the tabular silver halide grains is defined by an XPS method (X-ray Ph
otoelectron Spectroscopy:
X-ray photoelectron spectroscopy) refers to the silver halide composition 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 a probe X-ray 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 silver iodide localized phase is preferably at most 5 mol%, more preferably at most 1.0 mol%.

The method for producing a silver halide emulsion of the present invention comprises:
It is characterized in that nucleation is carried out in the presence of bromine ion or both of iodine ion and bromide ion and in the absence of chloride ion. For example, nuclei can be formed with low pBr in the presence of iodine ions under conditions that facilitate formation of the (100) plane. 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. A method in which nucleation and growth are performed in the same vessel is also preferable. It should be noted that the growth is temporarily stopped in the middle, and this is used as seed particles,
The seed grains may be grown by a method of depositing silver halide.

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

Also, described in Japanese Patent Application No. 7-157670 are (1) a process in which silver salt is added in the absence of iodide to initiate nucleation, and (2) a process in which iodide is subsequently present. Step 2 of adding a silver salt and causing nucleation and / or crystal growth
It is also possible to use a method for producing a silver halide photographic emulsion characterized by having two steps.

Specifically, (a) nucleation is started in the absence of iodide, and nucleation is continued in the presence of iodide. (B) nucleation is started in the absence of iodide. Crystal growth in the presence of iodide (c) a production method having any of the steps of starting nucleation in the absence of iodide, and subsequently growing crystals simultaneously with nucleation in the presence of iodide. Is characterized in that iodide does not exist at the start of nucleation, but iodide immediately follows.

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 pBr at the start of nucleation is adjusted to a value that facilitates formation of 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 bromide, 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%. The pH is preferably at least 1.0, more preferably at least 1.5, even more preferably at least 2.0.
８8.0. Gelatin and gelatin derivatives are preferably used as the dispersion medium, and gelatin from which impurities have been removed is more preferable. Particularly, the methionine content is 3
0 μmol / less than 1 g of gelatin, preferably 15 μmol /
It is preferable to use so-called low methionine gelatin of less than 1 g of gelatin.

It is preferable to use a so-called low molecular weight gelatin having a molecular weight of 1,000 to 10 × 10 ⁴ , preferably 2000 to 6 × 10 ⁴ . These gelatins may be used alone or as a mixture of two or more. The concentration of the dispersion medium is preferably 0.1 to 10% by weight.
3-5% by weight is more preferred. The addition time of the silver salt solution during nucleation is preferably 5 seconds or more and less than 1 minute. During this time, the halide salt 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 0.1 to 10 mol% of the total silver.

(2) Ripening Step The method for producing a silver halide photographic emulsion of the present invention preferably has a ripening step. In the ripening process, tabular grains generated during nucleation by Ostwald ripening can be further grown and other grains can be eliminated.
The temperature during aging is preferably from 20 to 90 ° C, and from 30 to 85 ° C.
Is more preferably, 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 advantageously used. PBr during aging
Is preferably 0.5 to 3.5, more preferably 1.0 to 3.0. At the time of ripening, it is also preferable to add chloride ions and perform ripening in the presence of chloride ions. In that case, pCl is preferably 0.5 to 3.5, and more preferably 1.0 to 3.0. 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 Process The method for producing a silver halide emulsion of the present invention preferably has a crystal growth process. During crystal growth, chlorine ions are preferably present. The pCl during crystal growth is 0.5-3.
5, but is preferably adjusted to 1.0 to 3.0, more preferably 1.5 to 2.5. Further, the pH is preferably 1 to 12, more preferably 2 to 8, and most preferably 2 to 6. Temperature during crystal growth is 40-90 ° C
Is preferred, more preferably 45 to 80 ° C, and most preferably 50 to 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 preferably 0.15 μm or less, more preferably 0.1 μm or less, and most preferably 0.06 μm or less.

Further, a method in which the growth is temporarily stopped in the middle, and then used as seed grains to grow silver halide by precipitation on the seed grains can also be preferably used.

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 of growing by adding silver halide fine particles, dissolving and recrystallizing as described in the 88th Annual Meeting of the 1983 Annual Meeting of the Photographic Society of Japan is also preferably used. Especially silver iodide fine grains,
Silver bromide fine grains, silver iodobromide fine grains, silver bromochloride fine grains, and silver chloride fine grains are preferably used.

The tabular silver halide grains of the present invention may be so-called halogen conversion type (conversion type) grains. The halogen conversion amount is preferably from 0.2 mol% to 0.5 mol% with respect to the silver amount, and the conversion may be performed during physical ripening or after completion of physical ripening.

As a halogen conversion method, usually, an aqueous halogen solution or fine silver halide particles having a smaller solubility product with silver than the halogen composition on the grain surface before the halogen conversion is added. The particle size at this time is 0.2 μm
The following is preferable, and more preferably 0.02 to 0.1 μm
It is.

When silver iodide and / or silver bromide is 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 time for adjusting the silver iodide and / or silver bromide content on the outermost surface is determined 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 in the range of 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 production are extremely important. As the stirring device, a device in which an additive liquid nozzle disclosed in JP-A-62-160128 is installed in the liquid near the mother liquor suction port of the stirrer is particularly preferably used. At this time, the stirring rotation speed is preferably set to 100 to 1200 rpm.

The silver halide emulsion of the present invention may form silver nuclei during grain formation. The silver nucleation is carried out by adding a reducing agent to the silver halide photographic emulsion or the mixed solution for grain growth, or the silver photographic emulsion or the mixed solution for grain growth is prepared at a low pAg of 7 or less.
The ripening or particle growth is performed under Ag or under high pH conditions of pH 7 or more. A method performed by combining these methods is a preferred embodiment of the present invention.

Reduction sensitization has long been known as a technique for forming silver nuclei. 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) Ag2 + h ⁺ → Ag ⁺ + Ag (2) Ag → Ag ⁺ + e ⁻ (3) where h ⁺ and e ⁻ are free holes and free electrons generated by exposure, hv Indicates a photon, and Ag2 indicates a silver nucleus formed by reduction sensitization.

Preferred examples of the reducing agent include 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.

In order to perform 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 ⁺ ]).

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 of 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.

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,
Thiosulfonic acid compound chloramine T; The amount of the oxidizing agent depends on the type of the reducing agent, the conditions for forming silver nuclei, the timing of adding the oxidizing agent, and the adding conditions. The amount is 10 ⁻² to 10 ⁻⁵ mol per mol of the reducing agent used. Is preferred. The oxidizing agent may be added at any time during the silver halide photographic emulsion manufacturing 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.

The silver halide photographic emulsion of the present invention can use heavy metal ions. As heavy metal ions,
Periodic Table VI of iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, etc.
Group II metals, cadmium, zinc, mercury and other Group II transition metals, and various ions such as lead, rhenium, molybdenum, tungsten, and chromium, among which iron, iridium, platinum, ruthenium, and osmium Transition metal ions 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. Preferred heavy metal compounds are shown below.

(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 the 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, a thiocyanate compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) is used in an amount of 1 × 10 ⁻³ mol or more and 3 × 10 ³ mol or more per mol of silver.
It is preferable to add ^-2 mol or less.

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: 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
rc Disclosure. RD)
76 volume No. 17643 (December 1978).

In the production of the silver halide photographic emulsion of the present invention, unnecessary soluble salts may be removed during the growth of silver halide grains, or may be kept contained. When removing the salts, see RD Vol. 1764
The method can be carried out based on the method described in 3 II. When seed particles are used, desalination is preferably performed once seed particle formation is completed.

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

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, it may contain a substituted aminostilbene compound or aromatic organic acid formaldehyde condensate, cadmium salt, azaindene compound or the like which is a nitrogen-containing heterocyclic nucleus group.

The sensitizing dye may be added during or during each step of nucleation, growth, desalting, and chemical sensitization, or after the chemical sensitization.

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 used. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and selenoureas (eg, N, N-dimethylselenourea, N, 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 (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids, and selenoesters (eg, , 2-selenopropionic acid, methyl-3-selenobutyrate, etc.),
Selenophosphates (eg, tri-p-triselenophosphate, etc.) and selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.) are exemplified. Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenoketones, selenides.

The amount of the selenium sensitizer varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used. 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.

Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-).
Dimethyltellurourea, N, N'-dimethyl-N'phenyltellurourea), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride,
Butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (e.g., telluroacetamide, N, N-dimethyltellurobenzamide), telluroketones, telluroesters, and isotellurocyanates.

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 to the present invention include:
Preferred 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. It is listed as. In addition, as the simple substance of 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, the ripening conditions and the like.
It is preferably from 1 × 10 ^-4 mol to 1 × 10 ^-9 mol per mol. More preferably, 1 × 10 ⁻⁵ mol to 1 × 1
^0-8 mol.

The method of adding the sulfur sensitizer and the gold sensitizer may be such that they are dissolved in water or alcohols or other inorganic or organic solvents, and added in the form of a solution. It may be added in the form of a dispersion obtained by emulsifying and dispersing using such a medium.

The selenium and / or tellurium sensitization, the sulfur sensitization, and the 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 and 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).

As the water-soluble silver salt, silver nitrate is preferable. 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, and the stabilizer disclosed in JP-A-57-82831 can be used. Inhibitors and / or V.I. S. A paper by Gahler [Zeithlift fur wissens]
chaftliche 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.

The light-sensitive material of the present invention preferably has an emulsion layer containing the emulsion of the present invention on both sides or one side of a support. When a silver halide emulsion layer is provided on both sides of the support, the amount of silver per side is 1.8 g / m ² or less. When a silver halide emulsion layer is provided on one side, the amount of silver is 3.6 g / m ² or less. It is preferable that each has a value of 0.1.
5~1.5g / m ^2, is 1.0 to 3.0 g / m ^2.

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 processing, high sensitivity, high sharpness and rapid processing can be achieved. A light-sensitive material having appropriate properties is obtained, which is preferable. The dye to be used can 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. 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. 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. Specifically, JP-A-7-5629, page (3) [0017] to page (16) [0042] The dye described in [0042] is preferably contained as a solid dispersed fine particle in the constituent layer of the silver halide photographic light-sensitive material.

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 not more than 3.0 g / m ^2, more preferably not less than 1.0 g per 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.

In the silver halide photographic light-sensitive material of the present invention,
A composite latex can be included. The amount of the composite latex was 0.1% based on the amount of gelatin in the hydrophilic colloid layer.
It is preferable to contain them in a weight ratio of 3 to 1.1.

As the composite latex to be used, a dispersion of composite polymer fine particles composed of inorganic fine particles and a hydrophobic polymer, or a composite high polymer formed by polymerizing a composition having a hydrophobic monomer in the presence of inorganic fine particles. It is a dispersion of molecular fine particles.

Examples of the inorganic fine particles used in the composite latex include inorganic oxides, nitrides, and sulfides.
Preferably, it is an oxide. Specifically, Si, Na,
K, Ca, Ba, Al, Zn, Fe, Cu, Sn, I
n, W, Y, Sb, Mn, Ga, V, Nb, Tu, A
Single or composite oxides such as g, Bi, B, Mo, Ce, Cd, Mg, Be, Pb and the like are preferable, and particularly, Si, Y, S
Single or composite oxides of n, Ti, Al, V, Sb, In, Mn, 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.

[0122] _{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-29 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.

The hydrophobic polymer refers to a polymer that does not substantially elute in an aqueous solution such as a developing solution, and the hydrophobic monomers forming the hydrophobic polymer include vinyl esters and acrylic acid. 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 a composite latex used in the present invention are preferably at least one selected from vinyl esters, acrylic esters and methacrylic esters. One or styrenes, particularly preferred as the former The number of carbon atoms of the ester group is of 6 or more. 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.

Examples of the polymerization method of the composite latex include an emulsion polymerization method, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and a radiation polymerization method.

(Production Example 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.

In the silver halide photographic light-sensitive material of the present invention,
Various additives can be added to the silver halide emulsion depending on the purpose. Examples of additives and others used are RD-17643 (December 1978),
8716 (November 1979) and 308119 (1
(December 989). The locations of those descriptions are listed below.

[0127]

[Table 1]

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.

A suitable support is polyethylene terephthalate or the like. The surface of these supports may be provided with an undercoat layer to improve the adhesion of the coating layer, or may be subjected to corona discharge, ultraviolet irradiation, or the like.

Next, a preferred photographic processing method of the silver halide photographic light-sensitive material of the present invention (hereinafter sometimes referred to as a 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 processed in a development time of 1 second to 7 seconds. The development time here is
It refers to the time during which the photosensitive material is immersed in the developer, but more specifically, when processing with a roller-conveying type automatic developing machine, refers to the time from the moment the tip of the photosensitive material enters the developer to the moment it exits. . The development time is preferably from 1 second to 7 seconds, more preferably from 2 seconds to 7 seconds. The temperature of the development treatment is preferably 25 to 50 ° C, more preferably 30 to 40 ° C. The fixing processing time is preferably from 1 second to 10 seconds, more preferably from 2 seconds to 7 seconds. Fixing temperature is 20 ~
50 ° C is preferred, and 30 to 40 ° C is more preferred. The temperature and time of the water washing treatment are preferably 0 to 50 ° C for 2 seconds to 15 seconds, and more preferably 15 to 40 ° C for 2 seconds to 8 seconds.

The developed, fixed and washed (or stabilized) photosensitive material is dried through a squeeze roller for squeezing the washing water. Drying is performed at 40 to 100 ° C., and the drying time can be appropriately changed depending on the environmental temperature.
It may be 2 seconds, particularly preferably at 40 to 80 ° C. for 3 to 8 seconds. More preferably, a far infrared heater is used. Furthermore, the total processing time (Dry to Dr)
y) is preferably 10 seconds to 30 seconds, more preferably 10 seconds to 25 seconds.

As a developing solution for processing the silver halide photographic light-sensitive material of the present invention, as a developing agent, for example, JP-A No. 4-1
No. 5641, JP-A-4-16841 and the like, 3-pyrazolidones such as hydroquinone, paraaminophenols such as p-aminophenol, N-methyl-p-aminophenol and 2,4-diamiphenol. Examples thereof include 1-phenyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and 5,5-dimethyl-1-phenyl-3. Pyrazolidone and the like, and further, ascorbic acids, which can be used alone or in combination as needed.

The preferred amount of the above-mentioned para-aminophenols and 3-aminopyrazolidones is 0.004 mol / l, more preferably 0.04 to 0.12 mol / l.

The total molar number of dihydroxybenzenes, paraaminophenols, 3-pyrazolidones, and ascorbic acids contained in these developer components is preferably 0.1 mol / liter or less.

In the method for processing a silver halide photographic light-sensitive material of the present invention, a developing solution containing substantially no dihydroxybenzene-based developing agent and containing the compound represented by formula (A) and / or It is preferable to process with an automatic developing machine using a developing replenisher.

The term “substantially” as used herein means that a dihydroxybenzene compound is not contained in an amount having a developing ability.

In the compound of the present invention represented by the general formula (A), R ₁₅ and R ₁₆ each represent a hydroxy group or an amino group (substituted alkyl group having 1 to 10 carbon atoms;
For example, those having a substituent such as methyl, ethyl, hydroxyethyl and the like), acylamino group (acetylamino, benzoylamino group and the like), arylsulfonylamino group (benzenesulfonylamino, p-toluenesulfonylamino group and the like), Represents an alkoxysulfonylamino (such as a methoxycarbonylamino group), a mercapto group, or an alkylthio group (such as a methylthio or ethylthio group). Preferred examples of R ₁₅ and R ₁₆ include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group. P, Q in the formula
Alkyl group, alkoxy group, hydroxy group, hydroxyalkyl group, carboxyl group, carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, in addition to a mercapto group, R ₁₅ by bonding P and Q , R ₁₆ are substituted with two vinyl carbon atoms;
Represents an atomic group necessary for forming a 5- to 8-membered ring together with the substituted carbon atom.

Specific examples of the ring structure include -O- and -C (R
_{16), R 17) -,} C (R 18) =, - C (= O) -, - N
(R ₁₉ )-and -N = are combined. Where R
_{16 to} R ₁₉ 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), or an allyl group which may be substituted having 6 to 15 carbon atoms ( Examples of the substituent 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, it is 0.02 to 0.4 mol.

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

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

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

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

The preservative may contain a sulfite such as potassium sulfite, sodium sulfite, or a reductone such as piperidinohexose reductone, preferably 0.2 to 1 mol / l. Liter, more preferably 0.3 to 0.6 mol / liter. Also, the addition of a large amount of ascorbic acids leads to processing stability. Examples of the alkaline agent include pH adjusters 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. Inorganic inhibitors include sodium bromide, potassium bromide, potassium iodide and the like. In addition, L. F.
A. Menson, Photographic Processing Chemistry, Focal Press (1966)
226-229, U.S. Pat. No. 2,193,015,
Nos. 2,592,364 and JP-A-48-64933 may be used.

[0153] Chelating agents for masking calcium ions mixed in tap water used in the treatment liquid include chelating agents having a chelate stabilization constant of 8 or more with iron described in JP-A-1-193853 as an organic chelating agent. 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 developing solution replenishes the processing agent fatigue and the oxidation 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.

When the processing method of the silver halide photographic material of the present invention is a method in which the processing solution is continuously replenished in accordance with the photographic material to be processed, the replenishment amount of the developing solution is processed. photosensitive material 1 m ² per 1~100ml is replenished. More preferably, it is 15 to 100 ml.

In the processing method of the present invention, a fixing material generally used in the art can be used as the fixing solution. The pH of the fixing solution is 3.8 or more, preferably 4.2 to
5.5. Ammonium thiosulfate as a fixing agent,
It is a thiosulfate such as sodium thiosulfate, and 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.

In the processing method of the present invention, 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 a moisture-proof treatment as required. The powder refers to an aggregate of fine crystals. Granules are obtained by adding a granulation step to powder, and refer to granules having a particle size of 50 to 5000 μm. Tablets are obtained by compressing powder or granules into a certain shape.

To solidify the photographic processing agent, a concentrated liquid 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 formed 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 the 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, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a pre-ketting 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 the tablet processing agent is described in, for example, JP-A-51-61837, JP-A-54-155038, and JP-A-52-55038.
-88025, British Patent 1,213,808, etc., and can be produced by a general method.
For example, JP-A-2-109042 and JP-A-2-109043
And JP-A-3-39735, JP-A-3-39939, and the like. Further, powder processing agents are disclosed in, for example, JP-A-54-133332, British Patent 72
5,892, 729,862 and German Patent 3,
It can be produced by a general method as described in, for example, US Pat.

The solid processing agent has a bulk density of 1.0 to 2.
Preferably 5 g / cm ^3, preferably in terms of the strength of the resulting solids greater than 1.0g / cm ^3, 2.5g / cm
^{A value of} less than ³ is preferred in terms of the solubility of the obtained solid.

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. The developer has a great effect of stabilizing photographic performance. Although the solid processing agent may solidify only a part of a component of a certain processing agent, it is preferable that all 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 processing agents to be replenished into each processing tank in accordance with 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.

The silver halide photographic light-sensitive material of the present invention is preferably subjected to X-ray photography using 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 to 250 μm.
m is preferred. This is because if the thickness of the phosphor layer is less than 150 μm, sharpness sharply 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.

The fluorescent intensifying screen preferably has an X-ray absorption of 30% or more per 100 μm thickness of the phosphor layer by increasing the filling rate of the phosphor particles. The amount of X-ray absorption was determined as follows. That is, the intrinsic filtration is 2.2 m of aluminum with three-phase power supply.
X-rays generated from a tungsten target operated at 80 kVp from an X-ray generator equivalent to m are transmitted through an aluminum plate having a thickness of 3 mm and a purity of 99% or more and fixed at a position 200 cm from the tungsten anode of the target tube. The X-ray was arrived at the intensifying screen, and then measured at a position 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.

For the radiographic intensifying screen used in the X-ray image forming method of the present invention, for example, the following phosphors can be used.

Tungstate phosphors (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 [BaSO4: Pb, Ba
SO ₄ : Eu ²⁺ , (Ba, Sr) SO ₄ : Eu ²⁺ etc.], 2
Eurobium-activated alkaline earth metal phosphate-based phosphor [Ba ₃ (PO ₄ ) ₂ : Eu ²⁺ , (Ba, Sr) ₃ , (PO
₄ ) ₂ : Eu ²⁺ etc.] divalent eurobium-activated alkaline earth metal fluorohalide-based phosphor [BaFCl: E
u ²⁺ , BaFBr: Eu ²⁺ , BaFCl: Eu ²⁺ , T
b, BaFBr: Eu ²⁺ , Tb, BaF ₂ , BaCl ₂ ,
XBaSO ₄ , KCl: Eu ²⁺ , (Ba, Mg) F ₂ , B
aCl ₂ , KCl: Eu ²⁺ etc.], iodide-based phosphor (CS
I: Na, CSI: Tl, NaI, KI: Tl, etc.) Sulfide-based phosphor [ZnS: Ag, (Zn, Cd) S: Ag,
(Zn, Cd) S: Cu, (Zn, Cd) S: Cu, A
l etc.], a hafnium phosphate-based phosphor (HfP ₂ O ₇ : Cu
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.

[0178]

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

Example 1 Preparation of Emulsion Em-1 (Comparative Emulsion) A1 Ossein gelatin 75.0 g KI 1.25 g NaCl 33.0 g Make up to 15000 ml with distilled water B1 Silver nitrate 410 g Make up to 684 ml with distilled water C1 Silver nitrate 590 g Distillation Make up to 19316 ml with water D1 KI 4.0 g NaCl 140 g Make up to 684 ml with distilled water E1 NaCl 2272 g KBr 3377 g Make up to 19274 ml with distilled water At 40 ° C., JP-B-58-58288, 58-58
No. 58289 to Solution A1 in a mixing stirrer
1 and the total amount of solution D1 were added over 1 minute.

The EAg was adjusted to 149 mV, and after Ostwald ripening for 20 minutes, the total amount of solution C1 and solution E1 was reduced to 3%.
Added over 20 minutes. Meanwhile, EAg was controlled at 100 mV. Immediately after the addition was completed, desalting and washing were performed.

Emulsion Em-1 thus prepared was
65% of the total projected area of the silver halide grains is composed of tabular grains having a (100) plane as a main plane, and has an average thickness of 0.14.
Electron microscope observation revealed that the average particle diameter was 0 μm, the average particle diameter was 1.00 μm, and the coefficient of variation was 25%.

Preparation of Emulsion Em-2 (Emulsion of the Present Invention) In the above Em-1, the solution A1 was added to the solution A2, and the solution D1 was added.
Was changed to solution D2, and solution E1 was changed to solution E2.
m-2 was prepared.

A2 Ossein gelatin 75.0 g KI 1.25 g KBr 67.2 g Make up to 15000 ml with distilled water D2 KI 4.0 g KBr 285 g Make up to 684 ml with distilled water E2 NaCl 2445 g KBr 3125 g Make up 19274 ml with distilled water Emulsion Em-2 prepared above was composed of tabular grains having 79% of the total projected area of silver halide grains having a (100) plane as a main plane, an average thickness of 0.142 μm, an average grain size of 1.00 μm, Electron microscope observation revealed that the coefficient of variation was 22%.

Preparation of Emulsion Em-3 (Comparative emulsion) In Em-1, the solution A1 was changed to the solution A3, the solution D1 was changed to the solution D3, and the solution E1 was changed to the solution E3.
3 was prepared.

A3 Ossein gelatin 75.0 g NaCl 33.0 g Make up to 15000 ml with distilled water D3 NaCl 140 g Make up with 684 ml with distilled water E3 NaCl 2274 g KBr 3377 g Make up with distilled water 19274 ml Emulsion Em-3 prepared in this way Is that tabular grains having 60% of the total projected area of the silver halide grains having the (100) plane as a main plane, having an average thickness of 0.154 μm, an average grain size of 0.96 μm, and a variation coefficient of 26%. Was found by electron microscope observation.

Preparation of Emulsion Em-4 (Emulsion of the Invention) In Em-1, the solution A1 was changed to the solution A4, the solution D1 was changed to the solution D4, and the solution E1 was changed to the solution E4.
4 was prepared.

A4 Ossein gelatin 75.0 g KBr 67.2 g Make up to 15000 ml with distilled water D4 KBr 285 g Make up to 684 ml with distilled water E4 NaCl 2447 g KBr 3125 g Make up with distilled water 19274 ml Emulsion Em-4 prepared in this way Means that 75% of the total projected area of the silver halide grains is composed of tabular grains having a (100) plane as a main plane, the average thickness is 0.159 μm, the average grain size is 0.94 μm, and the variation coefficient is 23%. Was found by electron microscope observation.

Preparation of Emulsion Em-5 (Comparative Emulsion) Emulsion Em-5 was prepared in the same manner as in Em-1, except that the addition time of solution C1 and solution E1 was changed to 275 minutes. .

Em-5 thus prepared is a tabular grain having 65% of the total projected area of the silver halide grains having the (100) plane as the main plane, and has an average thickness of 0.191 μm.
m, the average particle diameter was 0.86 μm, and the coefficient of variation was found to be 25% by electron microscope observation.

Preparation of Emulsion Em-6 (Emulsion of the Invention) Emulsion Em-6 was prepared in the same manner as Em-2 except that the addition time of solution C1 and solution E2 was changed to 275 minutes. Prepared.

Em-6 thus prepared is a tabular grain having 80% of the total projected area of the silver halide grains having the (100) plane as the main plane, and has an average thickness of 0.191 μm.
m, the average particle size was 0.86 μm, and the coefficient of variation was found to be 21% by electron microscope observation.

Subsequently, the prepared emulsions Em-1 to Em-
The temperature of Sample No. 6 was set to 55 ° C., and spectral sensitization and chemical sensitization were performed according to the following sensitization formula [sensitization-1].

[Sensitization-1] 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 diisopropyl phosphine telluride was added and stirred for 20 minutes, and then 0.1 mol% of a silver bromide fine particle emulsion was added, followed by ripening 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 (T
AI) was added.

The amounts of the added compounds (per mole of silver halide) are shown below.

Spectral sensitizing dye (A) 350 mg Spectral sensitizing dye (B) 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 In addition, solid fine particles of spectral sensitizing dye The dispersion was prepared by adding a predetermined amount of the following spectral sensitizing dye to water whose temperature had been previously adjusted to 27 ° C., and mixing with a high-speed stirrer (dissolver). At rpm 30~1
Obtained by stirring for 20 minutes.

[0196]

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Next, the additives described in the following second layer (emulsion layer) were added to the obtained emulsion to obtain 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 amount of 1.6 g / m ² per side and a gelatin amount of 2.5 g / m ^2.
The sample was coated on the support at the same time on both sides at a speed of 80 m / min using two slide hopper type coaters, dried for 2 minutes and 20 seconds. 1-6 were obtained.

Glycidimethacrylate 5 was used as a support.
Aqueous copolymer dispersion and colloidal tin oxide dispersion obtained by diluting a copolymer composed of three monomers of 0 wt%, methyl acrylate 10 wt%, and butyl methacrylate 40 wt% to 10 wt% Ganpei 7-
175 was used as a subbing liquid
A polyethylene terephthalate film base colored blue to a concentration of 0.15 for a μm X-ray film 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 Gelatin 0.2 g Sodium dodecylbenzenesulfonate 5 mg Compound (I) 5 mg 2,4-dichloro-6-hydroxy-1,3,5- Triazine sodium salt 5 mg Colloidal silica (average particle size 0.014 μm) 10 mg Latex (L) 0.2 g Potassium polystyrene sulfonate 50 mg Second layer (emulsion layer) Potassium tetrachloropalladium (2) 100 mg Compound (G) 0.5 mg 2,6-bis (hydroxyamino) -4-diethylamino 1,3,5-triazine 5 mg t-butyl-catechol 5 mg polyvinylpyrrolidone (molecular weight 10,000) 20 mg styrene-maleic anhydride copolymer 80 mg sodium polystyrene sulfonate 3 0 mg Trimethylolpropane 50 mg Diethylene glycol 50 mg Nitrophenyl-triphenyl-phosphonium chloride 1 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 50 mg 2-Mercaptobenzimidazole-5-sodium sodium sulfonate 5 mg Compound (H) 0.5 mg n- _{C 4 H 9 OCH 2 CH (} OH) CH 2 N (CH 2 COOH) 20mg compound (M) 5 mg compound (N) 5 mg composite latex (L-1) 1.0 g dextrin (average molecular weight of about 1000) 0.2 g dextran (Average molecular weight: about 40,000) 0.2 g Sodium styrenesulfonate (molecular weight: about 500,000) 7 mg However, the amount of gelatin was adjusted so as to be 0.8 g / m ² .

Third Layer (Protective Layer Lower Layer) Gelatin 0.2 g Tricresyl phosphate 0.2 g Latex (L) 0.2 g Sodium polyacrylate (average molecular weight 50,000) 30 mg Sodium styrene sulfonate (molecular weight about 50) 10,000 mg 4th layer (protective layer upper layer) Gelatin 0.2 g Matting agent composed of polymethyl methacrylate (area average particle size 7.0 μm) 27 mg 2,4-dichloro-6-hydroxy-1,3,5-triazine Sodium salt 10 mg Latex (L) 0.2 g Colloidal silica (average particle size 0.014 μm) 50 mg Polyacrylamide (average molecular weight 10,000) 0.1 g Sodium polyacrylate 30 mg Polysiloxane (SI) 50 mg Compound (I) 30 mg Compound (J) ) 2 mg compound (S-1) 7 g Compound (K) 15 mg Compound (O) 50 mg Compound (S-2) 5 mg Compound (F-1) 3 mg Compound (F-2) 2 mg Compound (F-3) 1 mg Compound (F-4) 10 mg Compound (P) 50mg

[0202]

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[0203]

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[0204]

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<Sensitometric evaluation> Sample N obtained
Photographic characteristics were evaluated using o1 to o6. First, a sample is sandwiched between two screens (KO-250, manufactured by Konica Corporation), exposed to X-rays at a tube voltage of 80 kVp, a tube current of 100 mA and a tube current of 0.05 second through an aluminum wedge, and exposed for 0.05 seconds. -1 photographic processing was performed.

After the treatment, fog, sensitivity and gamma (γ) were measured. Fog is represented by the lowest density, sensitivity is represented by the reciprocal of the amount of exposure that gives fog +1.0 density, and γ is represented by the slope between the points giving fog +0.5 and fog +1.5 density on the characteristic curve. did.

The sensitivity and γ were the same as those of Sample No. It is shown as a relative value when the value in the process 1 is 100.

<Evaluation of Covering Power> The obtained Sample Nos. 1 to 6 were exposed to sunlight for one hour, and then subjected to photographic processing of the following processing-1. After the processing, the amount of silver per unit area (the amount of developed silver) and the optical density were measured, and the covering power (CP) was determined by the following equation.

CP = (optical density) / (developed silver amount) It is shown as a relative value when 1 is set to 100. The results obtained are shown in Table 1 below.

<Process-1> (Development with a solid processing agent containing hydroquinone as a developing agent) A tablet for developing replenishment was prepared according to the following procedures (A, B). Preparation 3000 g of hydroquinone as a developing agent is crushed in a commercially available Bandham 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 25 g.
After mixing uniformly for 10 minutes using a mixer in a room humidified at 40 ° C. and below 40% RH, one tablet of the obtained mixture was obtained using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Compression tableting was performed with the filling amount per unit being 3.84 g to prepare 2500 tablets A for development replenishment.

Operation (B) Preparation of tablet B for developing replenishment 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 is pulverized and granulated in the same manner as in the operation (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 thus obtained was subjected to compression tableting using a tableting machine similar to the above, with the filling amount per tablet being 1.73 g, and compression tableting was carried out.
00 development replenishing tablets B were prepared.

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

Operation (C) Preparation of Tablet C for Fixing Replenishment Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is pulverized in the same manner as in the operation (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), the amount of water
Granulate to 0 ml. After granulation, the granulated product is
After drying for 0 minutes, the water content of the granules is almost completely removed. 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 the same tableting machine as described above, with the filling amount per tablet being set to 6.202 g.
500 fixing replenishing tablets C were prepared.

Operation (D) Preparation of Tablet D for Fixing Replenishment 1000 g of boric acid, 150 parts of aluminum sulfate / 18 hydrate
0 g, sodium hydrogen acetate (3,000 g of glacial acetic acid and sodium acetate mixed and dried), 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 after mixing for 3 minutes, the obtained mixture was compressed to a filling amount of 4.562 g per tablet using the same tableting machine as described above. Tableting was performed to prepare 1250 fixing replenishing tablets D.

[0215]

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

The photosensitive material prepared above was exposed to light so that the optical density after development processing was 1.0, and the photosensitive material 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 was 0.6
The above-mentioned ^two agents A and B and 76 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. The fixing solution contains 0.
2 pieces of the above C agent, 1 piece of the D agent and 7 pieces of water per 62 m ^2.
4 ml was added. 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.

[0219] Developer composition The composition per 1000 ml of water is shown below.

Potassium carbonate 100.0 g Hydroquinone 75.0 g Dimezone S 25.0 g Diethylenetriaminepentaacetic acid.5Na 2.5 g (DTPA) 5-methylbenzotriazole 0.25 g 1-Phenyl-5-mercaptotetrazole 0.18 g 2 -Mercaptohypoxanthine 0.13 g Sodium sulfite 75.0 g Potassium sulfite 62.5 g KOH 5.0 g Diethylene glycol 125.0 g N-acetyl-D, L-penicillamine 0.25 g The pH of this developer was 10.70.

Fixing solution composition The composition per 1000 ml of water is shown below.

Sodium thiosulfate 84.0 g Potassium thiosulfate 196.0 g Sodium sulfite 30.0 g Boric acid 20.0 g Sodium hydrogen acetate 60.0 g Glacial acetic acid 34.6 g Sodium acetate 25.4 g Tartaric acid 4.0 g pH of this fixing solution Was 4.50.

The results obtained are shown in Table 2 below.

[0224]

[Table 2]

As is clear from the table, the sample of the present invention containing no chlorine in the nucleus portion of the silver halide grains was the sample of the present invention. 2, 4, 6
Is the sample No. containing chlorine in the core. It can be seen that the film has high sensitivity, high γ, low fog, and excellent covering power as compared with 1, 3, and 5.

Example 2 Preparation of Emulsion Em-7 A7 Ossein gelatin 75.0 g KI 1.25 g NaCl 33.0 g Make up to 15000 ml with distilled water B7 Silver nitrate 410 g Make up to 684 ml with distilled water C7 Silver nitrate 590 g With distilled water 19316 ml D7 KI 4.0 g NaCl 140 g Make up to 684 ml with distilled water E7 NaCl 3807 g KBr 352 g Make up to 19274 ml with distilled water At 40 ° C., JP-B-58-58288, 58-58
The total amount of the solution B7 and the solution D7 was added over 1 minute to the solution A7 in the mixing stirrer described in No. 58289. EA
g was adjusted to 149 mV, and after Ostwald ripening for 20 minutes, the total amount of Solution C7 and Solution E7 was added over 320 minutes. Meanwhile, EAg was controlled at 143 mV.

Immediately after the addition was completed, desalting and washing were performed.
Emulsion Em-7 thus prepared is composed of tabular grains having a (100) plane as the main plane and 65% of the total projected area of the silver halide grains, and has an average thickness of 0.15 μm and an average grain size of 0%. It was found by electron microscope observation that the dispersion coefficient was 0.99 μm and the coefficient of variation was 26%.

Preparation of Emulsion Em-8 Emulsion Em-7 was prepared by changing solution A7 to solution A8, solution D7 to solution D8, and solution E7 to solution E8.
8 was prepared.

A8 Ossein gelatin 75.0 g KI 1.25 g KBr 67.2 g Make up to 15000 ml with distilled water D8 KI 4.0 g KBr 285 g Make up to 684 ml with distilled water E8 NaCl 3980 g Make up to 19274 ml with distilled water Em-8 thus prepared was composed of tabular grains having a (100) plane as a main plane, with 65% of the total projected area of the silver halide grains having an average thickness of 0.15 μm and an average grain diameter of 0.15 μm.
Electron microscope observation revealed that the particle size was 99 μm and the coefficient of variation was 23%.

Preparation of Emulsion Em-9 Solution E8 was changed from solution E8 to solution E9 in Em-8.
9 except that EAg at the time of addition of 9 was changed to 138 mV.
Emulsion Em-9 was prepared in the same manner as in Emulsion 8.

E9 NaCl 3531 g KBr 913 g Make up to 19274 ml with distilled water Em-9 produced in this way is composed of tabular grains having 65% of the total projected area of the silver halide grains having the (100) plane as the main plane. , Average thickness 0.15 µm, average particle size 0.
Electron microscope observation revealed that the particle size was 99 μm and the coefficient of variation was 23%.

Preparation of Emulsion Em-10 The solution E8 was changed to the solution E10 in Em-8,
0 except that the EAg at the time of addition of 0 was changed to 133 mV.
In the same manner as in 8, Em-10 was prepared.

E10 NaCl 3116 g KBr 1759 g Make up to 19274 ml with distilled water Em-10 thus produced is composed of tabular grains in which 65% of the total projected area of silver halide grains has a (100) plane as a main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 23%.

Preparation of Emulsion Em-11 The solution E8 was changed to the solution E11 in Em-8,
Em- except that the EAg at the time of addition of 1 was changed to 129 mV.
In a similar manner to 8, Em-11 was prepared.

E11 NaCl 2700 g KBr 2605 g Make up to 19274 ml with distilled water Em-11 produced in this way is composed of tabular grains having 65% of the total projected area of the silver halide grains having the (100) plane as the main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 23%.

Preparation of Emulsion Em-12 The solution E8 was changed to the solution E12 in Em-8,
2 except that the EAg at the time of addition 2 was changed to 124 mV.
In the same manner as in 8, Em-12 was prepared.

E12 2285 g of NaCl, 3450 g of KBr, and 19274 ml of distilled water Em-12 prepared in this manner is composed of tabular grains having 65% of the total projected area of silver halide grains having a (100) plane as a main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 23%.

Preparation of Em-13 In Em-8, the solution E8 was changed to the solution E13, and
3 except that EAg at the time of addition was changed to 118 mV.
In a similar manner to 8, Em-13 was prepared.

E13 NaCl 1870 g KBr 4296 g Make up to 19274 ml with distilled water Em-13 produced in this way is composed of tabular grains having 65% of the total projected area of the silver halide grains having the (100) plane as the main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 23%.

Preparation of Emulsion Em-14 The solution E8 was changed to the solution E14 in Em-8,
4 except that the EAg at the time of addition was changed to 114 mV.
In a similar manner to 8, Em-14 was prepared.

E14 1454 g of NaCl, 5142 g of KBr, and 19274 ml of distilled water Em-14 produced in this manner is composed of tabular grains having 65% of the total projected area of silver halide grains having a (100) plane as a main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 23%.

Preparation of Emulsion Em-15 The solution E8 was changed to the solution E15 in the Em-8.
5 except that the EAg at the time of addition was changed to 108 mV.
In a similar manner to 8, Em-15 was prepared.

E15 NaCl 1039 g KBr 5988 g Make up to 19274 ml with distilled water Em-15 produced in this way is composed of tabular grains having 65% of the total projected area of silver halide grains having a (100) plane as a main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 23%.

Preparation of Emulsion Em-16 The solution E8 was changed to the solution E16 in Em-8.
6 except for changing the EAg at the time of addition to 102 mV.
In a similar manner to 8, Em-16 was prepared.

E16 NaCl 623 g KBr 6834 g Make up to 19274 ml with distilled water Em-16 made in this way is composed of tabular grains having 65% of the total projected area of the silver halide grains having the (100) plane as the main plane. The average thickness was 0.15 μm, the average particle size was 0.99 μm, and the coefficient of variation was 25%.

Preparation of Emulsion Em-17 The solution D8 was changed to the solution D17 and the solution E8 was changed to the solution E17 in Em-8, and the EAg when E17 was added was changed to 105 m.
Except for changing to V, Em-17 was prepared in the same manner as Em-8.

D17 KI 4.0 g NaCl 140 g distilled water 684 ml E17 NaCl 899 g KBr 6273 g distilled water 19274 ml 65% of the total projected area of the silver halide grains of Em-17 thus prepared was ( Electron microscopic observation revealed that the particles were composed of tabular grains having a (100) plane as a main plane, and had an average thickness of 0.15 μm, an average particle diameter of 0.99 μm, and a coefficient of variation of 26%.

Emulsions Em-7 to Em-17 prepared above
Are as shown in Table 3 below.

[0249]

[Table 3]

Subsequently, the above emulsions Em-7 to Em-1
No. 7 was subjected to [Sensitization-1], and the coating samples Nos. 7
~ 17 were created.

The obtained sample No. With respect to 7 to 17, evaluation was performed in the same manner as in Example 1 except that the fluorescent intensifying screen of Example 1 was changed to the following S1 and the photographic processing was changed from the processing-1 to the following processing-2. Table 4 shows the obtained results.
Note that the sensitivity, γ, and CP are the values of Sample No. It was expressed as a relative value when 7 was taken as 100.

<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-5-2525 <solid content: 40%> (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 prepare a coating solution for forming a phosphor layer having a viscosity of 25 PS (25 ° C.). (Binder / phosphor ratio = 1/22).

Separately, as a coating liquid for forming an undercoat layer, 90 g of soft acrylic resin solids and 50 g of nitrocellulose were used.
Is added to methyl ethyl ketone, dispersed and mixed to obtain a viscosity of 3 to
A 6PS (25 ° C.) dispersion was prepared.

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 (thickness of the coating film: 15 μm).

The above-mentioned coating solution for forming a phosphor layer was uniformly coated with a doctor blade to a thickness of 240 μm, dried, and then compressed. Compression was performed using a calender roll at a thickness of 300 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 screen obtained were as follows.
60 μm, phosphor filling rate 68%, sharpness (CTF) 48
%Met.

<Process-2> (Development using a solid processing agent not containing hydroquinone as a developing agent) Operation (A) Preparation of tablet E for replenishment of development 13,000 g of sodium erythorbate as a developing agent was placed in a commercially available vandam mill. Grind to an average particle size of 10 μm. To this fine powder, 4877 g of sodium sulfite, 975 g of phenidone and 1,635 g of DTPA (pentasodium diethylenetriaminepentaacetic acid) were added, mixed in a mill for 30 minutes, and mixed in a commercially available stirring granulator at room temperature for about 10 minutes.
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.

To the prepared granules, 2167 g of polyethylene glycol 6000 was uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. 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.

Operation (B) Preparation of Tablet F for Replenishment for Development 19500 g of potassium carbonate, 8.15 g of 1-phenyl-5-mercaptotetrazole, sodium hydrogencarbonate
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. Using a tableting machine similar to the above, the obtained mixture was filled with 9.9 per tablet.
It was compressed to 0 g and compressed and tableted to prepare 2500 replenishing tablets F for development.

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

Operation (C) Preparation of Tablet G for Fixing Replenishment 18560 g of ammonium thiosulfate, 1392 g of sodium sulfite, 580 g of sodium hydroxide and 2.32 g of disodium ethylenediaminetetraacetate were crushed and granulated in the same manner as in operation (A). I do. 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 compressed and tableted with the same tableting machine at a filling amount of 8.214 g per tablet to prepare 2500 fixing supplement replenishing tablets G.

Operation (D) Preparation of Fixing Replenishing Tablet H Formulation 1860 g of boric acid, 6500 aluminum sulfate / 18-hydrate
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 compressed and tableted using the same tableting machine as described above with a filling amount per tablet of 4.459 g to prepare 2500 fixing replenishing tablets H.

Developer Starter The same composition as in Example 1 was used.

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 photosensitive material prepared above was exposed to light so that the optical density after the development processing was 1.0, and the photosensitive material was run. For the running, an automatic developing machine SRX-502 (manufactured by Konica Corp.) equipped with a solid processing agent charging member and modified so as to be able to process at a processing speed of 15 seconds was used.

During running, the developing solution contains 1 m ² of photosensitive material.
One E agent, two F agents, and 20 ml of water were added. The pH when each of E and F was dissolved in 20 ml of water was 10.70. At this time, the replenishing amount of the developing solution is 34 ml as the processing solution per m ^{2 of the} photosensitive material to be processed.
Is equivalent to

The fixing solution contains the above G per 1 m ² of the photosensitive material.
Four agents, two H agents and 50 ml of water were added. For each treatment agent, the addition rate of water was started almost simultaneously with the addition of the treatment agent, and was added at a constant speed for 10 minutes almost in proportion to the dissolution rate of the treatment agent.

(Processing conditions) Current image 39 ° C. 5.0 seconds Fixing 36 ° C. 3.5 seconds Rinsing at room temperature 2.5 seconds Squeeze 1.5 seconds Drying 50 ° C. 2.5 seconds (15 seconds in total) 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 amino 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

[0270]

[Table 4]

As is clear from the table, the sample of the present invention used a solid processing agent containing no hydroquinone, the developing time was 5 seconds, and the replenishment rate of the developing solution was 34 ml / m ² , which was rapid and low. Even if replenishment processing is performed, low fog, high sensitivity, and excellent covering power (C
It can be seen that P) can be obtained.

As for the halogen composition of the grains, Comparative Sample No. 1 using an emulsion having a silver chloride content of less than 20 mol% was used.
In the case of Comparative Sample No. 16, There was no particular advantage as compared with No. 7, and the level was practically problematic. Therefore, it is understood that the silver chloride content needs to be 20% or more.

[0273]

As has been demonstrated in the examples, according to the present invention, rapid processing and low fog can be achieved even when processing at a low replenishment rate.
A silver halide photographic light-sensitive material having high sensitivity and excellent covering power was obtained. Further, after X-ray photography with a high-sensitivity intensifying screen, the same performance could be obtained when processing was performed using a developing solution having environmental suitability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/015 G03C 1/015 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 (9)

[Claims] 1. Tabular silver halide grains having a core portion composed of silver bromide or silver iodobromide and having a (100) major plane and a silver chloride content of 20 to 99 mol%. A silver halide photographic emulsion. 2. The silver halide according to claim 1, wherein the core portion comprising silver bromide or silver iodobromide is formed in the presence of bromine ions or in the presence of bromine and iodine ions. Manufacturing method of photographic emulsion. 3. A silver halide photographic material comprising the silver halide photographic emulsion according to claim 1. 4. A method for processing a silver halide photographic light-sensitive material, comprising subjecting the silver halide photographic light-sensitive material according to claim 3 to photographic processing including development processing. 5. The method according to claim 4, wherein the development time is 1 to 7 seconds. 6. A photosensitive material 1 m in which a replenishing amount of a developing solution is processed.
6. The method for processing a silver halide photographic light-sensitive material according to claim 4, wherein the amount is 1 to 100 ml per ² pieces. 7. 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): 7. The method for processing a silver halide photographic light-sensitive material according to any one of items 1 to 6, Embedded image In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group,
Represents 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 mercapto group, an alkyl group or an aryl group;
And Q represent an atom group necessary for bonding to form a 5- to 8-membered ring. Y represents ＝ O or ＮN—R ₃ , and 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. 8. The silver halide photographic light-sensitive material according to claim 4, 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. Material treatment method. 9. The processing of the silver halide photographic light-sensitive material according to claim 4, wherein the silver halide photographic light-sensitive material according to claim 3 is sandwiched between high-sensitivity intensifying screens and X-ray photographing is performed. An X-ray image forming method characterized by processing by a method.