JPH08334851A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PURPOSE: To provide the silver halide photographic sensitive material high in sensitivity and image quality and superior in rapid processing aptitude and storage stability. CONSTITUTION: (1) The silver halide photographic sensitive material has at least one silver halide photosensitive emulsion layer on a support and the emulsion layer contains silver halide grains having a sensitizing dye and a chemical sensitizer added at the temperature ranging from 25 deg.C to 45 deg.C and then subjected to sensitization ripening at a temperature higher than the addition temperature of the sensitizing dye, and this sensitizing dye forms a characteristic J-band in the wavelength region of <=550nm. (2) The silver halide photographic sensitive material described in (1) and containing silver halide grains having an average silver iodide content of <=1.0mol% and a crystal face (100) proportion of >=50%. (3) The method for processing the silver halide photographic sensitive material described in (1) or (2) the total processing time required for executing the processing the method comprising development and fixation and drying steps is <=30sec.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention has high sensitivity and good storability,
And regarding the silver halide photographic light-sensitive material excellent in pressure resistance,
In particular, the present invention relates to a silver halide photographic light-sensitive material for X-ray medical treatment and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, the demand for rapid processing of silver halide photographic light-sensitive materials has been increasing more and more, and the demand is remarkable in the field of medical X-ray films. In recent years, the number of inspection items has increased in order to popularize medical examinations or improve the diagnostic accuracy, and as a result, the number of X-ray photographs taken has increased. In addition, it is necessary to inform the examinee of the diagnosis result sooner, and it is strongly desired to make the processing extremely quick.

However, in order to speed up the processing, development,
Although it is necessary to shorten the processing time of each processing step such as fixing, washing with water, and drying, the load on each processing increases.
For example, if the developing time is simply shortened, the density of the conventional photosensitive material is lowered, that is, the sensitivity is lowered and the gradation is deteriorated. Further, if the fixing time is shortened, the fixing of silver halide becomes incomplete, which causes deterioration of image quality. Furthermore, shortening of each processing time is development,
The elution of the sensitizing dye in each process of fixing and washing is not sufficient, so that the image quality is deteriorated by the residual dye (residual color). Therefore, in order to solve such a problem, it is necessary to accelerate the developing speed or the fixing speed, to reduce the amount of dye, and to promote the desorption and / or decolorization of the dye.

On the other hand, in order to reduce the waste liquid of the development processing, it is necessary to reduce the fatigue of the processing liquid and / or the replenishing liquid, but this is accompanied by the problems common to the speeding up.

As techniques for improving these problems, European Patent No. 0,506,584, Japanese Unexamined Patent Publication No. 5-88293,
No. 5-93975 and the like disclose a technique of using benzimidazolocarboxycyanines having good decolorizing performance as a spectral sensitizing dye. Further, in JP-A-5-61148, oxacarbocyanines and benzimidazolocarboxycyanines are used in combination at a specific ratio as a spectral sensitizer in a silver halide emulsion having an iodine content of 1 mol% or less, and a selenium compound. And / or a technique of chemically sensitizing with a tellurium compound is disclosed.

However, while these techniques disclosed alone improve the residual color property or the rapidity of development, they are still insufficient to satisfy the recent demand levels for various performances. In particular, when the light-sensitive material was stored under high humidity and high temperature for a long period of time, there was a drawback that the sensitivity was greatly reduced. Further, there are problems in pressure resistance and illuminance failure of the film, and further improvement has been desired.

In the field of medical X-ray photographic light-sensitive materials, in order to improve patient service and workability, there is a strong demand for speeding up development processing, reducing processing waste liquid, and simplifying processing operations in general. ing. However, the liquid processing agent that dilutes the concentrated processing solution and replenishes it in the processing layer is heavy and has a large volume, so the work efficiency is poor. A solid processing agent supplied with a solid component and dilution water has been proposed. As a result, transportation cost, storage space can be reduced, work efficiency can be improved, and packaging materials can be reduced.

However, in this method, since the solubility of the solid component is involved, the development processing becomes uneven especially when the development processing is carried out for an extremely short time, and it is difficult to obtain sufficiently stable running performance. Had a point.

[0009]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide high sensitivity in rapid processing, excellent storability with time under high humidity and high temperature, good pressure resistance of the film, and uneven development and illuminance failure. It is an object of the present invention to provide a small amount of silver halide photographic light-sensitive material and a processing method thereof. It is another object of the present invention to provide a silver halide photographic light-sensitive material for X-ray which can obtain such performance.

[0010]

The above problems have been solved by the present invention described below. (1) In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, the photosensitive silver halide emulsion layer is characterized by having a reflection spectrum of 550 nm or less. A sensitizing dye capable of forming a typical J-band and a chemical sensitizer are added at a temperature of 25 ° C. or higher and 45 ° C. or lower, and then sensitized and aged at a temperature higher than the addition temperature of the sensitizing dye. A silver halide photographic light-sensitive material containing an emulsion comprising silver halide grains.

(2) The average silver iodide content of the silver halide grains is 1.0 mol% or less, and the (100) plane ratio of the grains is 50% or more. The described silver halide photographic light-sensitive material.

(3) A processing method including development, fixing and drying steps of a silver halide light-sensitive material, wherein the total processing time is 30 seconds or less, (1) or (2). A method for processing a silver halide photographic light-sensitive material.

(4) Developing a silver halide photographic light-sensitive material,
In a method of continuously treating in a treatment step including each fixing step, the treatment is carried out while continuously supplying a solid treatment agent to the treatment liquid of each treatment step (1) to (3) 2. The method for processing a silver halide photographic light-sensitive material as described in 1 above.

(5) The present invention is characterized in that a silver halide photographic light-sensitive material is sandwiched between high-sensitivity intensifying screens and an X-ray is photographed (1).
The silver halide photographic light-sensitive material according to the item (2).

Was achieved by

The present invention will be described in detail below.

In the silver halide grains of the present invention, silver chloride, silver iodochloride, silver iodochlorobromide, silver chlorobromide and the like can be used as the silver halide composition. Of these, silver chloride and silver iodochloride are preferable. The silver halide grains contained in the silver halide emulsion of the present invention preferably contain 50 mol% or more of silver chloride, more preferably have a silver chloride content of 70 mol% or more, and contain 90 mol% or more. More preferably.

In the case of silver iodochloride, the content of silver iodide is preferably 0.01 mol% or more and 1.0 mol% or less, but 0.01 mol% or less, as the average iodide content of the entire silver halide grains. % Or more and 0.5 mol% or less is particularly preferable.

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

The silver halide photographic light-sensitive material of the present invention may have a photosensitive silver halide emulsion layer containing tabular silver halide grains as a silver halide emulsion. The tabular silver halide grains preferably have a more uniform iodide content between grains.

When the distribution of the iodide content between the grains is measured by the EPMA method, the relative standard deviation is 35% or less, and further 2
It is preferably 0% or less.

The tabular silver halide grains preferably contain silver iodide, but it is preferred that they are contained at least at the inside. In the case of the inside, it is more preferable that it exists at least in the central portion. In this case, the internal composition preferably contains silver iodide in an amount of 0.1 mol% or more and 5 mol% or less. Here, the halogen composition distribution inside the silver halide grain is obtained by pretreating the grain into an ultrathin section, and then observing and analyzing with a transmission electron microscope while cooling. Specifically, after taking out silver halide grains from the emulsion, they are embedded in a resin and cut with a diamond knife to prepare a slice having a thickness of 60 nm.
While cooling this section with liquid nitrogen, observation and point analysis were performed with a transmission electron microscope equipped with an energy dispersive X-ray analyzer, and it was obtained by quantitative calculation (Inoue, Nagasawa: Photographic Society, 1987) Conference Proceedings p6
2).

It is also preferable that silver iodide is present on the outermost surface. In this case, the silver iodide content on the outermost surface is preferably 1 mol% or more and 10 mol% or less. Here, the silver iodide content on the outermost surface of the tabular silver halide grains means X
PS method (X-ray Photoelectron S
This refers to the silver iodide content of a portion up to a depth of 50Å analyzed by X-ray photoelectron spectroscopy, and can be determined as follows.

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

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

The tabular silver halide grains have an average aspect ratio of 8 or less, preferably less than 7, and most preferably less than 5.

The present invention is characterized in that 50% or more of the total projected area of the silver halide grains contained in the emulsion is composed of tabular silver halide grains having the (100) plane as the main plane. 70% or more, and more preferably 90% or more of the total projected area is composed of tabular silver halide grains having the (100) plane as the main plane. The main plane is (100)
The surface can be confirmed by an X-ray diffraction method or the like.

In the present invention, the shape of the main plane of the tabular silver halide grain is a right-angled parallelogram or a right-angled parallelogram with the corners missing or rounded. The ratio of adjacent sides of the right-angled parallelogram is less than 10, preferably less than 5, more preferably less than 2. In addition, the length of the side when the corner is missing or rounded is the length up to the intersection with the line that extends the straight line part of the side of the right parallelogram and extends the straight line part of the adjacent side. It is represented by

The tabular silver halide grains have an average grain size of 0.
It is preferably 15 to 5.0 μm, and 0.4 to 3.
It is more preferably 0 μm, most preferably 0.
It is 4 to 2.0 μm.

The average thickness of the tabular silver halide grains is 0.
It is preferably from 01 to 1.0 μm, more preferably from 0.02 to 0.40 μm, further preferably from 0.02 to
It is 0.30 μm.

Particle size and thickness can be optimized to optimize sensitivity and other photographic properties. Optimum particle size and optimum thickness depending on sensitivity and other factors that make up the photographic properties of the photosensitive material (thickness of hydrophilic colloid layer, hardness, chemical ripening condition, sensitivity of photosensitive material, silver coverage, etc.) Different.

The tabular silver halide grains are monodisperse grains having a narrow grain size distribution. Specifically, when the width of the distribution is defined by (standard deviation of particle diameter / average particle diameter) × 100 = width of particle diameter distribution (%), it may be 20% or less, preferably 18% or less. However, it is more preferably 15% or less.

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

The tabular silver halide grains may have dislocations. The dislocation is described in, for example, J. F. Hamilton, P
hot. Sci. Eng, 57 (1967) and T.W. S
hiozawa, J .; Soc. Photo. Sci. Ja
It can be observed by a direct method using a transmission electron microscope at low temperature described in Pan, 35, 213 (1972). That is, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on the mesh for electron microscope observation, and the sample to prevent damage (printout etc.) due to electron beam In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, the high pressure type (200 kv or more for particles having a thickness of 0.25 μm)
It can be observed more clearly by using the electron microscope.

Spectral sensitizing dyes are those which are adsorbed on silver halide grains and contribute to sensitization. The spectral sensitizing dye used in the present invention is optional as long as it has a spectral sensitizing function. When the sensitizing dye according to claim 1 is adsorbed on silver halide emulsion grains and the reflection spectrum is measured, J −
The maximum absorption wavelength of the band needs to be 555 nm or less. In addition, in the application to an X-ray medical light-sensitive material using a fluorescent substance that emits green light, the spectral sensitizing dye of the present invention is adsorbed on silver halide emulsion grains and the fluorescent substance is measured when its reflection spectrum is measured. It is preferable that the J-band is formed in the same wavelength range as the green light from the.
That is, the maximum absorption wavelength is preferably 520 nm to 555 n
It is preferable to select and combine the spectral sensitizing dyes so that the J-band having the maximum absorption in the m region is formed. The thickness is more preferably 530 to 553 nm, and most preferably 540 to 550 nm. The addition temperature of the spectral sensitizing dye of the present invention needs to be 25 ° C to 45 ° C. Preferably 30 ° C to 40 ° C, more preferably 35 ° C
It can be set to any temperature in the range of -40 ° C. The sensitizing aging temperature is preferably 50 ° C to 80 ° C, more preferably 50 ° C.
It can be set to any temperature in the range of -60 ° C.

Examples of the spectral sensitizing dye having a maximum absorption wavelength of J-band of 555 nm or less in the present invention include benzimidazolocarbocyanine. A preferred benzimidazolocarbocyanine dye can be represented by the following general formula (I).

[0037]

Embedded image

In the formula, R ₁ and R ₃ are methyl or ethyl, and at least one of R ₁ and R ₃ is methyl. R ₂
And R ₄ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl, butyl, pentyl and hexyl groups. Examples of substituents include one or more sulfone, sulfide, carboxy, fluoro, amides, esters, cyano, substituted or unsubstituted aryls and other substituents commonly used in photographic sensitizing dyes. Examples of the substituted alkyl of R ₂ and R ₄ include sulfopropyl, sulfobutyl, trifluoroethyl, allyl, 2-butynyl, N, N-dimethylcarbamoylmethyl, methylsulfonylcarbamoylmethyl, cyanomethyl, cyanoethyl, ethoxycarbonylmethyl and the like. To be

Z _{1 to} Z ₄ are each methyl, methylthio, fluoro-substituted methylthio, or hydrogen. Fluoromethyl, difluoromethyl, trifluoromethyl, fluoromethylthio, difluoromethylthio and trifluoromethylthio.

Depending on the substituents R ₂ and R ₄ , the counterion X ₁ may be necessary to neutralize the charge on the dye molecule. For example, if the dye molecule is substituted with two anionic substituents (eg sulfone), X ₁ will be a cation. If the dye molecule is substituted with only one anionic substituent, then the counterion X ₁ is absent. The dye molecule will consist of anionic substituents. Such counterions are well known in the art and include cations such as sodium, potassium, triethylammonium and the like, and anions such as chloride, bromide,
Examples thereof include iodide, p-toluene sulfonate, methane sulfonate, methyl sulfate, ethyl sulfate, perchlorate and fluoroborate.

Next, the above-mentioned general formula (I) used in the present invention is used.
Specific examples of the benzimidazolocarbocyanine dye represented by are shown below, but the compounds usable in the present invention are not limited to these.

[0042]

Embedded image

As the benzimidazolocarbocyanine dye represented by the above general formula (I) of the present invention, in addition to the above specific examples, for example, Table 1 of Japanese Patent Application No. 261264/1993.
Also, the compound examples described in Table 2 and Table 1 of JP-A-5-88293 can be similarly used.

As a spectral sensitizing dye that is preferably used in the present invention, a combination technique of the above-mentioned two spectral sensitizing dyes of benzimidazolocarbocyanine dye and oxacarbocyanine dye will be described below. The combined use technique of two kinds of spectral sensitizing dyes, which are a benzimidazolocarbocyanine dye and an oxacarbocyanine dye, is extremely useful in a light-sensitive material that requires sensitivity to green light. In particular, it is remarkably effective in the application to an X-ray recording material using a phosphor that emits green light in order to increase the recording sensitivity to X-rays, and is particularly effective in a light-sensitive material for X-ray medical treatment.

In order to further improve the sensitivity and to improve the residual color, it is preferable that the benzimidazolocarbocyanine dye of the present invention is used in an amount of 40% or more of the total amount of the dye in the light-sensitive material.

Specific examples of the oxacarbocyanine dyes preferably used in the present invention will be given below, but the present invention is not limited thereto.

[0047]

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[0048]

[Chemical 4]

The maximum absorption wavelength of the J-band of the present invention is 55.
The spectral sensitizing dye having a wavelength of 5 nm or less may be used in combination with other spectral sensitizing dyes other than the above. The dyes used include cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar dye, hemicyanine, styryl type and hemioxonol dyes. Particularly useful dyes are those belonging to cyanine, merocyanine and complex merocyanine dyes. For these dyes, any of the nuclei normally used for dyes as a chemical structure can be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc., and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei, that is, India A renin nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may have substituents on carbon atoms.

The merocyanine or complex merocyanine dye has pyrazoline-5-containing nuclei having a ketomethine structure.
On nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazoline-2,4-dione nucleus,
A 5- to 6-membered heterocyclic nucleus such as a rhodanine nucleus and a thiobarbituric acid nucleus can be applied.

Along with these spectral sensitizing dyes, a dye having no spectral sensitizing property or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect is added to the emulsion layer. May be.

The addition amount of the spectral sensitizing dye in the present invention is
Kind of dye and structure of silver halide, composition, ripening condition,
Depending on the purpose and application, the monolayer coverage of each photosensitive grain in the silver halide emulsion is 40% or more, 9
It is preferable to set it to 0% or less, and further 50%
-80% is especially preferable.

In the present invention, the monolayer coverage is 5
The saturated adsorption amount when the adsorption isotherm is created at 0 ° C. is relatively determined as the amount corresponding to 100% coverage.

The appropriate amount per mol of silver halide varies depending on the total surface area of silver halide grains in the emulsion, but is 6
Less than 00 mg is preferred. Further, it is preferably 450 mg or less.

As a solvent for the sensitizing dye, a conventionally used water-miscible organic solvent can be used. For example, alcohols, ketones, nitriles, alkoxy alcohols, etc. have been used. As specific examples, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol,
There are 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol, 2-ethoxyethanol and the like.

Surfactants have been conventionally used as dispersants for spectral sensitizing dyes. The surfactant includes anionic, cationic, nonionic and amphoteric surfactants, and any of these surfactants can be used in the present invention.

In the present invention, the effect is increased by adding the spectral sensitizing dye as a solid fine particle dispersion, as compared with the case of adding it as a solution of an organic solvent. In particular, at least one of the spectral sensitizing dyes is substantially organic solvent and / or
Alternatively, it is preferably added in the form of a solid fine particle dispersion substantially insoluble in water dispersed in an aqueous system in which no surfactant is present.

In the present invention, the sensitizing dye and the chemical sensitizer are added at a temperature of 25 ° C. or higher and 45 ° C. or lower. As a more preferable temperature, the sensitizing dye is 30 ° C to 40 ° C and the chemical sensitizer is 30 ° C to 40 ° C.

The spectral sensitizing dye according to the present invention can be added at the time of chemical ripening, particularly preferably at the start of chemical ripening, and from the step of nucleating the silver halide emulsion of the present invention to the desalting step. By adding by the end,
Although a high-sensitivity silver halide emulsion with excellent spectral sensitization efficiency can be obtained, any of the above steps (from the nucleation step to the de-salting step, from the chemical ripening step to immediately before the coating step) can be performed. The spectral sensitizing dye according to the present invention, which is the same as or different from the dye added before the salting step), may be additionally added.

The order of adding the sensitizing dye and the chemical sensitizer is arbitrary, but it is preferable to add the chemical sensitizer after the sensitizing dye.

Next, the chemical sensitizer that may be used in the present invention will be described.

In the present invention, the conditions of the chemical sensitization step, such as pH, pAg, temperature and time, are not particularly limited, and the conditions generally used in the art can be used.

A sulfur sensitizing method using a compound containing sulfur capable of reacting with silver ions for chemical sensitization or active gelatin, a selenium sensitizing method using a selenium compound, a tellurium sensitizing method using a tellurium compound, a reducing substance. Can be used alone or in combination, and selenium sensitization, tellurium sensitization, reduction sensitization and the like are preferably used, particularly sulfur. A sensitizing method, a gold sensitizing method and a selenium sensitizing method are preferably used. Regarding the chemical sensitization method used in the chemical sensitization of the present invention, the sensitization method described in Japanese Patent Application No. 5-261264 can be referred to.

The selenium sensitizers used in the chemical sensitization of the present invention include a wide variety of selenium compounds. For example, in this regard, US Pat. Nos. 1,574,944 and 1,60
2,592, 1,623,499, JP-A-60-
150046, JP-A-4-25832 and 4-10.
Nos. 9240 and 4-147250. Examples of useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylseleno). Urea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N '
-Trimethyl-N'-4-nitrophenylcarbonyl selenourea etc.), selenoketones (eg selenoacetone, selenoacetophenone etc.), selenoamides (eg selenoacetamide, N, N-dimethylselenobenzamide etc.), selenocarboxylic acids And selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), selenides triphenylphosphine selenide (diethyl) Selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenium ketones. However, in the present invention, the effect is increased by adding the selenium sensitizer as a dispersion in the form of solid fine particles, as compared with the case where it is added as a solution of an organic solvent.

As the gold sensitizer, chloroauric acid, gold thiosulfate,
In addition to gold thiocyanate, thioureas, rhodanines,
Other examples include gold complexes of various compounds.

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

The silver halide photographic light-sensitive material of the present invention comprises J
-A sensitizing dye having a maximum absorption wavelength of 555 nm or less and a chemical sensitizer are added at a temperature of 25 ° C or higher and 45 ° C or lower, and then sensitized aging is performed at a temperature higher than the addition temperature of the sensitizing dye. Be seen.

Here, sensitizing ripening at a temperature higher than the temperature at which the sensitizing dye is added means that, for example, when the sensitizing dye and the chemical sensitizer are added at 40 ° C., the sensitizing dye and the chemical sensitizer are added at 40 ° C. for 5 minutes to It means ripening for 30 minutes, subsequently raising the temperature to higher than 40 ° C., and then adding a chemical sensitizer again to carry out chemical ripening.

In this case, the chemical sensitizer may not be added at the time of adding the sensitizing dye, and may be added only after the subsequent temperature increase.

When at least one of any of the layers containing the light-sensitive silver halide emulsion of the present invention or the constituent layers other than the emulsion layer contains a dye capable of being decolorized or / and flowed out during the development processing, it becomes high. A light-sensitive material having high sensitivity, high sharpness and little dye stain can be obtained. The dye used in the light-sensitive material may be appropriately selected from dyes capable of improving sharpness by absorbing a desired wavelength and removing the influence of the wavelength, depending on the light-sensitive material. I can. It is preferable that the dye be decolorized or flowed out during the development processing of the light-sensitive material, and the coloring should not be visible when the image is completed.

The dye used in the light-sensitive material of the present invention has a pH of 7.
Below, it is substantially insoluble in water, has a pH of 8 or more, and is substantially water-soluble. The addition amount can be changed according to the sharpness target. Preferably 0.2 mg / m ² to 2
0 mg / m ² , more preferably 0.8 mg / m ^{2 to} 15 m
g / m ² .

The silver halide photosensitive material according to the present invention comprises
Various photographic additives can be used. Known additives include, for example, Research Disclosure (R
D) No. 17643 (December 1978), the same No.
18716 (November 1979) and No. 3081
19 (December 1989).

The types of compounds and the places where they are described in these three Research Disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IIIA Desensitizing dye 23 IV 998 IIIB Dye 25 ~ 26 VIII 649 ~ 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Surfactant 26 ~ 27 XI 650 Right 1005 ~ 6 XI Charge Inhibitor 27 XII 650 Right 1006 to 7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008 to 9 XVI Binder 26 XXII 1009 to 4 XXII Support 28 XVII 1009 XVII Photosensitive material according to the present invention Examples of the support that can be used as the material include the above-mentioned RD-17643, page 28 and RD.
The thing described in page 1009 of -308119 is mentioned.

A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer, corona discharge, or ultraviolet irradiation in order to improve the adhesion of the coating layer.

In the photographic light-sensitive material of the present invention, when a silver halide emulsion layer and a crossover cut layer are provided on both sides of a support, a light-sensitive material having high sensitivity, high sharpness and excellent processability can be obtained. The total amount of gelatin in the silver halide emulsion layer, the surface protective layer and the other layers is 1.5 to 10 on the one side of the support.
It must be in the range of 3.5 g / m ² . The range of 2.0 to 3.0 g / m ² is particularly preferable.

Next, the solid processing agent of the present invention will be described.

The solid processing agent in the present invention is a powder processing agent or a solid processing agent such as tablets, pills and granules, which is optionally moisture-proofed. The powder means an aggregate of fine crystal grains. Granules are obtained by adding a granulation step to powders, and are granular materials having a particle size of 50 to 5000 μm. The tablet in the present invention refers to a powder or granules compression-molded into a certain shape.

To solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binding agent is formed on the surface of the temporarily molded photographic processing agent. Arbitrary means such as forming a coating layer by spraying can be employed (Japanese Patent Application Nos. 2-135887 and 2-2).
03165, 2-203166, 2-2031
67, ibid. 2-203168, ibid. 2-34009).

A preferable tablet manufacturing method is a method in which a solid processing agent in powder form is granulated and then a tableting step is performed. There is an advantage that the solubility and the storability are improved and the photographic performance becomes stable as compared with the solid processing agent formed by the tableting step by simply mixing the solid processing agent components.

As the granulation method for tablet formation, known methods such as rolling granulation, extrusion granulation, compression granulation, crushing 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, nonuniformity of the components, so-called segregation does not easily occur. Is preferably used, and more preferably 200 to
750 μm.

Further, the particle size distribution is preferably such that 60% or more of the granulated particles are within a deviation of ± 100 to 150 μm. When compressing the obtained granulated product under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a preketching machine can be used. The solid processing agent obtained by compression under pressure can have any shape, but from the viewpoint of productivity, handleability, or from the problem of dust when used on the user side, a cylindrical type, a so-called tablet is 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.

A method for producing a tablet treating agent is described in, for example, JP-A-51.
-61837, 54-155038, 52-8.
It can be produced by a general method described in the specifications such as 8025 and British Patent No. 1213808, and the granule treating agent is, for example, JP-A Nos. 2-109042 and 2-109043.
No. 3-39735, and No. 3-39739, and the like. Further, the powder processing agent can be produced by a general method as described in the specifications of JP-A-54-133332, British Patents 725892 and 729862, and German Patent 3,733,861.

[0085] The bulk density of the solid processing agent, and in view of its solubility, if a tablet from the viewpoint of the effect of the object of the present invention 1.0g / cm ³ ~2.5g / cm ³ is preferably 1. 0 g
/ Cm ³ in terms of strength of the obtained solid matter,
If it is less than 2.5 g / cm ³ , it is more preferable in terms of 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 .

The solid processing agent used in the present invention is a developer,
Although it is used as a fixing agent, a rinsing agent, and the like for a photographic processing agent, it is the developer that has a large effect of stabilizing the photographic performance of the present invention.

It is within the scope of the present invention to solidify only a part of the components of a certain treating agent in the solid treating agent used in the present invention, but preferably all components of the treating agent are solidified. Is. It is desirable that each component be molded as a separate solid processing agent and packaged in the same manner. It is also desirable that the individual components are packaged in the order in which they are periodically added repeatedly in a package.

It is preferable to add all the processing agents to be replenished to the respective processing tanks as solid processing agents according to the processing amount information.
When replenishment water is required, it is replenished based on the throughput information or other replenishment water control information. In this case, the liquid to be replenished in the processing tank can be only replenishing water. That is, when there are two or more types of processing tanks that need to be replenished, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the automatic developing machine can be made compact. The replenishing water tank may be placed outside or may be built in the automatic developing machine, and it is preferable to install the replenishing water tank from the viewpoint of space saving.

In the case of solidifying the developer of the present invention, it is necessary to make all the alkali agents and reducing agents into solid processing agents, and in the case of tablets, at least 3 agents or less, most preferably 1 agent. It is a preferred embodiment of the solid processing agent used. When two or more agents are divided into solid processing agents, it is preferable that the plurality of tablets or granules be packed in the same package.

In the present invention, as the means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Utility Model Publication Nos. 63-137783 and 63-9752.
There are known methods such as No. 2 and Jitsukaihei 1-85732.
In short, any method may be used as long as it has at least the function of supplying tablets to the processing tank. Further, when the solid processing agent is granules or powders, it is disclosed in JP-A-62-81964 and 6-62.
3-84151, the gravity drop method described in JP-A-1-292375, and the like, JP-A-63-105159, and JP-A-6-105159.
The method using a screw or a screw described in JP-A-3-195345 and the like is a known method, but the method is not limited thereto.

However, the preferable method is, as a supply means for supplying the solid processing agent to the processing tank, for example, a predetermined amount of the solid processing agent which is previously weighed and divided and packaged is opened in accordance with the processing amount of the photosensitive material, and the package is opened. A method of taking it out is possible. Specifically, the solid processing agent is sandwiched and housed in a package composed of at least two packaging materials by a predetermined amount, preferably one replenishment amount, and the package is separated in two directions or one of the packages is separated. The part is opened so that it can be taken out. The solid processing agent that can be taken out can be easily supplied to the processing tank having the filtering means by spontaneous fall. A predetermined amount of the solid processing agent is housed in a package that is divided and hermetically sealed so that the air permeability between the solid processing agent and the adjacent solid processing agent is blocked. Therefore, moisture resistance is guaranteed unless the package is opened.

As an embodiment, it is conceivable that a package composed of at least two packaging materials sandwiching the solid processing agent is closely adhered or adhered to each other so that the periphery of the solid processing agent can be separated. . By pulling the respective packaging materials sandwiching the solid processing agent in different directions, the closely contacted or adhered contact surfaces are separated, and the solid processing agent can be taken out.

As another embodiment, it is conceivable that at least one of the packages made of at least two packaging materials can be opened by an external force so as to sandwich the solid processing agent. The term "opening" as used herein means a cut or break that leaves a part of the packaging material. As the unsealing method, the solid processing agent is forcibly pushed out by applying a compressive force from the packaging body on the non-opening side to the packaging body which can be opened through the solid processing agent, or on the packaging body on the openable side. It is considered that the solid processing agent can be taken out by making a cut with a sharp member.

The supply start signal is obtained by detecting the processing amount information. The supply stop signal is obtained by detecting the information that the supply of the predetermined amount is completed. Further, when the treatment agent is packaged and needs to be opened, the driving means for separating or opening based on the obtained supply start signal operates, and the driving means for separating or opening based on the supply stop signal is It can be controlled to stop.

The above-mentioned solid processing agent supply means has a control means for charging a fixed amount of the solid processing agent in accordance with information on the processing amount of the photosensitive material, which is an important requirement in the present invention.
That is, in the automatic processor of the present invention, it is necessary to keep the component concentration of each processing tank constant and to stabilize the photographic performance. What is the processing amount information of silver halide photographic light-sensitive materials?
It is a value proportional to the processing amount of the silver halide photographic light-sensitive material processed with the processing liquid, the processing amount of the processed silver halide photographic light-sensitive material or the processing amount of the silver halide photographic light-sensitive material being processed. Indirectly or directly indicates the amount of reduction of the treating agent in the liquid. It may be detected before or after the photosensitive material is carried into the processing liquid, or at any timing during immersion in the processing liquid. Further, it may be a physical parameter such as the concentration of the composition in the treatment liquid or a change in the concentration, pH and specific gravity. Further, it may be the amount of the treatment liquid which is discharged to the outside after drying.

The solid processing agent of the present invention may be placed in a processing tank, but preferably, it is communicated with a processing section for processing a light-sensitive material, and a processing solution flows between the processing section and the processing section. It is preferable that the structure is such that the dissolved components move to the processing section because there is a certain amount of processing liquid circulation between the processing section and the processing section. The solid processing agent is preferably added to the temperature-controlled processing liquid.

In the developer used in the present invention, in addition to dihydroxybenzenes, aminophenols and pyrazolidones described in Japanese Patent Application No. 4-286232 (pages 19 to 20) as developing agents, JP-A-5-165161 is used. The reductones described in No. 1 are also preferably used. Among the pyrazolidones to be used, those substituted at the 4-position (dimesone, dimeson S, etc.) are particularly preferable because their water solubility and the solid treating agent themselves do not change over time.

As the preservative, an organic reducing agent can be used as the preservative in addition to the sulfite described in Japanese Patent Application No. 4-286232. In addition, Japanese Patent Application No. 4-586323 (20
The chelating agent described in page) and the bisulfite adduct of the hardening agent described in the same (page 21) can be used. Also, as a silver sludge inhibitor, Japanese Patent Application Nos. 4-92947 and 5-96
It is also preferable to add the compound described in No. 118 (general formula [4-a] [4-b]). Addition of a cyclodextrin compound is also preferable, and the compounds described in JP-A No. 1-124853 are particularly preferable.

An amine compound may be added to the developer, and the compounds described in US Pat. No. 4,269,929 are particularly preferable.

It is necessary to use a buffer for the developer,
As the buffer, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate,
Tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
2-hydroxybenzoic acid potassium (potassium 5-sulfosalicylate) etc. can be mentioned.

As a development accelerator, JP-B-37-1608
No. 8, No. 37-5987, No. 38-7826, No. 4
Nos. 4-12380 and 45-9019 and U.S. Pat.
No. 81347 and other thioether compounds, JP-A Nos. 52-49829 and 50-15554, p-phenylenediamine compounds, and JP-A-50-
137726, JP-B-44-30074, JP-A-5
Quaternary ammonium salts represented by US Pat. Nos. 6,156,826 and 52-43429, and US Pat.
2 and 4,119,462, p-aminophenols, US Pat. Nos. 2,494,903 and 3,12.
8,182, 4,230,796, 3,25
3, 919, Japanese Examined Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582.346, and amine compounds described in Japanese Examined Patent Publication No. 37-16088. 42-25201, U.S. Pat. No. 3,128,183, Japanese Patent Publication No. 41-11431,
42-23883 and U.S. Pat. No. 3,532,501.
No. 1 and other polyalkylene oxides, other 1-
Phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

As the antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, A nitrogen-containing heterocyclic compound such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine can be mentioned as a representative example 1-phenyl-5-mercaptotetrazole.

Further, in the developer composition used in the present invention, if necessary, methyl cellosolve, methanol,
Acetone, dimethylformamide, cyclodextrin compound, other Japanese Patent Publication Nos. 47-33378 and 44-9
The compounds described in JP-A No. 509 can be used as an organic solvent for increasing the solubility of the developing agent.

Furthermore, other various additives such as stain inhibitors, sludge inhibitors, and stacking effect accelerators can be used.

A compound known as a fixing agent can be added to the fixing agent used in the present invention. Fixing agents and chelating agents, p
An H buffer, a hardener, a preservative and the like can be added, and these are described in, for example, JP-A-4-242246 (page 4) and JP-A-5-11.
Those described in 3632 (pages 2 to 4) can be used. In addition, as a hardener, a chelating agent described in Japanese Patent Application No. 4-586323 (page 20), a bisulfite adduct of the hardener described in the same (page 21), or a known fixing accelerator can be used.

Prior to the treatment, it is also preferable to add a starter, and it is also preferable to solidify the starter and add it. As the starter, in addition to organic acids such as polycarboxylic acid compounds, halides of alkaline earth metals such as KBr, organic inhibitors, and development accelerators are used.

Next, preferable development processing of the light-sensitive material of the present invention will be described.

A preferred developing solution for developing the light-sensitive material of the present invention is a developing agent disclosed in JP-A-4-15641.
Dihydroxybenzenes such as those described in JP-A-4-16841, such as hydroquinone, para-aminophenols such as p-aminophenol, N-methyl-p-aminophenol, 2,4-diamiphenol, and the like, 3-
Examples of the pyrazolidones include 1-phenyl-3-pyrazolidones, 1-phenyl-3-pyrazolidone, 1-
Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone and the like are preferably used in combination.

The above-mentioned para-aminophenols, 3-
The amount of aminopyrazolidones used is preferably 0.004 mol / liter, more preferably 0.04 to 0.1.
It is 2 mol / liter.

Further, the total number of moles of dihydroxybenzenes, paraaminophenols and 3-pyrazolidones contained in these components of all developing solutions is preferably 0.1 mol / liter or less.

Preservatives may include sulfites such as potassium sulfite, sodium sulfite, reductones such as piperidinohexose reductone,
These are preferably used in an amount of 0.2 to 1 mol / liter, more preferably 0.3 to 0.6 mol / liter. Further, addition of a large amount of ascorbic acid also leads to processing stability.

As the alkaline agent, sodium hydroxide,
Includes pH adjusters such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate. Further, even if a borate described in JP-A No. 61-28708 or a buffer such as saccharose, acetoxime, 5-sulfosalicylic acid, phosphate or carbonate described in JP-A-60-93439 is used. Good. The content of these agents is such that the pH of the developer is 9.0 to 13, preferably p.
Choose to be H10-12.5.

As the solubilizing agent, polyethylene glycols and their esters, and as the sensitizing agent,
For example, a development accelerator, a surfactant, etc. such as a quaternary ammonium salt can be contained.

As a silver sludge-preventing agent, JP-A-56-
No. 106244, a silver stain inhibitor, JP-A-3-518.
The sulfides and disulfide compounds described in No. 44, and the cysteine derivatives or triazine compounds described in Japanese Patent Application No. 4-92947 are preferably used.

As the organic inhibitor, an azole type organic antifoggant, for example, an indazole type, imidazole type, benzimidazole type, triazole type, benztriazo type, tetrazole type or thiadiazole type compound is used. Inorganic inhibitors include sodium bromide, potassium bromide, potassium iodide and the like. In addition, L. F.
A. Menson's "Photographic Processing Chemistry" published by Focal Press (1966)
226-229, U.S. Pat. No. 2,193,015,
Those described in JP-A No. 2,592,364 and JP-A-48-64933 may be used. As a chelating agent for masking calcium ions mixed in tap water used as a treatment liquid, an organic chelating agent is disclosed in JP-A-1-193.
A chelating agent having a chelate stabilization constant of 8 or more with iron described in No. 853 is preferably used. Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate.

As the development hardening agent, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used.

The silver halide light-sensitive material of the present invention has a total processing time of 30 by a processing method including development, fixing and drying steps.
It is characterized by being less than a second. Total processing time is Dry
The toDry time is preferably 15 to 30 seconds, more preferably 20 to 30 seconds.

The processing temperature of the developer is preferably 25 to 50.
C., more preferably 30 to 40.degree. The development time is 3 to 15 seconds, more preferably 4 to 10 seconds.

The processing temperature of the developing solution is preferably 25 to 50.
C., more preferably 30 to 40.degree. The development time is 3 to 15 seconds, more preferably 4 to 10 seconds.

The treatment liquid is replenished by the amount corresponding to the treatment agent fatigue and oxidation fatigue. As a replenishment method, JP-A-55-126
Replenishment according to the width and feed rate described in Japanese Patent No. 243, JP-A-60.
Area replenishment described in JP-A-104946, JP-A 1-1491
Area replenishment controlled by the number of continuous treatments described in No. 56 may be used, and the preferable replenishment amount is 500 to 150 ml /
m ² .

In the present invention, the fixing liquid means the liquid in the fixing tank. Preferred fixing solutions can include fixing materials commonly used in the art. The iodine content is preferably 0.3 g / liter or less, more preferably 0.1 g / liter or less. The pH is 3.8 or higher, preferably 4.2 to 5.5. Preferred replenishment rate is 500
Is about 100 cc / m ² .

The fixing agent is a thiosulfate salt such as ammonium thiosulfate and sodium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The concentration of ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / liter, more preferably 0.8 to 3 mol / liter.

The fixing solution may be one that performs acid hardening. In this case, aluminum ions are preferably used as the hardener. For example, it is preferably added in the form of aluminum sulfate, aluminum chloride, potassium alum, or the like.

If desired, the fixing solution may include sulfite,
Preservatives such as bisulfite, pH buffers such as acetic acid and boric acid, mineral acids (sulfuric acid, nitric acid) and organic acids (citric acid, oxalic acid, malic acid, etc.), various acids such as hydrochloric acid, and metal hydroxides ( A pH adjusting agent such as potassium hydroxide or sodium) and a chelating agent having the ability to soften water can be contained.

As the fixing accelerator, for example, Japanese Patent Publication No. 45-3
No. 5754, No. 58-122535, No. 58-122.
A thiourea derivative described in US Pat. No. 4,126,
Examples thereof include thioethers described in No. 459.

The silver halide emulsion layer of the present invention preferably has a swelling ratio during development of 150 to 250% and a film thickness after expansion of 70 μm or less. Water swelling rate is 250%
If it exceeds the above range, poor drying occurs, and, for example, defective transport occurs in automatic processor processing, especially in rapid processing. Further, if the water swelling ratio is less than 150%, uneven development and residual color tend to be deteriorated during development. Here, the water swelling rate is the difference between the film thickness after swelling in each processing solution and the film thickness before the development processing,
This is divided by the film thickness before processing and multiplied by 100.

In the present invention, X-ray photography can be carried out by sandwiching the silver halide photographic light-sensitive material of the present invention between high-sensitivity intensifying screens. Here, the filling rate of the phosphor in the phosphor layer of the radiation intensifying screen of the high-sensitivity intensifying screen according to the present invention is 68%.
It is at least 70%, more preferably at least 72%.

In the present invention, the thickness of the phosphor layer is 15
It is 0 μm or more and 250 μm or less. Here, if the thickness of the phosphor layer is less than 150 μm, the sharpness is sharply deteriorated.

The radiographic intensifying screen of the present invention is preferably filled with a phosphor in a gradient grain size structure. In particular, it is preferable to apply phosphor particles having a large particle size on the surface protective layer side and phosphor particles having a small particle size on the support side, and those having a small particle size are 0.5 to 2.0 μm. 10 to 30 for particles
The range of μm is preferred.

In the fluorescent intensifying screen used in the combination of the present invention, the X-ray absorption of each intensifying screen is 30% per 100 μm of the thickness of the phosphor layer by increasing the packing ratio of the phosphor particles. The above is preferable. The X-ray absorption amount was determined as follows. That is, an X-ray generated from a tungsten target operated at 80 KVP from an X-ray generator having an aluminum 2.2 mm equivalent intrinsic filtration with a three-phase power supply is transmitted through an aluminum plate having a thickness of 3 mm and a purity of 99% or more. Then, the target tube was made to arrive at a radiographic intensifying screen fixed at a position 200 cm from the tungsten anode, and then the X-ray absorption amount was measured at a position 50 cm after the phosphor layer of the radiographic intensifying screen using an ionization dosimeter. I asked. As a reference, the X-ray dose at the above-mentioned measurement position measured without passing through the intensifying screen was used.

Preferred binders used in the radiation intensifying screen of the present invention 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, fluororubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber and silicone rubber. At least one thermoplastic elastomer may be mentioned.

The filling rate of the phosphor in the present invention can be obtained from the following formula from the porosity of the phosphor layer formed on the support.

[0133]

[Equation 1]

Preferred phosphors used in the radiation intensifying screen according to the present invention include those shown below.

Tungstate phosphor (CaWO ₄ ,
MgWO ₄ , CaWO ₄ : Pb, etc.), terbium-activated rare earth oxysulfide 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 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-based phosphors (LaOBr: Tm, LaOCl: Tm)
Etc.), a barium sulfate-based phosphor [BaSO ₄ : Pb, Ba
SO ₄ : Eu ²⁺ , (Ba.Sr) SO ₄ : Eu ^2+, etc.], 2
-Valent 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 .
XBaSO4. KCl: Eu ²⁺ , (Ba.Mg) F ₂ ..
BaCl ₂ . KCl: Eu ^2+, etc.], iodide type phosphors (CSI: Na, CSI: Tl, NaI.KI:Tl
Etc.) Sulfide-based phosphor [ZnS: Ag, (Zn.Cd)
S: Ag, (Zn.Cd) S: Cu, (Zn.Cd)
S: Cu. Al, etc.], Hafnium phosphate-based phosphor (HfP
₂ O ₇ : Cu, etc., but the phosphor used in the present invention 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.

[0136]

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

Example 1 (Preparation of Em-1) Referring to the production method described in the Example of JP-A-5-281640, the main plane was (1
A silver iodobromide tabular grain emulsion having a (00) plane was prepared as follows.

Gelatin solution-1 {Pure water 120
0 ml, 24 g of deionized alkali treated gelatin, 5 ml of potassium nitrate (1N), pH with nitric acid (1N) solution
4.0 was added} and the temperature was kept constant at 40 ° C. 10m of silver nitrate-1 solution (3g of silver nitrate / 100ml of water) while stirring
5 minutes later, a silver nitrate-1 solution and a halide-1 aqueous solution (KBr: KI = 98.5: 1.
(5 molar ratio) was added at 48 ml / min for 1 minute by the precision mixing pump by the simultaneous mixing method. After stirring for 1 minute, the pH was adjusted to 6.1 using nitric acid solution and potassium hydroxide solution, and the silver potential was adjusted to 160 mV using silver nitrate-1 solution and potassium bromide-1 solution. Next, the temperature was raised to 75 ° C. in 10 minutes and aging was performed for 30 minutes. Next, 5 ml of ammonium nitrate aqueous solution-1 (50% by weight) and 5 ml of ammonium nitrate aqueous solution-1 (25% by weight) were added, and then silver nitrate-2 solution (silver nitrate 10 g / water 100 ml) and halide-2 aqueous solution (potassium bromide 7. Simultaneous mixing (contro) using 0 g / 100 ml of water while keeping the silver potential at 120 mV.
lled double jet) method. The initial flow rate was 10 ml / min, and 570 ml was added by the linear flow rate accelerated addition method of 0.05 ml / min. After stirring for 2 minutes,
The temperature was lowered to 30 ° C., and the precipitate was washed with water by sedimentation. An aqueous gelatin solution was added to redisperse the emulsion, pH 6.0, pBr 2.8
Adjusted to.

The following results were obtained from a TEM image of the obtained emulsion grain replica. That is, the main plane is the (100) plane, the shape of the main plane is substantially quadrangular, the projected area ratio of the tabular grains is about 93%, and the average projected grain size is 1.1 μm.
m, the average aspect ratio was 4.6, and the variation coefficient of the particle size distribution was 25%. The particles are core / shell type particles, and the iodine content is higher in the core part.

Subsequently, the above-mentioned emulsion Em-1 was divided into predetermined amounts, and the addition temperatures shown in Table 1 were applied. Then, predetermined amounts of the exemplified spectral sensitizing dyes I-11 and II-5 were dispersed in the form of solid fine particles. After the addition as a substance, a solid fine particle dispersion of ammonium thiocyanate, chloroauric acid, a sulfur sensitizer, and triphenylphosphine selenide was added and stirred for 15 minutes. Thereafter, the temperature was raised to 55 ° C., and 1 hour later, an aqueous solution of a gold sensitizer or a methanol solution shown below was added, and aging was carried out for a total of 2 hours. At the end of aging, 1-phenyl-5-mercaptotetrazole (PMT) and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) were added as stabilizers.

The additives and their addition amounts (per 1 mol of AgX) are shown below.

Spectral sensitizing dye I-11 (λmax = 550 nm) 185 mg Spectral sensitizing dye II-5 (λmax = 546 nm) 170 mg Ammonium thiocyanate 95 mg Chloroauric acid 12.5 mg Sodium thiosulfate (pentahydrate) (sulfur sensitization) Sensitizer) 10.0 mg Triphenylphosphine selenide 2.0 mg Stabilizer (TAI) 200 mg Stabilizer (PMT) 5 mg (Preparation of Em-2) A tabular silver iodochloride emulsion Em was prepared using the following three solutions. -2 was prepared.

A1 low methionine gelatin 214.37 g sodium chloride 1.995 g potassium iodide 149.6 mg with water to make 6090 ml B1 sodium chloride 10.48 g potassium iodide 149.4 g with water to make 90 ml C1 silver nitrate 30.58 g with water Finish to 90 ml D1 Sodium chloride 165.0 g Finish to 5640 ml with water E1 Silver nitrate 479.0 g Finish to 5640 ml with water Stir vigorously while keeping solution A1 at 40 ° C in the reaction vessel, and add all the amounts of solution B1 and solution C1 to it. 180 ml per minute
Was added by the simultaneous mixing method at a flow rate of 30 seconds.

Next, this mixed solution was kept at 40 ° C. for 10 minutes, and then the solution D1 and the solution E1 were mixed at a flow rate of 24 ml / min.
Add by the simultaneous mixing method over 0 minutes, and then simultaneously add the remaining total amount of the solution D1 and the solution E1 over 130 minutes while linearly increasing the flow rate so that the initial flow rate is 24 ml and the final flow rate is 48 ml. Method was added. During this time,
The pCl was kept at 2.35 throughout. Then, it was adjusted to 1.30 with sodium chloride, pCl was adjusted to 2.0 using an ultrafiltration membrane, and pCl was adjusted to 1.65 by adding sodium chloride.

The obtained silver halide emulsion has an iodide of 0.0
6 mol% is contained, and when observed by an electron microscope, the average particle diameter (converted to a circle diameter) is 0.58 μm, and the average thickness is 0.13 μ.
It was a right-angled parallelogrammatic tabular silver halide grain having an average aspect ratio of 4.5.

Subsequently, each of the above emulsions Em-2 was divided into predetermined amounts, and the addition temperatures shown in Table 2 were obtained.
Solid spectroscopic dispersions of ammonium thiocyanate, chloroauric acid, sulfur sensitizer, and triphenylphosphine selenide after addition of predetermined amounts of the exemplified spectral sensitizing dyes I-11 and II-5 as solid fine particle dispersions And a silver iodide fine grain emulsion were added and stirred for 15 minutes. Thereafter, the temperature was raised to 55 ° C., and 1 hour later, an aqueous solution of a gold sensitizer or a methanol solution shown below was added, and aging was carried out for a total of 2 hours. At the end of aging, (PMT) and (TAI) were added as stabilizers.

The additives and their addition amounts (per mol of AgX) are shown below.

Adenine 15 mg Spectral sensitizing dye I-11 (λmax = 550 nm) 250 mg Spectral sensitizing dye II-5 (λmax = 546 nm) 200 mg Ammonium thiocyanate 145 mg Chloroauric acid 18.5 mg Sodium thiosulfate (pentahydrate) 15 0.0 mg triphenylphosphine selenide 3.0 mg silver iodide fine particles 200 mg stabilizer (TAI) 100 mg stabilizer (PMT) 15 mg A solid fine particle dispersion of a spectral sensitizing dye is disclosed in Japanese Patent Application No. 4-994.
It was prepared by a method similar to that described in No. 37.

That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature was previously adjusted to 27 ° C., and the mixture was mixed with a high-speed stirrer (dissolver) for 3,5
Obtained by stirring at 00 rpm for 30-120 minutes.

The following additives were added to the obtained emulsion to prepare an emulsion layer coating solution. At the same time, a protective layer coating solution described below was also prepared. Using both coating solutions, two slide hopper type coaters were used so that the coated amount was 1.6 g / m ² per side and the amount with gelatin was 2.7 g / m ²
Simultaneous coating on both sides on a support at a speed of 0 m, followed by drying for 2 minutes and 20 seconds, and sample No. 1 to 8 were obtained. As a support, a copolymer aqueous dispersion obtained by diluting the copolymer consisting of three kinds of monomers of glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%, and butyl methacrylate 40 wt% to 10 wt% is undercoated. As a liquid, a polyethylene terephthalate film base colored blue with a concentration of 0.15 for a 175 μm X-ray film was used.

The additives used in the emulsion are as follows.
The amount of addition is shown in an amount per mole of silver halide.

First layer (dye layer) Solid fine particle dispersion dye (AH) 180 mg / m ² gelatin 0.2 g / m ² sodium dodecylbenzenesulfonate 5 mg / m ² 2,4-dichloro-6-hydroxy-1, 3,5-Triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² Second layer (emulsion layer) The following various additives were added to each emulsion obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone ( Molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / M ² 1,3-dihydroxybenzene-4-sulfonic acid ammonium salt 500 mg / m ² 2-mercaptobenzimidazole-5-sulfonic acid sodium salt 5 mg / m ² compound (H) 0.5 mg / m ² n-C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N ( CH ₂ COOH) ₂ 350 mg / m ² compound (M) 5 mg / m ² compound (N) 5 mg / m ² colloidal silica 0.5 g / m ² latex (L) 0.2 g / m ² dextrin (average molecular weight 1000) 0 .2g / m ^2, however, was adjusted to 1.0 g / m ² as gelatin.

Third Layer (Protective Layer) Solid Fine Particle Dispersion Dye (AH) 50 mg / m ² Gelatin 0.8 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene Table 3 Matting agent consisting of polymethylmethacrylate 50 mg / m ² (area average particle size 7.0 μm) Formaldehyde 20 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² Bis-vinylsulfonylmethyl ether 36 mg / m ² latex (L) 0.2 g / m ² polyacrylamide (average molecular weight 10000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (S1) 20 mg / m ² compound (I) 12mg / m ² compound (J) 2mg / m ² compound (S-1) 7mg / m 2 compound (K) 1 mg / m ² Compound (O) 50mg / m ² Compound (S-2) 5mg / m 2 C 9 F 19 O (CH 2 CH 2 O) 11 H 3mg / m 2 C 8 F 17 SO 2 N (C 3 H ₇ ) (CH ₂ CH ₂ O) ₁₅ H 2 mg / m ² C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ SO ₃ Na 1 mg / m ²

[0155]

Embedded image

[0156]

[Chemical 6]

[0157]

[Chemical 7]

Next, each sample was stored for 7 days under the following two conditions.

Condition A: 23 ° C., 55% RH Condition B: 40 ° C., 80% RH Photographic properties were evaluated using 1-8. First, the sample is two screens (Konica Corporation)
Made. KO-250), and a tube voltage of 80 kvp, a tube current of 100 m, A, and an X-ray of 0.05 second for irradiation through an aluminum wedge for exposure.

Next, an automatic developing machine (manufactured by Konica Corporation) SR
Treated with X fixer. A development supplement tablet was prepared according to the following procedure (A, B).

Operation (A) 3000 g of hydroquinone as a developing agent is ground in a commercially available bandam mill until the average particle size becomes 10 μm. 3000g of sodium sulfite and 20g of potassium sulfite in this fine powder
00g, Dimezone S1000g were added, mixed in a mill for 30 minutes and mixed in a commercial stirred granulator at room temperature for about 10 minutes,
After granulating by adding 30 ml of water, the granulated product is dried in a fluidized bed dryer at 40 ° C. for 2 hours to remove almost completely the water content of the granulated product. 25 g of 100 g of polyethylene glycol 6000 was added to the granules thus prepared.
After uniformly mixing with a mixer for 10 minutes in a room controlled to 40 ° C. or less and 40% RH or less, the obtained mixture was tableted by a tableting machine modified from Kikusui Seisakusho's Tough Press Collect Was compressed into tablets to make 3.84 g, and 2500 tablets of developer replenishment tablet A were prepared.

Operation (B) 100 g of DTPA, 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 7 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohypoxanthine, 200 g of KOH, N-acetyl-D, L-penicillamine were operated. It grind | pulverizes and granulates like (A). The amount of water added was 30.0 ml, and after granulation, the granulated product was dried for 30 minutes at 50 ° C. to almost completely remove water. The mixture thus obtained was compressed into tablets using a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. so that the filling amount per tablet was 1.73 g and the mixture was compressed to 250
0 developing replenishing tablet B agents were prepared. Next, a fixing supplementary tablet was prepared by the following procedure.

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is pulverized in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), add 500 ml of water.
And granulate. After the granulation, the granulated product is dried at 60 ° C. for 30 minutes to almost completely remove the water content of the granulated product. 4 g of sodium N-lauroylalanine is added to the granulated product thus prepared, and mixed for 3 minutes using a mixer in a room where the humidity is adjusted to 25 ° C. and 40% RH or less. Next, the obtained mixture was tough pressed collect 15 manufactured by Kikusui Seisakusho KK
Using a tableting machine modified from 27HU, the filling amount per tablet was 6.202 g, and compression tableting was performed to prepare 2,500 fixing replenishing tablet A agents.

Operation (D) Boric acid 1000 g, aluminum sulfate 18-hydrate 1500
g, sodium hydrogen acetate (3000 g of glacial acetic acid and sodium acetate mixed and dried), 3000 g, tartaric acid 200 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 1
The volume of the granules is adjusted to 00 ml, and after granulation, the granules are dried at 50 ° C. for 30 minutes to almost completely remove water. 4 g of sodium N-lauroylalanine was added to the thus-prepared product, and the mixture was mixed for 3 minutes, and then the obtained mixture was mixed with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. The filling amount was 4.562 g and compression tableting was performed to prepare 1250 fixing replenishment tablet D agents.

Developer starter Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make 1 liter.

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

The light-sensitive material prepared above was exposed to light so that the optical density after development was 1.0, and running was carried out.

For running, an automatic processor SRX-502 is used.
A solid processing agent charging member was attached to and modified so that the processing speed could be 15 seconds. During the running, the developer was added to each of the above-mentioned ^two A and B agents and 76 ml of water per 0.62 m ² of the light-sensitive material. 3 for A and B
The pH when dissolved in 8 ml of water was 10.70. To the fixing solution, ² parts of the above C agent, 1 part of D agent and 74 ml of water were added per 0.62 m ² of the light-sensitive material. The rate of water addition to each of the treatment agents was started almost at the same time as the addition of the treatment agent, and was added at a constant rate for 10 minutes in proportion to the dissolution rate of the treatment agent.

[0169] Developer composition Potassium carbonate 40 g Hydroquinone 30 g Dimezone S 10 g Diethylenetriamine pentaacetic acid-5Na 1 g (DTPA) Potassium bromide 1 g 5-Methylbenzotriazole 0.1 g 1-Phenyl-5-mercaptotetrazole 0.07 g 2-mercaptohypoxanthine 0.05 g sodium sulfite 30 g potassium sulfite 25 g KOH 2 g diethylene glycol 50 g N-acetyl-D, L-penicillamine 0.1 g These are dissolved in 300 ml of water and finally 400 m with pure water.
finished to 1. This concentrate was diluted with water to 1 liter to prepare a replenisher. The pH of this replenisher was 10.70.

Fixer composition Sodium thiosulfate 42.0 g Potassium thiosulfate 98.0 g Sodium sulfite 15.0 g Boric acid 10.0 g Sodium hydrogen acetate 30.0 g Glacial acetic acid 17.3 g Sodium acetate 12.7 g Tartaric acid 2.0 g Dissolve in 400 ml of water and finally with pure water 500 m
finished to 1. This concentrate was diluted with water to 1 liter to prepare a replenisher. The pH of this replenisher was 4.50.

The processing stability was evaluated by uniformly exposing the prepared sample with tungsten light so that the transmitted light blackening concentration would be 1.0 until the processing level reached an equilibrium state (quarter size. Was performed for 2000 sheets), and sensitometry was performed at the initial level and the level after running for comparison.

Similar effects can be obtained by using sodium erythorbate instead of hydroquinone as a developing agent.

The photographic performance of each sample was measured. Sample No. Based on the result of condition A of 1 (10
It was shown as a relative value when it was set to 0). The smaller the difference between the condition A and the condition B, the smaller the variation and the better.

Regarding evaluation of pressure fog, condition A
A load of 5 g was applied to the unexposed sample stored in 1 above by a scratch hardness meter with a needle head of 0.3, the same development processing as above was performed, and the pressure fog density was measured with a microdensitometer.

[0175]

[Table 1]

Sample No. marked with * in Table 1 5 and No. 10
Used the sensitizing dye Comparative A (566 nm / AgX). When a dye having a long absorption wavelength in the J-band as in Comparative A is used, the sensitivity is low, the storage stability is not good, and the pressure resistance is not good.

As is clear from Table 1, the samples of the present invention are
The sensitivity is high, and the pressure resistance is excellent, and the sensitivity processing fluctuation range is small even when stored under high temperature and high humidity. It can be seen that, when the solid processing agent of the present invention is used, sensitivity is hardly impaired even in rapid processing of 15 seconds, and pressure resistance is good.

Example 2 (Preparation of seed emulsion-1) Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 bromide Potassium 824 g Potassium iodide 11.7 g Water 2825 ml D1 1.75N potassium bromide aqueous solution Silver potential control amount at 42 ° C. Japanese Patent Publication Nos. 58-58288 and 58-5828
The solution B1 was added to the solution A1 using the mixing stirrer shown in No. 9.
And 464.3 ml of each of Solution C1 were added by the simultaneous mixing method over 1.5 minutes to perform nucleation.

After stopping the addition of the solution B1 and the solution C1, it took 60 minutes to raise the temperature of the solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then re-solution. B1 and solution C1 were each mixed by the simultaneous mixing method at 55.4.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was made + using the solution D1.
It was controlled to be 8 mv and +16 mv.

After completion of the addition, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of hexagonal tabular grains is 0.06 μm, and the average grain size is 0.06 μm. It was confirmed with an electron microscope that the diameter (converted to a circle diameter) was 0.59 μm.
The variation coefficient of thickness was 40%, and the variation coefficient of distance between twin planes was 42%.

(Preparation of Em-3) A tabular silver halide emulsion Em-3 having an average silver iodide content of 0.5 mol% was prepared using seed emulsion-1 and the following four kinds of solutions.

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

B2 Potassium bromide 1967 g Make up to 4151 ml with water.

C2 Silver nitrate 2468 g Water is made up to 151 ml.

D2 3% by weight of gelatin, and silver iodide grains (average grain size: 0.05 μm) as a fine grain emulsion (*) equivalent to 0.073 mol (*) fine grain emulsion 0.06 mol of potassium iodide Two aqueous solutions each containing 7.06 mol of silver nitrate and 3.53 mol of potassium iodide in 6.64 liters of 5.0 wt% gelatin aqueous solution.
L was added over 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After the particles were formed, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution.

Solution A2 was vigorously stirred in the reaction vessel while maintaining the temperature at 60 ° C., and part of solution B2, part of solution C2 and solution D2 were added thereto by the simultaneous mixing method over 46 minutes, After that, the remaining amount of the solution B2 and the solution C2 is 24
It was added by the double-sided mixing method over minutes. During this time, the pH was 5.
At 8, pAg was kept at 9.0 throughout. Solution B2 here
The addition rate of the solution C2 and the solution C2 was changed in a function-like manner with respect to time so as to match the critical growth rate. That is, the addition was performed at an appropriate addition rate so that small particles were not generated other than the growing seed particles and polydispersion did not occur due to Ostwald ripening. Regarding the addition rate of the solution D2, the rate ratio (molar ratio) with the solution C2 was kept at 0.11.

After the addition is complete, the emulsion is cooled to 40.degree.
As an aggregating polymer agent, 1800 ml of a 13.8% (weight) modified gelatin aqueous solution modified with a phenylcarbamoyl group (substitution rate 90%) was added and stirred for 3 minutes. afterwards,
A 56% (weight) aqueous acetic acid solution was added to adjust the pH of the emulsion to 4.6, the mixture was stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then, 9.0 liters of distilled water at 40 ° C. was added, and the supernatant was drained after standing with stirring, and 11.25 liters of distilled water was further added and the mixture was allowed to stand with stirring, and the supernatant was drained. Then add a gelatin aqueous solution and a 10% (weight) aqueous solution of sodium carbonate,
The pH was adjusted to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, the pH was adjusted to 5.8 at 40 ° C.
0, pAg was adjusted to 8.06.

The obtained silver halide emulsion having an average iodine of 0.5 mol% was observed by an electron microscope to find that the average grain size was 0.5.
The average aspect ratio is 9 μm, the average thickness is 0.13 μm, the average aspect ratio is about 4.5, and the ratio of the (111) plane is 85%.

A sample was obtained by applying Em-3 by the same preparation method as Em-2 in Example 1.

The obtained sample was sandwiched between two screens,
Tube voltage 60kvp, tube current 20 through aluminum wedge
Exposure was performed by irradiation with X-rays at 0 mA for 0.05 seconds. Example 2 is a conventional radiographic intensifying screen [Konica Corporation].
Made. The following radiation intensifying screen was used instead of KO-250] for evaluation.

(Production of high-sensitivity intensifying screen) Phosphor Gd ₂ O ₂ S: Tb (average particle size 1.8 μm) 200 g Binder Polyurethane thermoplastic elastomer (Demolac TPKL-5-2625) <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 obtain a coating solution for forming a phosphor layer having a viscosity of 25 PS (25 ° C.). Prepared.

(Binder / phosphor ratio = 1/22) Separately, 90 g of a soft acrylic resin solid content and 50 g of nitrocellulose as a coating liquid for forming an undercoat layer were added to methyl ethyl ketone, dispersed and mixed to give a viscosity of 3 to. A 6PS (25 ° C) dispersion was prepared.

Next, a titanium dioxide having a thickness of 25 was kneaded.
0 μm polyethylene terephthalate (support) was placed horizontally on a glass plate, and the coating solution for forming the undercoat layer was uniformly applied on the support using a doctor blade, and then 25
The coating film was dried by gradually increasing it from 100 ° C. to 100 ° C. to form an undercoat layer on the support (coating film thickness 15 μm
m).

Onto this, the above coating liquid for forming a phosphor layer was uniformly coated and dried to a thickness of 240 μm using a doctor blade, and then compressed. The compression was performed using a calender roll at a pressure 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 characteristic of the obtained screen is that the phosphor thickness is 1
60 μm, phosphor filling rate 68%, sharpness (OTF) is 4
It was 8%.

The evaluation of the low illuminance failure characteristic was carried out by sandwiching the sample between two screens so that the exposure amount was the same as that of normal exposure, and a tube voltage of 60 kvp, a tube current of 50 mA, and 0.2 through an aluminum wedge. It was exposed to X-rays for a second. The smaller the difference between the low illuminance exposure sensitivity and the normal exposure sensitivity, the less the fluctuation.
Show that you are excellent. Sample No. Using the result of 11 as the reference (100), the measured values of other samples were relatively determined.

The development unevenness was evaluated by uniformly exposing each sample of 35 cm × 43 cm to a density of 1.0, and
The above-mentioned development processing was performed, and the processed film was visually evaluated according to the following four-step evaluation levels.

⊚: No unevenness was observed at all ◯: Some unevenness was observed at Δ: Some unevenness was observed at X: Unevenness was observed on the entire surface The results obtained are shown in Table 2 below.

[0200]

[Table 2]

As is clear from the results shown in Table 2, the sample of the present invention has high sensitivity, little influence of low illuminance failure, and no development unevenness even when the solid processing agent is used for 15 seconds. You can see that it is not accepted.

[0202]

As demonstrated by the examples, the present invention provides a silver halide photographic light-sensitive material having a high sensitivity, a high pressure resistance and a good storability during rapid processing, and less unevenness in development processing, and a processing method thereof. Was obtained. Further, according to the present invention, a method for photographing a silver halide photographic light-sensitive material for X-rays, which has less performance fluctuation due to low illuminance failure, can be obtained by using a high-sensitivity intensifying screen.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location G03C 5/17 G03C 5/17 5/26 5/26 520 520 G21K 4/00 G21K 4/00 A

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the light-sensitive silver halide emulsion layer being characterized by having a reflection spectrum of 550 nm or less. A sensitizing dye capable of forming a typical J-band and a chemical sensitizer at 25 ° C. or higher for 45
A silver halide photographic light-sensitive material comprising an emulsion comprising silver halide grains which have been added at a temperature of not higher than 0 ° C. and subsequently sensitized and ripened at a temperature higher than the addition temperature of the sensitizing dye. 2. A silver halide grain having an average silver iodide content of 1.0 mol% or less, and a (100) plane ratio of the grain of 50% or more. Silver halide photographic light-sensitive material. 3. The silver halide according to claim 1 or 2, wherein the total processing time is 30 seconds or less in a processing method including development, fixing and drying steps of the silver halide light-sensitive material. Processing method of photographic light-sensitive material. 4. A method of continuously processing a silver halide photographic light-sensitive material in processing steps including development and fixing steps, which comprises continuously supplying a solid processing agent to a processing solution in each processing step. The method for processing a silver halide photographic light-sensitive material according to any one of claims 1 to 3, wherein 5. The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the silver halide photographic light-sensitive material is sandwiched between high-sensitivity intensifying screens and X-rayed.