JPH10254083A - Silver halide photographic sensitive material, its treating method and photographing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material with low fog. high sensitivity and excellent storage stability with time, and to provide an X-ray photographing method of the silver halide photographic sensitive material by which high performance can be obtd. even when the material is treated with a developer containing ascorbic acids and with a solid treating agent and by which the performance above described can be obtd. by using a high-sensitivity intensifying paper. SOLUTION: This photosensitive material contains such silver halide particles that particles are subjected to reductive sensitization and sensitization with selenium and/or tellurium in a desired period in the production process. Moreover, the emulsion layer containing the silver halide particles above described and a hydrophilic colloid layer adjacent to the emulsion layer contain at least one kind of compd. expressed by formula R1 -(S)n -R2 , wherein R1 , R2 may be same or different and substd. or unsubstd. aliphatic groups, aromatic groups, heterocyclic groups, or R1 , R2 may be bonded to form a ring, n is an integer 2 to 6.

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 material having improved photographic performance, a processing method thereof, and an X-ray photography method.

[0002]

2. Description of the Related Art Regarding silver halide photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials), there is a strong demand from the market for higher sensitivity and higher image quality. I have.

Hitherto, it has been found that making silver halide particles finer is the most effective in improving the image quality of a photographic material, but there is a problem in that the sensitivity becomes insufficient in exchange for the fineness.
Therefore, there is inevitably a problem of preparing fine silver halide emulsions with high sensitivity.

In recent years, sensitization techniques of using selenium and tellurium as a chemical sensitization method for silver halide grains and further performing reduction sensitization have been vigorously studied. There is a problem that fogging is increased during storage over time, especially when the photosensitive material is stored raw.

For example, Japanese Patent Laid-Open No.
No. 172337 discloses that fog can be suppressed by using thiosulfonic acid in a combined sensitization system of selenium sensitization and reduction sensitization. However, this technique does not have a sufficient fog suppression effect and requires further study.

[0006] In recent years, the problem of environmental pollution has been taken up greatly. For example, a developing solution using ascorbic acids for environmental and safety reasons rather than hydroquinones as a developing agent is disclosed in US Pat. No. 5,236. No. 816.

However, a developing solution using ascorbic acids has a disadvantage that the deterioration with time is larger and the activity is lower than hydroquinones (dihydroxybenzenes), so that it is difficult to obtain high sensitivity and high concentration. There is a problem.

On the other hand, medical photosensitive materials are strongly required to reduce the X-ray exposure of the human body, and further higher sensitivity is required. As described above, there is an urgent need to increase the sensitivity including the photosensitive material and the processing system.

[0009]

SUMMARY OF THE INVENTION Accordingly, it is a first object of the present invention to provide a silver halide photographic light-sensitive material having low fog, high sensitivity, and excellent storage stability over time. A second object of the present invention is to provide a halogen which does not contain hydroquinones (dihydroxybenzenes), is processed with a developer containing ascorbic acids, and has high performance even when processed with a solid processing agent. An object of the present invention is to provide a silver halide photographic light-sensitive material and a processing method thereof.

A third object of the present invention is to provide an X-ray imaging method capable of obtaining the above-mentioned performance in an X-ray imaging method using a high-sensitivity intensifying screen.

[0011]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
This has been achieved by the following configuration.

(1) In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer and a hydrophilic colloid layer adjacent to the silver halide emulsion layer on a support, The silver halide grains of the silver halide emulsion layer are subjected to reduction sensitization and selenium and / or tellurium sensitization at any time during the production process, and the photosensitive silver halide emulsion layer and the adjacent hydrophilic colloid layer A silver halide photographic material, characterized in that at least one layer selected from the group consisting of at least one compound represented by the following general formula (1).

Formula (1) R _1- (S) _n -R _{2 In the} formula, R ₁ and R ₂ may be the same or different,
Each represents a substituted or unsubstituted aliphatic group, aromatic group, or heterocyclic group, and R ₁ and R ₂ may combine with each other to form a substituted or unsubstituted ring. n represents an integer of 2 to 6.

(2) The silver halide light-sensitive material according to (1), wherein the average aspect ratio of the silver halide grains in the light-sensitive silver halide emulsion layer is 2 to 10.

(3) A method of imagewise exposing the silver halide photographic light-sensitive material as described in (1) or (2) above, followed by continuous processing in an automatic developing machine. A method for processing a silver halide photographic light-sensitive material, wherein a solid processing agent is supplied to each processing solution while continuously processing the same.

(4) In the method for processing a silver halide photographic material described in the above (3), the developer is substantially free of a dihydroxybenzene-based developing agent and is represented by the following general formula (2): A method for processing a silver halide photographic light-sensitive material, comprising processing with a developer containing a compound.

[0017]

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(Wherein R ₃ and R ₄ each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. Hydroxy group, carboxy group, alkoxy group, hydroxyalkyl group, carboxyalkyl group,
Represents a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, a methylcapto group, an alkyl group or an aryl group, or two vinyl carbon atoms to which P and Q are bonded and R ₃ and R ₄ are bonded. And Y represent an atomic group necessary for forming a 5- to 8-membered ring together with the carbon atom to which they are bonded. Y
Represents a is = O or = N-R _5,. R ₅ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group. (5) A method for photographing a silver halide photographic light-sensitive material, comprising sandwiching the silver halide photographic light-sensitive material according to the above (1) or (2) with a high-sensitivity intensifying screen, and performing X-ray photography.

Hereinafter, the present invention will be described in detail.

The photosensitive silver halide grains of the silver halide photographic light-sensitive material of the present invention are subjected to reduction sensitization. The type of reduction sensitizer is arbitrary, but preferred examples include thiourea dioxide, ascorbic acid, and derivatives thereof.

Another preferred reducing agent is hydrazine,
Examples thereof include polyamines such as diethylenetriamine, dimethylamine borane, and sulfite.

The amount of the reduction sensitizer added to the silver halide grains depends on the type of the reduction sensitizer, the particle size of the silver halide grains,
It is preferable to change the composition, crystal habit, reaction system temperature, pH, pAg, and the like. For example, in the case of thiourea dioxide, a preferable result can be obtained by using a range of 0.001 to 2 mg per mol of silver halide as a rough guide. In the case of ascorbic acid, the amount is preferably in the range of about 50 mg to 2 g per mol of silver halide.

In the present invention, the timing of the above-mentioned reduction sensitization is optional, but it is most preferable to apply it during the growth of silver halide grains. As a method of applying during growth,
In addition to the method of performing reduction sensitization in a state where silver halide grains are growing, reduction sensitization is performed in a state where growth of silver halide grains is interrupted, and then the reduction sensitized silver halide grains are used. Includes growing methods.

The conditions for reduction sensitization in the present invention include:
Aging temperature is about 40-70 ° C, time is about 10-200 minutes,
The pH is preferably in the range of about 5 to 11, and the pAg is preferably in the range of about 1 to 10 (where the pAg value is the reciprocal of the Ag ⁺ ion concentration).

A sensitization method may be performed by adding a water-soluble silver salt (for example, silver nitrate), and the addition of the water-soluble silver salt is performed by so-called silver ripening, which is a kind of reduction sensitization technique. The pAg at the time of silver ripening is suitably 1 to 6, preferably 2 to 4.
It is. The temperature, pH, time and the like at the time of silver ripening are preferably within the above-described reduction sensitization condition range.

The following stabilizers can be used as stabilizers for the reduction-sensitized silver halide grains. The stabilizers described below are disclosed in JP-A-57-82831. . S. Gahler [Zeits
lift fur wissenschaftlic
he Photographie Bd. 63,133
(1969)] and thiosulfonic acids described in JP-A-54-1019. In addition,
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 reduction-sensitized photosensitive silver halide grains of the present invention are subjected to selenium sensitization or tellurium sensitization. As the selenium sensitizer to be used, a wide variety of selenium compounds can be used, and useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, , N, N
-Dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylseleno Urea, N, N,
N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), seleno Carboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-
3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.),
Selenides (diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are
Selenoureas, selenoamides, and selenium ketones.

The amount of the selenium sensitizer varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally 10 ^-8 to 10 per mol of silver halide.
A range of ^-4 moles is used. More preferably silver halide 1
The use of a range of 10 ^-7 to 10 ^-5 mole per mole is used.

Depending on the properties of the selenium compound to be used, the method of addition may be a method of adding it alone or in a mixed solvent of water or an organic solvent such as methanol or ethanol, or a method of previously mixing with a gelatin solution. Alternatively, a method disclosed in JP-A-4-140739, that is, a method of adding in the form of an emulsified dispersion of a mixed solution with a polymer soluble in an organic solvent may be used. The temperature for chemical ripening using a selenium sensitizer is preferably in the range of 40 to 90 ° C. More preferably, it is 45 to 80 ° C.

The pH is 4 to 9 and the pAg is 6 to 9.5.
Is preferable.

Examples of tellurium sensitizers useful as tellurium sensitizers in the present invention include telluroureas (eg,
N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea, N, N'-dimethyl-N'phenyltellurourea), phosphine tellurides (for example, tributylphosphine) Telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (eg, telluroacetamide, N, N-dimethyltellurobenzamide), telluro ketones, telluro Esters, isotellocyanates and the like. The technology for using the tellurium sensitizer is based on the technology for using the selenium sensitizer.

In the present invention, the above-mentioned reduction sensitization may be carried out by combining two or more kinds of reduction sensitizations, for example, a combination of a water-soluble silver salt and a reducing agent.

In the present invention, the hydrophilic colloid layer adjacent to the reduction-sensitized and selenium- or tellurium-sensitized photosensitive silver halide emulsion layer contains at least a compound represented by the following general formula (1). One type is contained.

Formula (1) R _1- (S) _n -R _{2 In the} formula, R ₁ and R ₂ may be the same or different,
Represents a substituted or unsubstituted aliphatic group, aromatic group, or heterocyclic group, and R ₁ and R ₂ may combine with each other to form a substituted or unsubstituted ring. n represents an integer of 2 to 6.

In the general formula (1), the aliphatic group represented by R ₁ and R ₂ has 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms.
-20 linear, branched alkyl, alkenyl, alkynyl, or cycloalkyl groups. Specifically, methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl, isopropyl, t-butyl, 2-ethylhexyl, allyl, 2-butenyl, 7-octenyl,
Examples include groups such as propargyl, 2-butynyl, cyclopropyl, cyclopentyl, cyclohexyl, and cyclododecyl. Examples of the aromatic group represented by R ₁ and R ₂ include those having 6 to 20 carbon atoms, and specific examples include phenyl, naphthyl, and anthranyl. The heterocyclic group represented by R ₁ and R ₂ may be a single ring or a condensed ring, and includes a 5- to 6-membered hetero ring having at least one of O, S and N atoms in the ring.

Specifically, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, oxirane, morpholine, thiomorpholine, furfuryl, thiopyran, tetrahydrothiophene, pyrrole, pyridine, furan, thiophene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole , Triazole, tetrazole, thiadiazole, oxadiazole and the like, and their benzenologues.

R ₁ and R ₂ form a ring as 4
And a 7-membered ring, preferably a 5- to 7-membered ring. Preferred groups for R ₁ and R ₂ are heterocyclic groups, and more preferred are heteroaromatic ring groups. The aliphatic group, aromatic group, or heterocyclic group represented by R ₁ and R ₂ may be further substituted, and the substituent atom and the substituent may be a halogen atom (chlorine atom, bromine atom, etc.), an alkyl group (Eg, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (for example, phenyl group, naphthyl group, p-tolyl group, p
-Chlorophenyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), aryloxy group (for example, phenoxy group, etc.), cyano group, acylamino group (for example, acetylamino group, propionylamino Group), alkylthio group (eg, methylthio group, ethylthio group, n-butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group ( For example, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc., sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group) Group, dimethylcarbamoy Group), sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), sulfonyl Group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxy Group, nitro group, nitroso group, amine oxide group (for example, pyridine-oxide group), imide group (for example, phthalimide group), disulfide group (for example, benzene disulfide group, benzothiazolyl-2-disulfide group, etc.), heterocyclic group (for example, A pyridyl group, benzimidazolyl group, benzothiazolyl group, benzoxazolyl group). n is an integer of 2 to 6, preferably 2 to 5, and more preferably 2.

Hereinafter, specific examples of the compound represented by formula (1) of the present invention will be listed, but the present invention is not limited thereto.

[0039]

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[0040]

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[0041]

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[0042]

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The above compounds are fogging inhibitors for silver halide emulsions and are described, for example, in Pharm. Belg. , 22
(5-6) 213-219 (1967); U.S. Pat.
No. 759,932, J.I. Org. Chem. , Vol.
23, 64-66 (1967) J. Med. Che
m. , Vol. 10, No. 6,1170-1172
(1967) can be easily synthesized.

In order to incorporate the compound represented by the general formula (1) of the present invention into the hydrophilic colloid layer, preferably 1 × 10 ⁻ per mol of silver halide in the silver halide emulsion layer constituting the light-sensitive material. ⁷ to 1 × 10 ^-1 mol, particularly 1 × 10 ^-6 to
It is preferable to add 2 × 10 ⁻¹ mol to the hydrophilic colloid layer adjacent to the silver halide grains.

The compound represented by the above general formula (1) can be used by dissolving in a suitable water-miscible organic solvent, for example, alcohols, ketones, dimethyl sulfoxide, dimethylformamide, methyl cellosolve and the like.
It can also be added as an emulsified dispersion using a known oil. Further, the compound powder can be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or an ultrasonic disperser by a method known as a solid dispersion method.

The silver halide grains of the silver halide photographic light-sensitive material of the present invention have an aspect ratio (grain diameter / grain thickness).
It is preferable that the particles have an average aspect ratio of 2 to 10 in the range of 2 to 10. Further preferred are tabular silver halide grains having an average aspect ratio of 3 to 8.

The tabular silver halide grains are crystallographically classified as twins. Twins are silver halide crystals having one or more twin planes in one grain, and the classification of twin morphology is based on the report by Klein and Moiser, Photographic Correspondents (Photographis).
he Korespondenz), Vol. 99, p. 99, and Vol. 100, p. 57.

The silver halide grains preferably used in the present invention mainly have an even number of parallel twin planes, and these twin planes may or may not be parallel to each other. However, it is particularly preferable to have two twin planes.

In the tabular silver halide grains preferably used in the present invention, the outer wall of the crystal is substantially almost {111}.
Surface or a {100} surface. In addition, it may have both the {111} plane and the {100} plane. In this case, 50% or more of the particle surfaces are {111} planes, more preferably 60%.
% To 90% are {111} planes, particularly preferably 70%.
~ 95% are {111} planes. It is preferable that the plane other than the {111} plane is mainly the {100} plane. This plane ratio is determined by the {111} plane and the {10} plane in the adsorption of the sensitizing dye.
The difference in adsorption dependence with the 0 ° plane was used [T. Tan
i. ImagingSci, 29, 165 (198
5 years)].

The tabular silver halide grains preferably used in the present invention may be polydisperse or monodisperse, but are preferably monodisperse. Specifically, when the distribution width is defined by (standard deviation of particle diameter / average particle diameter) × 100 = relative standard deviation (coefficient of variation) expressed by the width (%) of particle size distribution, 25% or less is defined. Is preferably 20% or less, more preferably 15% or less.

The tabular silver halide grains preferably used in the present invention preferably have a small thickness distribution. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) × 100 = width (%) of the thickness distribution, 2
It is preferably at most 5%, more preferably at most 20%, particularly preferably at most 15%.

Further, the distribution of the halogen content of each grain in the emulsion containing tabular silver halide grains preferably used in the present invention is preferably small. Specifically, (standard deviation of halogen content / average halogen content) ×
100 = 25% or less, more preferably 20% or less, particularly preferably 15% or less when the area of distribution is defined by the area (%) of the halogen content.
% Or less.

In the present invention, the tabular silver halide grains are preferably hexagonal. Hexagonal tabular grains (hereinafter also referred to as hexagonal tabular grains) are those whose main plane ({111} plane) is hexagonal and whose maximum adjacent ratio is 1.0 to 2.0. Say that. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. In the present invention, the hexagonal tabular grains preferably have rounded corners if the maximum adjacent side ratio is 1.0 to 2.0. If the corner is rounded, the length of the side is
It is represented by the distance between the intersection of the straight line portion of the side and the line obtained by extending the straight line portion of the adjacent side. It is also preferred that the tabular grains are further rounded and are substantially circular.

In the present invention, it is preferable that at least one half of each side forming the hexagon of the hexagonal tabular grain is substantially a straight line. In the present invention, the adjacent side ratio is 1.0
More preferably, it is 1.5. The dislocation lines of the halogenated grains according to the present invention are described, for example, in J. Am. F. Hamilto
n, Photo. Sci. Eng. , 57 (1967)
And T. Shiozawa, J .; Soc. Photo. S
ci. Japan, 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.
(0 kV or more) can be observed more clearly by using an electron microscope.

From the photographs of the particles obtained by such a method, the position and number of dislocation lines for each particle can be determined. The position of the dislocation line of the silver halide grain is from 0.58 L to 1.
It is desirable that the occurrence occurs in the region up to 0L, but more preferably in the region of 0.80L to 0.98L. The direction of the dislocation line is approximately from the center to the outer surface, but often meanders.

The center of a silver halide grain is defined by dispersing silver halide microcrystals in a methacrylic resin and solidifying the same as in the method described in the abstract of Inoue et al. Focusing on the ultrathin section with a microtome, the specimen with the largest cross-sectional area and the specimen sample with a cross-sectional area of 90% or more than that, the circle when drawing the circumscribed circle with the smallest cross-section Is the center of In the present invention, the distance L from the center to the outer surface is defined as the distance between the point at which the line intersects the outer periphery of the particle when a straight line is drawn outward from the center of the circle and the center of the circle. Regarding the number of dislocation lines in the silver halide grains according to the present invention, it is desirable that 50% (number) or more of grains containing one or more dislocation lines exist, and the ratio (number) of the number of tabular grains having dislocation lines is present. The higher the value, the better.

The particle diameter is a diameter when a projected image of the particle is converted into a circular image having the same area. The projected area of a particle can be determined from the sum of the particle areas. In each case, a silver halide crystal sample distributed on a sample table to such an extent that no grain overlap occurs can be obtained by observing the sample with an electron microscope.

The average projected area diameter of the tabular silver halide grains is represented by the circle-equivalent diameter of the projected area of the grains and is preferably at least 0.30 μm, more preferably 0.30 to 0.30 μm.
5 μm, more preferably 0.40 to 2 μm.

The particle size can be obtained by projecting the particles at an enlargement of 10,000 to 70,000 times with an electron microscope and actually measuring the projected area on the print. The average particle diameter (φi) can be determined by the following equation, where n is the number of measured particle diameters and ni is the frequency of particles having the particle diameter φi.

Average particle size (φ) = Σnidi / n (The number of measured particles is indiscriminately 1,000 or more.) The thickness of the particles is obtained by observing the sample obliquely with an electron microscope. Can be. The preferred thickness of the tabular grains of the present invention is from 0.03 to 1.0 µm, more preferably from 0.05 to 0.5 µm.

The ratio (b / a) of the longest distance (a) between two or more parallel twin planes of the silver halide grains of the invention to the thickness (b) of the grains is preferably 5 or more. ,
It is preferable that the ratio is 50% (number) or more. The distance between twin planes (a) can be determined as follows.
That is, the section was observed using a transmission electron microscope, and arbitrarily selected 100 or more tabular silver halide grains exhibiting a cross section cut substantially perpendicular to the main plane, and (a) was determined for each grain. It can be measured and averaged.

In the present invention, the average value of (a) is 0.1.
It is preferably at least 008 μm, more preferably at least 0.010 μm and at most 0.05 μm. In the present invention, (a) is within the above-mentioned value range, and at the same time, its coefficient of variation is preferably 35% or less, more preferably 30% or less. Further, in the present invention, the tabularity represented by the following formula: A = ECD / b2 is preferably 20 or more, taking into account the factors of the aspect ratio and the grain thickness.

Here, ECD indicates the average projected diameter (μm) of tabular silver halide grains, and (b) indicates the thickness of the grains. Here, the average projected diameter represents the number average of the diameter of a circle having an area equal to the projected area of the tabular silver halide grains.

In the tabular silver halide grains of the present invention, the usual silver halides of silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride are used as the silver halide. Any one used for the grains can be used, and particularly preferred are silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide.
In particular, the silver chloride-containing grains preferably have a silver chloride content of 20 mol% or more and 90 mol% or less.

The tabular silver halide grains preferably used in the present invention may have a core / shell type structure having at least two layer structures having substantially different halogen compositions in the silver halide grains or may have a uniform composition. Preferably have a core / shell structure.

In this case, the grain center may have a halogen composition region different from that of the core. In such a case, as the halogen composition of the seed grains, any combination of silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride and the like is used.

The average silver iodide content of the silver halide emulsion preferably used in the present invention is preferably 2 mol% or less.
More preferably, it is 0.1 to 1.5 mol%. In a grain having a layer structure with a different halogen composition, a grain having a high silver iodide layer inside the grain and a low silver iodide layer or a silver bromide layer in the outermost layer is preferable. At this time, the silver iodide ratio of the inner layer (core) having the highest silver iodide content is preferably 2.5 mol% or more, more preferably 5 mol% or more. Has a silver iodide content of 0 to 5 mol%,
It is preferably 0 to 3 mol%, and the silver iodide content of the core is preferably at least 3 mol% or more than the silver iodide content of the shell.

Although the silver iodide distribution of the core is usually uniform,
It may have a distribution. For example, as the concentration goes from the center to the outside, the concentration may become higher, or the intermediate region may have a maximum or minimum concentration.

In the present invention, so-called halogen conversion type (conversion type) particles may be used. The halogen conversion amount is preferably from 0.2 to 2.0 mol% based on the silver amount, and the conversion may be carried out during physical ripening or after physical ripening. As a method of halogen conversion, an aqueous halogen solution or fine silver halide particles having a smaller solubility product with silver than the halogen composition of the grain surface before the halogen conversion is usually added. The fine particle size at this time is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm.

Silver halide grains are described, for example, in
It is preferable to grow the seed crystal by a method of depositing silver halide on the seed crystal as in the method described in Example of JP-A-138538.

In the method for producing silver halide grains according to the present invention, in which a water-soluble silver salt solution and a water-soluble halide solution are supplied to a protective colloid in order to obtain tabular silver halide grains, the following method is used. The following conditions are preferably used.

(A) The p of the mother liquor is not less than １ ／ from the beginning of the formation of silver halide precipitates having a silver iodide content of 0 to 5 mol%.
A nuclear particle generation step for keeping Br at 2.5 to -0.7 is provided,
(B) Subsequent to the nucleus grain forming step, the mother liquor contains a silver halide solvent in an amount of 1 × 10 ^{−5 to} 2.0 mol per mol of silver halide and is substantially monodisperse spherical twin. A seed particle forming step for forming silver seed particles is provided, or
Subsequent to the core particle generation step, the temperature of the mother liquor is set to 40 to 80 ° C
(C) Then, a water-soluble silver salt solution and a water-soluble halide solution and / or halogenated fine particles are added to form seed particles. Provide a growing process to enlarge.

Here, the mother liquor is a liquid (including a silver halide emulsion) which is used for preparing a silver halide emulsion up to a completed photographic emulsion. The silver halide grains formed in the nucleus grain forming step are twin grains composed of 0 to 5 mol% of silver iodide.

A water-soluble silver salt may be added for the purpose of adjusting ripening during the seed particle forming step. The seed grain growing step for enlarging the silver halide seed grains includes pAg during precipitation of the silver halide, pAg during Ostwald ripening, pH, temperature,
This can be achieved by controlling the concentration of the silver halide solvent and the silver halide composition, and the addition rate of the silver salt and halide solutions.

In the preparation of the emulsion, ammonia, thioether,
Known silver halide solvents such as thiourea can be present. Conditions for enlarging the produced seed grains in order to obtain tabular silver halide grains are described in JP-A-51-3.
Nos. 9027, 55-142329, 58-113
Nos. 928, 54-48521 and 58-4993
As can be seen in No. 8, a water-soluble silver salt solution and a water-soluble halide solution were added by the double jet method, and the addition rate was adjusted so that new nucleation did not occur and Ostwald ripening did not occur in accordance with the enlargement of the particles. Change gradually. As another condition for enlarging the seed grains, a method of adding silver halide fine grains, dissolving and recrystallizing the grains, as shown in Item 88 of the Abstracts of the 58th Annual Meeting of the Photographic Society of Japan, may be used.

For the growth, an aqueous solution of silver nitrate and an aqueous solution of halide can be added by double jet, but the iodine can also be supplied into the system as silver iodide. The addition rate is preferably such that no new nuclei are generated and at a rate such that the size distribution does not spread due to Ostwald ripening, that is, 30 to 100% of the rate at which new nuclei are generated.

In the production of a silver halide emulsion, stirring conditions during production are extremely important. Japanese Patent Application Laid-Open No. Sho 62
A device in which the additive liquid nozzle described in JP-A-160128 is installed in the liquid near the mother liquor suction port of the stirrer is particularly preferably used. In this case, the stirring rotation speed is 400 to 1200 r.
pm is preferable.

Further, the silver halide grains of the present invention can be used in the step of forming and / or growing grains, in the course of cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (complex salt). And at least one metal ion selected from iron salts (including complex salts), and these metal elements can be contained inside the particles and / or in the particle surface layer.

In the silver halide photographic emulsion of the present invention, unnecessary soluble salts may be removed at the end of the growth of the silver halide grains, or may be kept contained. When removing the salts, use Research Disclos
ure (RD) No. It can be performed based on the method described in 17643 No. II.

The silver halide emulsion layer containing the silver halide grains of the present invention may contain other grains as long as the effects of the present invention are not impaired.

Various photographic additives can be used in the silver halide light-sensitive material of the present invention. Known additives include, for example, (RD) 17643 (December 1978)
18716 (November 1979) and 308
119 (Dec. 1989). The compound types and locations described in these three (RD) are described below.

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[Table 1]

The emulsion layer or other layers of the silver halide photographic light-sensitive material of the present invention may contain a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone. Good.

Examples of the support usable for the light-sensitive material include the above-mentioned RD-17643, page 28 and RD-17643.
-308119 on page 1009. A preferred support is polyethylene terephthalate, and the undercoat layer may contain an antistatic agent such as tin oxide sol.

In the 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 photosensitive material having high sensitivity, high sharpness, and excellent processability can be obtained. The amount of gelatin in the silver halide emulsion layer, surface protective layer and other layers is 0.5 to 3.5 in total on one side of the support.
range of g / m ² are preferred, especially 1.5~3.0g / m ²
Is preferable.

The silver halide photographic material of the present invention is continuously processed using a solid processing agent. The solid processing agent referred to here is a solid processing agent such as a powder processing agent, a tablet, a pill, and a granule, which is subjected to a moisture-proof treatment as required. The powder is an aggregate of fine crystals, and the granule is a powder obtained by adding a granulation step to a powder, and refers to a granular material having a particle size of 50 to 5000 μm. A tablet means a powder or a granule obtained by compression molding into a certain shape.

To solidify the photographic processing agent, a concentrated solution or a fine powder or a granular photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded photographic processing agent is mixed with a water-soluble binder. Any means can be adopted such as forming a coating layer by spraying.

A preferred tablet production method is a method in which a powdery 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 simply mixing a solid processing agent component and forming a tablet.

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

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

The bulk density of the solid processing agent is 1.0 g / cm ³ or more in the case of a tablet from the viewpoint of solubility and effect.
2.5 g / cm ³ is preferred. When it is more than 1.0 g / cm ³ , the strength of the obtained solid is preferable,
When the diameter is smaller than ³ cm ³ , the solubility of the obtained solid is more preferable. When the solid processing agent is a granule or powder, the bulk density is preferably from 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.

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

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

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

In the present invention, as a supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Unexamined Utility Model Publication No. 63-137783 and 63-975.
No. 22, Japanese Utility Model Laid-Open No. 1-85732 and the like, but any method may be used as long as the function of supplying tablets to the processing tank is provided at a minimum. When the solid processing agent is in the form of granules or powder, it is disclosed in Japanese Utility Model Application Laid-Open No. 62-8196.
4, JP-A-63-84151, JP-A-1-292375
No., the gravity drop method described and the actual opening 63-105159
And a method using a screw or a screw described in JP-A-63-195345 are known methods, but the method is not limited thereto.

As a preferred method of supplying the solid processing agent to the processing tank, for example, a predetermined amount of the solid processing agent weighed in advance and divided and packaged is opened and taken out of the package according to the processing amount of the photosensitive material. A method is conceivable. Specifically, the solid processing agent is sandwiched and stored in a predetermined amount, preferably in a single replenishment amount, in a package composed of at least two packaging materials, and the package is separated in two directions or the package is separated. A part is opened to make it ready for removal. The solid processing agent in a removable state can be easily supplied to a processing tank having a filtering means by natural fall. Since a predetermined amount of the solid processing agent is stored in a separately sealed package so that the air permeability between the outside air and the adjacent solid processing agent is shut off, the moisture proof is guaranteed unless opened.

As an embodiment, a configuration is conceivable in which a package made of at least two packaging materials is adhered or adhered to each other so as to be able to separate the periphery of the solid processing agent so as to sandwich the solid processing agent. . By pulling each packaging material sandwiching the solid processing agent in a different direction, the contact surfaces adhered or adhered are separated, and the solid processing agent can be taken out.

As another embodiment, a configuration is conceivable in which 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 refers to a cut or break that leaves a part of the packaging material. As an opening method, the solid processing agent is forcibly extruded by applying a compressive force from the non-opening side package to the openable package through the solid processing agent, or the package is opened. It is conceivable 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 information on the processing amount. The supply stop signal is obtained by detecting information indicating that a predetermined amount of supply has been completed. In addition, when the processing agent is packaged and opening is required, a driving unit for separating or opening based on the obtained supply start signal operates, and a driving unit for separating or opening based on the supply stop signal is provided. Can be controlled to stop.

The supply means of the solid processing agent has a control means for supplying a fixed amount of the solid processing agent in accordance with the processing amount information of the photosensitive material, which is an important requirement in the present invention.
That is, in the automatic developing machine of the present invention, it is necessary to keep the component concentration in each processing tank constant and to stabilize 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 solution, 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. It indicates indirectly or directly the amount of reduction of the treating agent in the liquid. The detection may be performed at any time before or after the photosensitive material is carried into the processing solution, or during immersion in the processing solution. Further, physical parameters such as the concentration of the composition in the processing solution, a change in the concentration, pH, and specific gravity may be used. Further, the amount may be outside after the treatment liquid is dried.

The place where the solid processing agent is charged may be in the processing tank, but is preferably a place where the processing liquid is in communication with the processing section for processing the photosensitive material and the processing liquid flows between the processing section and the processing section. In addition, a structure is preferable in which there is a constant circulation amount of the processing liquid between the processing unit and the dissolved component moves to the processing unit. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

The silver halide photographic light-sensitive material of the present invention is substantially free of a dihydroxybenzene-based main ingredient, and is processed with a developer containing a compound represented by the above formula (2) as a main ingredient. Here, the expression "contains substantially no dihydroxybenzene-based active substance" means that it does not contain an amount having a developing ability.

The compound represented by the general formula (2) is preferably used in an amount of 0.005 to 0.5 mol, more preferably 0.02 to 0.4 mol, per liter of the developing solution. Specific examples of the compound represented by the general formula (2) include the following, but the present invention is not limited thereto.

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As a preservative of the developer in the present invention, an organic reducing agent can be used as a preservative in addition to sulfite. An amine compound can be added to the developer,
The compounds described in U.S. Pat. No. 4,269,929 are particularly preferred.

A buffer is used in the developing solution. Examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, and boric acid. Sodium, potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate,
Sodium 5-sulfo-2-hydroxybenzoate (5-
Sodium sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like.

The development accelerators include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, and other 1-phenyl-
If necessary, 3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added.

As an antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Examples thereof include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine. Representative examples include 1-phenyl-5-mercaptotetrazole.

Further, in the developer composition used in the present invention, if necessary, methylcellosolve, methanol, acetone, dimethylformamide, a cyclodextrin compound, and other organic solvents for increasing the solubility of the developing agent may be used. it can.

Further, various additives such as an anti-stain agent, an anti-sludge agent and an accelerator for layering effect can be used in the developer.

The fixing agent used in the present invention may contain a compound known as a fixing agent. Fixing agent, chelating agent, p
H buffers, hardeners, preservatives and the like can be added.

Prior to processing, it is preferable to add a starter to the developer, and it is also preferable to add the solidified starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkaline earth metal such as KBr, an organic inhibitor, and a development accelerator are used.

In the present invention, the development temperature is preferably 25 to 50 ° C., more preferably 30 to 40 ° C. The development time is 3 to 15 seconds, more preferably 4 to 15 seconds.
10 seconds. The total processing time is preferably from 10 to 30 seconds, more preferably from 15 to 30 seconds, in a dry-to-dry manner. The total processing time is a processing time including the steps of developing, fixing and drying the photosensitive material.

The replenishment of the developing solution in the present invention replenishes the amount corresponding to the processing agent fatigue and oxidative fatigue. As a replenishment method,
Replenishment by width and feed rate or area replenishment may be performed, and a preferable replenishment amount is 50 to 150 ml / m ² .

In the method for photographing a silver halide photographic light-sensitive material of the present invention, X-ray photography is carried out by sandwiching the light-sensitive material with a high-sensitivity intensifying screen.

In the high-sensitivity intensifying screen (also referred to as a radiographic intensifying screen) of the present invention, the filling rate of the phosphor in the phosphor layer is preferably at least 68%, more preferably 7%.
0% or more, more preferably 72% or more.

The thickness of the phosphor layer is 150 to 250 μm.
It is preferred that Here, the thickness of the phosphor layer is 150
If it is less than μm, the sharpness sharply deteriorates.

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

In the radiation intensifying screen of the present invention, by increasing the packing ratio of the phosphor particles, the X-ray absorption of each of the radiation intensifying screens is reduced by X per 100 μm of the thickness of the phosphor layer.
The linear absorptivity is preferably 30% or more. The amount of X-ray absorption was determined as follows. That is, X-rays generated from a tungsten target operated at 80 kVp from an X-ray generator equivalent to 2.2 mm of aluminum and passed through a 3 mm-thick aluminum plate having a purity of 99% or more are supplied by three-phase power supply. The X-ray absorption amount was measured by using an ionizing dosimeter at a position 50 cm after the phosphor layer of the radiographic intensifying screen, and arriving at a radiographic intensifying screen fixed at 200 cm from the tungsten anode of the target tube. I asked. As a reference, the X-ray dose at the above measurement position measured without passing through the intensifying screen was used.

Preferred binders used in the radiographic intensifying screen include thermoplastic elastomers.
Specifically, polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, ethylene vinyl acetate, polyvinyl chloride, natural rubber, fluoro rubber, polyisoprene, chlorinated polyethylene, styrene-
At least one type of thermoplastic elastomer selected from the group consisting of butadiene rubber and silicone rubber is used. The filling rate of the phosphor can be determined from the porosity of the phosphor layer formed on the support by an ordinary method.

Preferred phosphors used in the radiation intensifying screen according to the present invention include the following.

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 (L
aOBr: Tb, LaOBr: Tb. Tm, LaOC
l: Tb, LaOCl: Tb. Tm, GdOBr: T
b, GdOCr: Tb, etc.), thulium-activated rare earth oxyhalide-based phosphor (LaOBr: Tm, LaOC)
1: Tm, etc.), barium sulfate based phosphor [BaSO ₄ : P
b, BaSO ₄ : Eu ²⁺ , (Ba, Sr) SO ₄ : Eu ²⁺
Etc.] divalent eurobium-activated alkaline earth metal phosphate-based phosphor [Ba ₃ (PO ₄ ) ₂ : Eu ²⁺ , (Ba, S
r) ₃ , (PO ₄ ) ₂ : Eu ²⁺ etc.] divalent eurobium-activated alkaline earth metal fluorohalide-based phosphor [Ba
FCl: Eu ²⁺ , BaFBr: Eu ²⁺ , BaFCl: E
u ²⁺ . Tb, BaFBr: Eu ²⁺ . Tb, BaF ₂ . B
aCl ₂ . XBaSO ₄ . KCl: Eu ²⁺ , (Ba, M
g) F ₂ . BaCl ₂ . KCl: Eu ²⁺ etc.], iodide-based phosphors (CSI: Na, CSI: Tl, NaI.KI: T
l)), sulfide-based phosphors [ZnS: Ag, (Zn, C
d) S: Ag, (Zn, Cd) S: Cu, (Zn, C
d) S: Cu. Al etc.), hafnium phosphate phosphor (H
fP2O7: Cu, etc.) However, 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.

[0126]

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-1 (Hexagonal Tabular Grains of Silver Iodobromide) A1 Ossein gelatin 75.5 g 10% aqueous solution of surfactant (A) * in ethanol 6.78 ml Potassium bromide 64.7 g water B1 0.7N silver nitrate aqueous solution 1340ml C1 2.0N silver nitrate aqueous solution 1500ml D1 1.3N potassium bromide aqueous solution 410ml E1 2.0N potassium bromide aqueous solution Silver potential control amount below F1 ossein gelatin 125g water 4000ml G1 KSCN aqueous solution (2N) 30 ml H1 Fine particle emulsion composed of 3% by weight of gelatin and silver iodide particles (average particle diameter 0.05 μm) (*) Equivalent to 0.008 mol Surfactant (A) *: Polypropyleneoxy-polyethyleneoxy- Disuccinate sodium salt fine particle emulsion (*): 0. 5.0 wt% aqueous gelatin solution 6.64 l containing 6 mol of potassium iodide,
An aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide, 2 liters each, was added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

JP-B-58-58288, 58-58
Using a mixing stirrer described in No. 289, 400 ml of the solution (B1) was added to the solution (A1) and the total amount of the solution (D1) was 55%.
At 40 ° C., the mixture was added by a double jet method over 40 seconds to form nuclei.

After the addition of the solution (B1) and the solution (D1), the solution (F1) is added, and the temperature is raised to 70 ° C. to ripen. Further, after the remaining amount of the solution (B1) is added over 25 minutes, aging is performed for 10 minutes using a 28% aqueous ammonia solution, and the pH is returned to neutral with acetic acid. Solutions (C1) and (E
While maintaining the pAg at 7.8, 1) was simultaneously added and mixed at a rate commensurate with the critical growth rate. After adding (C1) in its entirety, (G1) and (H1) were added. After stirring for 5 minutes, soluble salts were desalted and removed by a sedimentation method.

When the total silver content was 50%, thiourea dioxide was added in an amount of 1 × 10 ⁻⁶ mol per mol of silver.
Reduction sensitization was performed.

In this emulsion, 90% or more of the total projected area of the 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 the hexagonal tabular grains is 0.20.
It was confirmed by an electron microscope that the average particle diameter (in terms of circular diameter) was 0.80 μm and the average aspect ratio was 4. The distribution of the circle equivalent diameter was 15%.

Subsequently, a predetermined amount of the above emulsion-1 was heated at a temperature of 55 ° C. and subjected to spectral sensitization and chemical sensitization according to the following sensitization prescription.

(Preparation of Solid Fine Particle Dispersion of Spectral Sensitizing Dye) The following spectral sensitizing dyes (A) and (B) were added to water previously adjusted to 27 ° C. in a ratio of 100: 1, and a high-speed stirrer ( (Dissolver) at 3,500 rpm for 30 to 120 minutes to obtain a solid fine particle dispersion of the spectral sensitizing dye. At this time, the sensitizing dye (A) was adjusted to have a concentration of 2%.

Spectral sensitizing dye (A): 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl)
Oxacarbocyanine salt anhydride Spectral sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine -Sodium salt anhydride (Preparation of selenium sensitizer solid fine particle dispersion) A selenium sensitizer dispersion was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., stirred and completely dissolved. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto.

Next, these two liquids were mixed to form a mixture having a diameter of 10%.
cm disperser with a high-speed stirring type disperser,
Dispersion was performed at 50 ° C. for 30 minutes at a dispersion blade peripheral speed of 40 m / sec. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3 wt% or less. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg. A part of the dispersion thus obtained was fractionated and used for experiments.

(Preparation of Solid Fine Particle Dispersion of Tellurium Sensitizer) A dispersion was prepared according to the above-described selenium sensitizer.

(Chemical Sensitization Formulation)
After adding the solid particulate dispersion of the spectral sensitizing dye,
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI), aqueous sodium thiosulfate solution,
Triphenylphosphine selenide solid fine particle dispersion, butyl-isopropylphosphine telluride solid fine particle dispersion, potassium thiocyanate, and chloroauric acid aqueous solution were added, and the mixture was aged for 90 minutes with stirring. At the end of ripening, 1-phenyl-5-mercaptotetrazole (P
(MT) and (TAI).

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

1-2 (compound of general formula (1) of the present invention) 5.0 mg spectral sensitizing dye 460 mg TAI 10.0 mg sodium thiosulfate (pentahydrate) 15.0 mg triphenylphosphine selenide 3.0 mg butyl- Isopropylphosphine telluride 0.5 mg Potassium thiocyanate 50.0 mg Chloroauric acid 18.5 mg <Preparation of coating sample> 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 later was also prepared, and the two coating solutions were used so that the coating amount was 1.6 g / m ² per side and the amount of gelatin was 2.5 g / m ² per side. 8 per minute using a slide hopper type coater
At the speed of 0 m, both sides were simultaneously coated on the support, dried for 2 minutes and 20 seconds, and dried. 1-10 were obtained. As a support, an aqueous copolymer dispersion and a colloid obtained by diluting a copolymer composed of three monomers of 50 wt% of glycidyl methacrylate, 10 wt% of methyl acrylate, and 40 wt% of butyl methacrylate so as to have a concentration of 10 wt% A polyethylene terephthalate film base which was colored blue to a concentration of 0.15 for a 175 μm X-ray film using a mixture of a tin oxide dispersion (described in Japanese Patent Application No. 7-231445) as an undercoating liquid was used.

The additives used in the emulsion are as follows.
The amount of addition was shown in an amount per m ² .

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

Compound (G) 0.5 mg 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg t-butyl-catechol 130 mg polyvinylpyrrolidone (molecular weight 10,000) 35 mg styrene-anhydrous Maleic acid copolymer 80 mg Sodium polystyrene sulfonate 80 mg Trimethylolpropane 350 mg Diethylene glycol 50 mg Nitrophenyl-triphenyl-phosphonium chloride 20 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg 2-Mercaptobenzimidazole-5-sodium sulfonate 5mg compound _{(H) 0.5mg n-C 4} H 9 OCH 2 CH (OH) CH 2 n (CH 2 COOH) 2 350mg compound (M) 5mg compound (n 5mg Colloidal silica 0.5g Latex (L) 0.2 g Dextrin (average molecular weight of about 1000) 0.1 g dextran (average molecular weight of about 40000) 0.1 g However, as the gelatin coating amount is 0.8 g / m ² Was adjusted.

Third layer (protective layer) Solid fine particle dispersion dye 50 mg Gelatin 0.8 g Polymethyl methacrylate matting agent (area average particle size 7.0 μm) 50 mg Formaldehyde 20 mg 2,4-dichloro-6-hydroxy-1 1,3,5-Triazine sodium 10 mg Bis-vinylsulfonylmethyl ether 36 mg Latex (L) 0.2 g Polyacrylamide (average molecular weight 10,000) 0.1 g Sodium polyacrylate 30 mg Polysiloxane (SI) 20 mg Compound (I) 12 mg Compound (J) 2 mg Compound (S-1) 7 mg Compound (K) 15 mg Compound (O) 50 mg Compound (S-2) 5 mg C ₉ F ₁₉ -O- (CH ₂ CH ₂ O) ₁₁ -H 3 mg C ₈ F _{17 SO 2 N- (C 3 H 7} ) (CH 2 CH 2 O) _{15 -H 2mg C 8 F 17 SO} 2 N- (C 3 H 7) (CH 2 CH 2 O) 4 - (CH 2) 4 SO 3 Na 1mg

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[0147] Thus, Sample 1 was produced.

As shown in Table 2, the sample N was prepared in exactly the same manner except that the compound represented by the general formula (1) of the present invention and the comparative compound were changed and the same molar amount was added.
o. 2 to 10 were produced. After the preparation of the sample, the sample was allowed to stand for three days under the following conditions A and B, and a storage test was performed.

Condition A: 23 ° C., RH 40% Condition B: 55 ° C., RH 40% Photographic properties were evaluated using 1 and 2 to 10. First, the sample was placed on two fluorescent intensifying screens (Konica Corporation)
KO-250), a tube voltage of 80 kVp, a tube current of 100 mA, and an X of 0.05 second through an aluminum wedge.
A line was irradiated and exposed.

Next, an automatic developing machine (manufactured by Konica Corporation, SR
X-502) and processed with a developing solution and a fixing solution having the following formulation.

A tablet for replenishing development was prepared according to the following operations (A, B).

Operation (A) 3,000 g of hydroquinone as a developing agent is pulverized in a commercially available bantam 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) 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, and 200 g of N-acetyl-D, L-penicillamine Pulverization and granulation are performed as in (A). The amount of water to be added is 30.0 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. The mixture 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 replenishing tablet for fixing was prepared in the following manner.

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is ground in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), the amount of water added was 500 m
and perform granulation. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules. 4 g of sodium N-lauroylalanine is added to the thus-prepared granules and mixed for 3 minutes in a room conditioned at 25 ° C. and 40% RH or less using a mixer. Next, the obtained mixture was subjected to compression tableting using a tableting machine similar to that described above with a filling amount per tablet of 6.202 g to prepare 2500 fixing supplementary tablets C.

Operation (D) Boric acid 1000 g, aluminum sulfate / 18-hydrate 150
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. In this way, 4 g of sodium N-lauroylalanine was added to the prepared mixture, and the mixture was mixed for 3 minutes. Then, the obtained mixture was adjusted to a filling amount of 4.562 g per tablet using the same tableting machine as described above. By compression tableting, 1250 fixing replenishing tablets D were prepared.

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

At the start of the processing of the developing solution (starting of running), the developing tank was filled with 16.5 liters of the developing solution prepared by diluting the developing tablet with diluting water and added with 330 ml of the above-mentioned starter as a starting solution to fill the developing tank. Started.
The pH of the developer to which the starter was added was 10.45.

The light-sensitive material prepared above was exposed to light so that the optical density after the development processing was 1.0, and running was performed. For running, a machine modified so that a processing member can be processed at a processing speed of 15 seconds by attaching an input member of a solid processing agent to an automatic developing machine SRX-502 was used.

During running, the photosensitive material was 0.6
2 m ² each of the above-mentioned A agent and B agent and 76 ml of water per 2 m ²
Was performed. When each of the A agent and the B agent was dissolved in 38 ml of water, the pH was 10.70. In the fixing solution, ^two C agents and one D agent were used per 0.62 m ² of the photosensitive material.
Pieces and 74 ml of water were 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.

[0161] Developing solution Potassium carbonate 40 g Hydroquinone 30 g Dimezone S 10 g Diethylenetriaminepentaacetic 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.
l. This concentrated solution was diluted to 1 liter with water to obtain a replenisher. The pH of this replenisher was 10.70.

Fixing solution 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 400 ml of these Dissolved in water and finally 500m with pure water
l. This concentrated solution was diluted to 1 liter with water to obtain a replenisher. The pH of this replenisher was 4.50.

Table 2 shows the contents of each sample and the results obtained. Note that the sensitivities in the table indicate sample No. The relative sensitivity when the sensitivity under the condition A of 10 is 100 is shown.

[0164]

[Table 2]

(Comparative-1: Ethylthiosulfonic acid) (Comparative-2: p-toluenethiosulfonic acid) As is clear from the results in Table 2, the sample of the present invention has high sensitivity and can be used under high temperature. Even when stored, the fogging was extremely small and excellent. The sample of the present invention maintained high sensitivity even when left at a high temperature. When particles outside the present invention which are not subjected to reduction sensitization are used, fog is not increased in a storage stability test (condition B), but high sensitivity is not obtained and the object of the present invention can be achieved. I could not do it.

Example 2 Emulsion-2 (Preparation of Tabular Grains of Pure Silver Chloride (100)) A2 Ossein Gelatin 37.5 g KI 0.625 g NaCl 16.5 g Make up to 7500 ml with distilled water B2 Silver nitrate 1500 g 2500 ml with distilled water C2 KI 4 g NaCl 140 g Make 684 ml with distilled water D2 NaCl 375 g Make 1816 ml with distilled water Emulsion was prepared in the same manner as Emulsion-1 except that EAg was adjusted to 150 mV using the above-mentioned additives A2 to D2. 2 was obtained.

When about 3000 of the obtained emulsion-2 were observed and measured by an electron microscope and analyzed for its shape, it was determined that the average circle equivalent diameter was 0.8 μm and the average thickness was 0.1 μm (average aspect ratio 8). ) Tabular grains having a major plane as the plane, and the coefficient of variation was 20%.

At the time when the total silver amount became 50%, thiourea dioxide was added in an amount of 1 × 10 ^-6 mol per mol of silver.

<Sensitization Formulation and Method for Preparing Coated Sample> Example 1
Sample No. 4, 5, 6, 7, 9, 10 11 to 16 were prepared.

<Preparation of High-sensitivity Intensifying Screen> Phosphor Gd ₂ O ₂ S: Tb (average particle size: 1.8 μm) 200 g Combined polyurethane thermoplastic elastomer Demolac TPKL-5-2625 Solid content 40% (Sumitomo Bayeru 20 g Nitrocellulose (digestibility: 11.5%) 2 g A methyl ethyl ketone solvent was added to the above 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 = 1/2
2).

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 with methyl ethyl ketone, dispersed and mixed to obtain a viscosity of 3 to 3.
A 6 ps (25 ° C.) dispersion was prepared.

A thickness of 250 μm into which titanium dioxide has been kneaded.
Polyethylene terephthalate base (support) is placed horizontally on a glass plate, and the above-mentioned coating solution for forming an undercoat layer is uniformly coated on the support using a doctor blade.
The coating film was dried by gradually raising the temperature from 100 ° C. to 100 ° C. to form an undercoat layer on the support. The thickness of the coating film is 15μ
m.

The above-mentioned coating solution for forming a phosphor layer was uniformly coated and dried to a thickness of 240 μm using a doctor blade, and then compressed. Compression was performed using a calender roll at a pressure of 800 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.

As described above, a fluorescent intensifying screen comprising a support, an undercoat layer, a phosphor layer and a transparent protective film was produced.

A developing tablet was prepared according to the following procedure.

Operation (A) 13000 g of sodium erythorbate as a developing agent is ground in a commercially available bantam mill until the average particle size becomes 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 humidified at 25 ° C. and 40% RH or less, and the mixture was tough by Kikusui Seisakusho. Presto Collect 15
The tableting machine modified from 27HU was used for compression and tableting at a filling amount of 8.715 g per tablet to prepare 2500 tablets E for development replenishment.

Operation (B) 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 tablet was prepared by the following operation.

Operation (C) 18560 g of ammonium thiosulfate, 1392 g of sodium sulfite, 580 g of sodium hydroxide, and 2.32 g of disodium ethylenediaminetetraacetate are pulverized and granulated in the same manner as in the operation (A). The amount of water to be added is 500 ml, and after granulation, it is dried at 60 ° C. for 30 minutes to almost completely remove water from the granulated material. The obtained mixture was 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) 1860 g of boric acid, aluminum sulfate / 18-hydrate 6500
g, glacial acetic acid 1860 g, sulfuric acid (50 wt%) 928 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water to be added is 100 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. The obtained mixture was compressed and tableted using the same tableting machine as described above, with the filling amount per tablet being 4.459 g, to thereby produce 2500 fixing replenishing tablets H.

Developing solution starter Same as in Example 1. At the start of developing solution processing (starting of running), a developing solution prepared by diluting a developing tablet with diluting water and adding a starter solution to 330 ml of a starting solution was added. The processing was started by filling the developing tank. 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 became 1.0, and the photosensitive material was run. For running, an automatic developing machine SRX-502 equipped with a charging member for a solid processing agent and modified so as to process at a processing speed of 15 seconds was used.

During running, the light-sensitive material 1. m
One E agent, two F agents and 20 ml of water were added per ² parts. The pH when each of E and F was dissolved in 20 ml of water was 10.70.

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.

[0186] Developer (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 bicarbonate 20.0 g 1-Phenyl-3- Pyrazolidone 3.0 g Sodium sulfite 15.0 g Polyethylene glycol 15.0 g Glutaraldehyde human sulfite adduct 4.0 g Fixer (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 disodium ethylenediaminetetraacetate / dihydrate 0.02 g <evaluation> The hydroquinone used in Example 1 was And samples treated with a developer to agent,
A sample treated with the above-mentioned developer using erythorbic acid as a developing agent was prepared, and the sensitivity was measured as in Example 1. Table 3 below shows the sensitivity fluctuation width (%) depending on the difference in the developer.

[0187]

[Table 3]

As is clear from the table, the sample according to the present invention has a small fluctuation in sensitivity and exhibits extremely stable performance even when processed with a developing solution containing erythorbic acid as a main agent which is friendly to the working environment and the global environment. It can be seen that it has.

[0189]

As demonstrated in the examples, according to the present invention, a silver halide photographic light-sensitive material having high sensitivity and having extremely little fog even when stored at a high temperature was obtained. Further, high performance was obtained even when a developer and a solid processing agent containing ascorbic acids were used, and an X-ray imaging method having the above performance was obtained even when photographing with a high-sensitivity intensifying screen.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03C 5/17 G03C 5/17 5/26 520 5/26 520 5/30 5/30 G21K 4/00 G21K 4/00 A

Claims (5)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer and a hydrophilic colloid layer adjacent to the silver halide emulsion layer on a support, wherein the photosensitive halogen The silver halide grains of the silver halide emulsion layer are subjected to reduction sensitization and selenium and / or tellurium sensitization at any time during the production process, and the silver halide grains from the photosensitive silver halide emulsion layer and the adjacent hydrophilic colloid layer A silver halide photographic material characterized in that at least one selected layer contains at least one compound represented by the following general formula (1). Formula (1) R _1- (S) _n -R _{2 In the} formula, R ₁ and R ₂ may be the same or different,
Each represents a substituted or unsubstituted aliphatic group, aromatic group, or heterocyclic group, and R ₁ and R ₂ may combine with each other to form a substituted or unsubstituted ring. n represents an integer of 2 to 6. 2. The silver halide light-sensitive material according to claim 1, wherein the average aspect ratio of the silver halide grains in the light-sensitive silver halide emulsion layer is from 2 to 10. 3. A method for continuously processing the silver halide photographic light-sensitive material according to claim 1 or 2 after imagewise exposure and using an automatic processor, wherein each processing solution in the processing step in the automatic processor is used. A method for processing a silver halide photographic light-sensitive material, wherein a solid processing agent is supplied while continuously processing the same. 4. The method for processing a silver halide photographic light-sensitive material according to claim 3, wherein the developer is substantially free of a dihydroxybenzene-based developing agent and contains a compound represented by the following general formula (2). A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed with a developing solution. Embedded image (Wherein R ₃ and R ₄ each represent a hydroxy group, an amino group,
Represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P, Q
Represents a hydroxy group, a carboxy group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, a methylcapto group, an alkyl group or an aryl group, or a combination of P and Q And 5 to 8 together with the two vinyl carbon atoms to which R ₃ and R ₄ are bonded and the carbon atom to which Y is bonded.
Represents the group of atoms necessary to form a member ring. Y represents ＯO or ＮN—R ₅ . R ₅ is a hydrogen atom, a hydroxyl group,
Represents an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group. ) 5. A method for photographing a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to claim 1 is sandwiched between high-sensitivity intensifying screens and X-ray photographing is performed.