JPH10319531A - Silver halide photographic sensitive material, its processing method and photographing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material high in CP and sensitivity and low in fog and superior in storage stability and to provide the processing method capable of obtaining processing stability and the above performances even in the case of using a fixed processing agent containing no dihydroxybenzene derivatives and to provide the X-ray photographing method by using a highly sensitive sensitizing paper. SOLUTION: The silver halide photographic sensitive material contains silver halide grains comprising an average aspect ratio of 3-15 and a thiocyanic acid compound present on the surface of each flat silver halide grain in an amount of 1×10<-4> -2×10<-3> mol/mol of silver halide, and a hydrophilic colloidal layer contains at least one of compunds represented by the formula: R-(SM)x in which R is an aliphatic, aromatic or heterocyclic group each substituted by a water-soluble group or an atomic group capabel of forming a ring together with each other; S(M)x is an group adsorbable to silver halide; M is an H or alkali metal atom or a cation; (x) is 0 or 1 and when (x) is 0, M is a cation.

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 In recent years, with respect to silver halide photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials), there has been a strong demand for simplification of development processing operations or improvement of processing methods which do not harm human bodies and the environment. . Various methods have been proposed as countermeasures. One of the methods is, for example, rapid processing and reduction of the amount of replenisher. The most reliable and effective technical means for achieving these is to reduce the amount of silver in the photosensitive material. However, a simple reduction in the amount of silver causes a significant deterioration in photographic density, so that it is necessary to provide a silver halide grain with a high covering power (high CP) technology and a high sensitivity technology.

It is already well known in the art that particles having a high aspect ratio are effective as a technique for achieving a high CP. Further, as a high CP technology, for example,
A technique for forming particles in the presence of a thiocyanate disclosed in Japanese Patent No. 18538 is known. However, this technique has a disadvantage that the raw preservability of the photosensitive material is deteriorated.

On the other hand, in order to improve this drawback, Japanese Patent Laid-Open No. 5-1732 discloses a technique in which raw storability is improved by defining the amount of thiocyanic acid present on the surface of silver halide grains.
No. 74, but still at an unsatisfactory level.

Further, the above technique achieves high CP by expanding the silver shape after development, but at the same time, fine developed silver filaments are easily generated, and the silver image generated by development has a yellow tint. It had a problem that was easily taken. The color tone of silver images is important for photosensitive materials for medical use,
When a doctor observes an image, it is most preferable to have a pure cold black tone that is easy to see.

Further, as a sensitization technique, studies on chemical ripening by reduction sensitization and selenium and / or tellurium sensitization have been energetically conducted. However, as fog increases, further studies are required. There is the present situation.

On the other hand, if we turn our attention to environmental improvement, in recent years, a developing solution using ascorbic acids for environmental and safety reasons, compared to hydroquinones (dihydroxybenzenes) as developing agents, is disclosed in US Pat. 236,816
The disclosure is made by

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

In medical photosensitive materials, there is a strong demand for a reduction in the amount of X-ray exposure to the human body, and there is an urgent need to increase the sensitivity of photosensitive materials and processing systems.

[0010]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a silver halide photographic material having high CP, high sensitivity, low fog and excellent storage stability over time. is there. A second object of the present invention is to provide a silver halide photographic light-sensitive material which is substantially free of hydroquinones and has excellent processing stability in addition to the above-mentioned properties even when processed using a solid processing agent. It is to provide a processing method. 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]

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

(1) In a silver halide photographic material having a hydrophilic colloid layer including at least one photosensitive silver halide emulsion layer on a support, the halogen in the photosensitive silver halide emulsion layer 50% or more of the total projected area of the silver halide grains is composed of tabular grains having an average aspect ratio of 3 to 15,
The content of the thiocyanate compound present on the surface of the tabular grains is from 1 × 10 ⁻⁴ mol to 2 × 10 ⁻³ mol per mol of silver, and the following general formula (1) A silver halide photographic material comprising at least one compound represented by the formula (1):

In the formula, R is an aliphatic group, an aromatic group, a heterocyclic group, or an atom capable of forming a ring by bonding to each other. Represents a group. S (M) x represents a group which can be adsorbed to silver halide, M represents a hydrogen atom, an alkali metal atom or a cationic group, x is 1 or 0, and when x is 0,
M represents a cationic group.

(2) The silver halide grains in the photosensitive silver halide emulsion layer have been subjected to reduction sensitization and selenium and / or tellurium sensitization at any time during the silver halide emulsion production process. (1) The silver halide photographic material as described in (1) above.

(3) A method for imagewise exposing the silver halide photographic light-sensitive material according to the above (1) or (2), followed by continuous processing in an automatic developing machine, wherein during the processing step of the automatic developing machine, Wherein a solid processing agent is supplied to each of the processing tanks.

(4) In the processing method for a silver halide photographic light-sensitive material described in the above item (3), the developing solution contains substantially no 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 the compound represented by the formula (I).

[0017]

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

(5) X-ray photographing of the silver halide photographic light-sensitive material described in the above (1) or (2), wherein the material is sandwiched between high-sensitivity intensifying screens and X-ray photographing is performed. Method.

Hereinafter, the present invention will be described in detail.

The silver halide grains of the silver halide photographic light-sensitive material of the present invention have an aspect ratio (grain diameter / grain thickness).
Are tabular grains having an average aspect ratio in the range of 3 to 15. Preferably the average aspect ratio is 3
To 10 tabular silver halide grains.

The tabular silver halide grains mentioned here are crystallographically classified as twins.

Twins are silver halide crystals having one or more twin planes in one grain, and the classification of twins is based on a report by Klein and Moiser.
Correspondents (Photographhish K
orrespondenz), Vol. 99, p. 99, and Vol. 100, p. 57.

The surface of the tabular silver halide grains of the present invention contains a thiocyanate compound as a chemical sensitizer. The thiocyanate compound preferably used in the present invention is not particularly limited as long as it functions as a solvent for silver halide grains, such as potassium thiocyanate and ammonium thiocyanate, but potassium thiocyanate is most preferred.

The amount of the thiocyanate compound present on the surface of the silver halide grain is from 1 × 10 ^-4 mol to 2 mol / mol of silver.
× 10 ^-3 mole, preferably 1 × 1 mole per mole of silver.
0 ^-4 mol to 3 × 10 ^-3 mol.

The timing and conditions for the addition of the thiocyanic acid compound may be arbitrarily set, but preferably the step from the point when the tabular silver halide grains of the present invention have grown 90% or more to the start of the desalting step is preferable, and more preferably. pBr is 2.5 to
Under the conditions of 3.5, the thiocyanate compound was added in an amount of 1 per mole of silver.
After adding from × 10 ^-2 mol to 2 × 10 ^-1 mol, pBr is adjusted to 0.5 to 1.5 before the desalting step.

In the present invention, thiocyanate ion is determined by the following method.

<Method for Quantifying Thiocyanate Ion on Silver Halide Grain Surface of Emulsion Before Coating> Silver halide 1.5 ×
10 ml of distilled water was added to the emulsion containing 10 ^-2 mol,
And stir for 30 minutes. Centrifuge this emulsion,
After the emulsion is completely separated, the supernatant is diluted 100-fold. After ultrafiltration of the diluent, thiocyanate ions in the diluent are quantified by ion chromatography. For the quantification, a calibration curve separately prepared using an aqueous solution of a thiocyanate compound in advance is used. By subtracting the value obtained in this manner from the value of all thiocyanate ions in the emulsion previously obtained, the amount of thiocyanate ion adhering to the target grain surface can be obtained.

<Method for Quantifying Thiocyanate Ion on Surface of Silver Halide Particles in Product-Type Photosensitive Material> The target emulsion layer containing 0.1 g of silver was peeled off from the photographic material to obtain 50 m
Immerse in 1 l of distilled water. The solution is ultrasonically stirred at 40 ° C. for 30 minutes. After further centrifugation, the supernatant is filtered. After diluting the filtrate 10-fold, the contained thiocyanate ion is quantified by ion chromatography. For the quantification, a calibration curve separately prepared using an aqueous solution of a thiocyanate compound in advance is used. By subtracting the value obtained in this manner from the value of all thiocyanate ions in the emulsion previously obtained, the amount of thiocyanate ion adhering to the target grain surface can be obtained. If this operation is performed after performing layer-by-layer peeling even in a multi-layer coated product photosensitive material,
Information about the emulsion in the intended layer is accurately determined.

The hydrophilic colloid layer of the light-sensitive material of the present invention contains the compound represented by the general formula (1).

The group represented by R in the general formula (1) is an aliphatic group, an aromatic group, a heterocyclic group, or a group of atoms which bond to each other to form a ring. Has been replaced. -SO ₃ H, -C Aqueous solutions group
OOH, mention may be made of the -OH and -NHR _2.
R ₂ may be any as long as it does not impair the water solubility, such as —COCH ₃ and —SO ₂ Na. Among the water-soluble substituents, -COOH is preferred.

The water-soluble substituent may be substituted by one or more. Further, as a substituent of R other than the water-soluble group,
It is more preferred to contain an electron withdrawing group. For example, a halogen atom (especially F, Cl), trifluoromethyl, cyano, carboxy, carbamoyl, ethynyl, acetyl,
Examples include groups such as ethoxycarbanyl, trifluoromethoxy, sulfamoyl, methanesulfonyl, benzenesulfonyl, trifluoromethylthio, isothiocyanate, 1-pyrroline, and 2-pyridyl.

Further, the compound represented by formula (1) of the present invention will be described.

In the general formula (1), the aliphatic group represented by R has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Linear or branched alkyl, alkenyl, alkynyl or cycloalkyl groups. Specifically, for example, 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. The aromatic group represented by R has 6 to 6 carbon atoms.
20 groups, and specific examples include groups such as phenyl, naphthyl, and anthranyl. The heterocyclic group represented by R may be a single ring or a condensed ring,
5 having at least one of O, S, and N atoms in a ring
And a 6-membered heterocyclic group. Specifically, for example,
Pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, oxirane, morpholine, thiomorpholine, thiopyran, tetrahydrothiophene, pyrrole,
Examples include pyridine, furan, thiophene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, tetrazole, thiadiazole, oxadiazole, and groups derived from these benzerogues.

The ring forming a ring with R includes a 4- to 7-membered ring. It is preferably a 5- to 7-membered ring.
Preferred groups for R are heterocyclic groups, and more preferred are heteroaromatic ring groups. In the present invention, the aliphatic group, aromatic group or heterocyclic group represented by R needs to be substituted with a water-soluble group, and groups other than the water-soluble group may be further substituted. .

These substituents include a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl, ethyl, isopropyl, hydroxyethyl, methoxymethyl, trifluoromethyl, t-butyl) Group), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group) ), An alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group, butoxy group, etc.), an aryloxy group (eg, phenoxy group, 4-methoxyphenoxy group, etc.), a cyano group, an acylamino group (eg, acetylamino group, propionyl) Amino group, etc., alkylthio group (for example, methylthio group Ethylthio group, butylthio group, etc.), arylthio group (eg, phenylthio group, p-methylphenylthio group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (eg, 3-methylureido group) ,
3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, diethylsulfamoylamino group, etc.), carbamoyl group (for example, methylcarbamoyl group,
Ethylcarbamoyl group, dimethylcarbamoyl group, etc.),
Sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, p-chlorophenoxycarbonyl group, etc.) ), A sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), an acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), an amino group (methylamino group, ethylamino group, dimethylamino group, etc.) ), A hydroxy group, a nitro group, a nitroso group, an amine oxide group (for example, a pyridine-oxide group), an imide group (for example, a phthalimide group), a disulfide group (for example, a benzene disulfide group, a benzothiazolyl-2-disulfide). Group), a Hajime Tamaki (e.g., pyridyl, benzimidazolyl group, benzothiazolyl group, benzoxazolyl group). R may have one or more of these substituents. Further, each substituent may be further substituted with the above substituent. R is particularly preferably a group containing an electron-withdrawing group.

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

[0038]

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[0039]

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[0040]

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[0041]

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The compound represented by the above general formula (1) needs to be added to the emulsion layer and / or the hydrophilic colloid layer adjacent to the emulsion layer before, during, or after the chemical ripening. The preferred addition amount is 0.1 to 5 mg / m
² , more preferably 1 to 3 mg / m ² . The compound represented by the general formula (1) can be dissolved in water or an organic solvent (eg, methanol) miscible with water, or can be added in a finely dispersed form in a gelatin solution or the like. The compound represented by the general formula (1) may be present as a silver salt compound in the emulsion and / or the light-sensitive material after addition.

The light-sensitive silver halide grains of the 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 40-70 ° C, time is 10-200 minutes, pH
Is preferably in the range of 5 to 11 and pAg is preferably in the range of 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.

As stabilizers for the reduction-sensitized silver halide grains, the following general stabilizers can be used, and the antioxidants disclosed in JP-A-57-82831 and V stabilizers can be used. . 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 to be used 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 (for example,
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-described reduction sensitization may be performed by combining two or more types of reduction sensitization, for example, a combination of a water-soluble silver salt and a reducing agent.

Next, the silver halide grains of the present invention will be described.

The silver halide grains preferably used in the present invention mainly have an even number of parallel twin planes. These twin planes may or may not be parallel to each other. Particularly preferably, it has two twin planes. In the tabular silver halide grains of the present invention, the outer wall of the crystal may substantially consist essentially of the (111) plane or may consist of the (100) plane. Also,
It may have both the (111) plane and the (100) plane. In this case, 50% or more of the particle surface is (11)
1) surface, more preferably 60% to
90% is the (111) plane, particularly preferably 70 to 9
5% is the (111) plane. It is preferable that the plane other than the (111) plane is mainly the (100) plane. This surface ratio utilizes the difference in the adsorption dependency between the (111) plane and the (100) plane in the adsorption of the sensitizing dye [T. Tani, J .;
ImagingSci, 29, 165 (1985)]
Can be obtained by

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

Further, the distribution of the halogen content of each grain in the emulsion containing the tabular silver halide grains of the present invention is preferably small. Specifically, (standard deviation of halogen content / average halogen content) × 100 = 2 when the width of distribution is defined by the width (%) of halogen content
It is preferably at most 5%, more preferably at most 20%, particularly preferably at most 15%.

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 obtained. 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 a circle equivalent diameter of the projected area of the grains, and is preferably 0.30 μm or more, more preferably 0.30 to 0.30 μm.
It is 5 μm, more preferably 0.40 to 2 μm.

The particle size can be obtained by projecting the particles at a magnification 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 assumed to be 1,000 or more indiscriminately.) The particle thickness 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 present 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 of 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 a uniform composition. It preferably has a / shell type 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 grains of the present invention is preferably 2 mol% or less, more preferably 0.1 mol% or less.
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 inner layer (core) having the highest silver iodide content
Is preferably 2.5 mol% or more, more preferably 5 mol% or more, and the outermost surface layer (shell)
Has a silver iodide content of 0 to 5 mol%, preferably 0 to 3 mol%.
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.

The silver halide grains are described in, for example,
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 of the present invention for producing tabular silver halide grains, a water-soluble silver salt solution and a water-soluble halide solution are supplied to a protective colloid in the presence of a protective colloid. The following conditions are preferably used.

(A) The mother liquor has a p content of 0 to 5 mol% in the mother liquor for a period of 1/2 or more from the initial stage of silver halide precipitation.
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 the 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 preparing 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. It can be gradually changed. 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 growth, an aqueous silver nitrate solution and an aqueous halide solution 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 course of grain formation and / or growth 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 silver halide grains, or may be kept contained. When removing the salts, use Research Disclosure (R
D) 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 light-sensitive material of the present invention. Known additives include, for example, (RD) 17643 (December 1978) and 1871
6 (November 1979) and 308119 (1989)
(December, 2000). The compound types and locations described in these three (RD) are described below.

[0090]

[Table 1]

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

Examples of the support which can be used for the light-sensitive material include 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 light-sensitive 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 liquid or a fine or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is added to the surface of the temporarily formed photographic processing agent. Any means can be adopted such as forming a coating layer by spraying.

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.

The granulation method for tablet formation is to use a known method such as tumbling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, and spray drying granulation. Can be done.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Furthermore, the particle size distribution is
Preferably, 0% or more is within a deviation of ± 100 to 150 μm. Next, when the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a 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 effect is further remarkable by separately granulating each component such as 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 its solubility and the 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.

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

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

In the case of solidifying the developer, it is preferable that all of the alkali agent and the reducing agent be solid-processed, and in the case of tablets, at least three or less, 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 tightly adhered or adhered to each other so as to sandwich the solid processing agent so as to be able to separate the periphery of 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 introduced may be in the processing tank, but is preferably a place where the processing liquid is communicated 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 does not substantially contain a dihydroxybenzene-based main agent, and is processed with a developer containing the compound represented by the formula (2) as a main agent. Here, the expression "contains substantially no dihydroxybenzene-based active substance" means that it does not contain an amount having a developing ability.

In the general formula (2), R ₁ and R ₂ are each a hydroxy group, an amino group (which may have an alkyl group such as ethyl, butyl or hydroxyethyl as a substituent), an acylamino group (acetylamino group). , Benzoylamino, etc.), alkylsulfonylamino group (methanesulfonylamino, butanesulfonylamino, etc.), arylsulfonylamino group (benzenesulfonylamino, p-toluenesulfonylamino, etc.), alkoxycarbonylamino group (methoxycarbonylamino, etc.), mercapto Represents a group or an alkylthio group (e.g., methylthio, ethylthio), and R ₁ and R ₂ preferably include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q are each a hydroxy group, a carboxyl group, an alkoxy group (methoxy, ethoxy, butoxy, etc.), a hydroxyalkyl group (hydroxymethyl, hydroxyethyl, etc.), a carboxyalkyl group (carboxymethyl, carboxyethyl, etc.), Sulfo group (including salt), sulfoalkyl group (sulfoethyl, sulfopropyl, etc.), amino group (including alkyl substitution), aminoalkyl group (aminoethyl, aminopropyl, etc.), alkyl group (methyl, ethyl, propyl, butyl) , Pentyl, etc.)
Or an aryl group (phenyl, p-tolyl, naphthyl, etc.)
Or a non-metallic atomic group bonded to each other to form a 5- to 8-membered ring together with two vinyl carbon atoms substituted by R ¹ and R ² and a carbon atom substituted by Y. These 5-8
The membered rings may form a saturated or unsaturated fused ring.

Examples of the 5- to 8-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring,
Examples thereof include an azacyclohexenone ring, a uracil ring, a cycloheptenone ring, a cyclohexanone ring, an azepine ring, and a cyclooctenone ring, and a 5- to 6-membered ring is preferable. Among them, preferred examples of the 5- to 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexanone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.

When Y represents ＮＲNR ₃ , R ₃ is a hydrogen atom,
It represents a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group, and specific examples of each substituent are the same groups as those described above for R ₁ , R ₂ , P and Q. Can be mentioned.

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.

[0117]

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[0118]

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[0119]

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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.

Examples of development accelerators include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, and other 1-phenyl compounds.
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, methylcellosolve, methanol, acetone, dimethylformamide, a cyclodextrin compound, and other organic solvents for increasing the solubility of the developing agent may be used, if necessary. it can.

Further, various additives such as a stain inhibitor, an anti-sludge agent and a layering effect promoter 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.

It is preferable to add a starter to the developer prior to processing, 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 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 of photographing a silver halide photographic light-sensitive material of the present invention, X-ray photography is performed by sandwiching the light-sensitive material with a high-sensitivity intensifying screen.

In the high-sensitivity intensifying screen (also referred to as a radiation intensifying screen) of the present invention, the filling rate of the phosphor in the phosphor layer is preferably 68% or more, 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 radiographic intensifying screen of the present invention, by increasing the packing ratio of the phosphor particles, the X-ray absorption of each radiographic intensifying screen 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 for use 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.

[0138]

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 (for comparison) A1 Ossein gelatin 75.5 g 10% aqueous solution of polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt 6.78 ml Potassium bromide 64.7 g To 10800 ml with water Finish B1 0.7N silver nitrate aqueous solution 1340ml C1 2.0N silver nitrate aqueous solution 1500ml D1 1.3N potassium bromide aqueous solution 410ml E1 2.0N potassium bromide aqueous solution The following silver potential control amount F1 ossein gelatin 125g water 4000ml G1 3% gelatin by weight Fine grain emulsion (*) comprising silver iodide grains (average grain size: 0.05 μm), equivalent to 0.008 mol Fine grain emulsion (*): 5.0 wt% gelatin aqueous solution containing 0.06 mol of potassium iodide 6.64 liters
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) is completed, the solution (F1) is added, and the temperature is raised to 70 ° C. for aging. 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 1) was kept at pAg = 7.8, simultaneous addition and mixing were performed at a speed commensurate with the critical growth rate, and (G1) was added after the entire amount of (C1) was added. After stirring for 5 minutes, soluble salts were desalted and removed by a sedimentation method.

In this emulsion, 90% or more of the total projected area of the silver halide grains consisted 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 was 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 16%. No residual amount of thiocyanic acid was found on the particle surface.

Preparation of Emulsion-2 (for the present invention) A1 Ossein gelatin 75.5 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt 10% aqueous solution 6.78 ml Potassium bromide 64.7 g Finish with water to 10800 ml B1 0.7N silver nitrate aqueous solution 1340ml C1 2.0N silver nitrate aqueous solution 1500ml D1 1.3N potassium bromide aqueous solution 410ml E1 2.0N potassium bromide aqueous solution The following silver potential control amount F1 ossein gelatin 125g water 4000ml G1 KSCN aqueous solution (2N) 30ml H1 Fine grain emulsion (*) composed of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) Equivalent to 0.008 mol Fine grain emulsion (*): 5.0 containing 0.06 mol of potassium iodide 6.6% by weight aqueous gelatin solution 4 liters,
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) is completed, the solution (F1) is added, and the temperature is raised to 70 ° C. for aging. 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.

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 to 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 16%. The residual amount of thiocyanic acid on the particle surface was 7.0 × per mole of silver.
It was 10 ^-4 mol.

Preparation of Emulsion-3 (for the present invention) A 30% aqueous KSCN solution (2N) of G1 solution of Emulsion-2 was prepared.
Emulsion-3 was prepared in the same manner except that the ml was changed to 100 ml. The average aspect ratio was confirmed by an electron microscope to be 4.1. The residual amount of thiocyanic acid on the surface of the grains was 3.0 × 10 ⁻³ mol per mol of silver.

Preparation of Emulsions 4 to 17 Subsequently, a predetermined amount of the above Emulsion-1 was heated to 55 ° C., and subjected to spectral sensitization and chemical sensitization according to the following sensitization prescription to prepare Emulsions 4 to 17 did.

(Preparation of Solid Fine Particle Dispersion of Spectral Sensitizing Dye) The following spectral sensitizing dyes (A) and (B) were added at a ratio of 100: 1 to water previously adjusted to 27 ° C., 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 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.

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

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 After the ripening, the compound represented by the general formula (1) of the present invention was prepared in a free form and a free form as shown in Table 2, and (TAI) was uniformly added as a stabilizer to 500 mg.
mg was added to prepare Emulsions-4, 5, and 6.

Similarly, Emulsions 7-1 to 1 were prepared using Emulsions-2 and 3.
7 was prepared.

[0157]

[Table 2]

<Preparation of Coated Sample> Emulsion Obtained 4-1
The following additives were added to No. 7 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. Using a slide hopper type coater, both sides were simultaneously coated on the support at a speed of 80 m / min, and dried for 2 minutes and 20 seconds. 1
To 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% Tin oxide dispersion (Japanese Patent Application No. Hei 7)
No. 231445) as a subbing liquid.
A polyethylene terephthalate film base colored blue to a concentration of 0.15 for an X-ray film of 5 μm 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 Matting Agent Containing Polymethyl Methacrylate (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

[0163]

Embedded image

[0164]

Embedded image

[0165]

Embedded image

[0166] Thus, Sample 1 was prepared.

As shown in Table 2, the sample N was prepared in exactly the same manner except that the compounds represented by the general formula (1) of the present invention and the comparative compounds were changed and the same molar amounts were added.
o. 2-14 were prepared. 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.

Incidentally, tablets for replenishment of development were 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) DTPA 100 g, potassium carbonate 4000 g, 5-methylbenzotriazole 10 g, 1-phenyl-5-mercaptotetrazole 7 g, 2-mercaptohypoxanthine 5 g, KOH 200 g, N-acetyl-D, L-penicillamine Pulverization and granulation are performed as in (A). The amount of water to be added is 30.0 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. The mixture 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): 1000 g of boric acid, 150 parts of aluminum sulfate / 18 hydrate
0 g, sodium hydrogen acetate (3,000 g of glacial acetic acid and sodium acetate mixed and dried), tartaric acid 200
g is ground and granulated in the same manner as in the operation (A). The amount of water to be added is 100 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. 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 processing of the developing solution (start of running), the developing tank was filled with 16.5 liters of developing solution prepared by diluting water for dilution with 330 ml of the above 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 photosensitive material prepared above was exposed to light so that the optical density after development processing was 1.0, and the photosensitive material was run. For 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 the running, the developing solution contains 0.6 photosensitive material.
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.

[0180] 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 3 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 condition A of 1 is 100 is shown.

[0183]

[Table 3]

As is clear from the results shown in Table 3, the sample of the present invention was excellent in low fog, high sensitivity, high CP, and extremely little fog even when stored at a high temperature. The sample of the present invention maintained high sensitivity even when left at a high temperature. In the case where particles other than the present invention containing no thiocyanate ion on the particle surface were used, fog was not increased in the storage stability test (condition B), but high sensitivity was not obtained and the object of the present invention was achieved. I couldn't do it. Sample No. Nos. 6 and 7 are compared. 7 is slightly better in terms of low fog and high CP, indicating that a larger number of water-soluble substituents is preferable.

Example 2 Preparation of Emulsion-4 A1 Ossein gelatin 75.5 g 10% aqueous solution of surfactant (A) * in ethanol 6.78 ml Potassium bromide 64.7 g Finished to 10800 ml with water B1 0.7N silver nitrate aqueous solution 1340ml C1 2.0N silver nitrate aqueous solution 1500ml D1 1.3N potassium bromide aqueous solution 410ml E1 2.0N potassium bromide aqueous solution The following silver potential control amount F1 ossein gelatin 125g water 4000ml G1 KSCN aqueous solution (2N) 30ml H1 3% by weight gelatin Emulsion (*) equivalent to 0.008 mol of silver iodide grains (average particle size: 0.05 μm) Surfactant (A) *: Polypropylene oxy-polyethylene oxy-disuccinate sodium salt fine grain emulsion (*): Containing 0.06 mol of potassium iodide 5.0 wt% aqueous gelatin solution 6.64 liters,
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%.

A predetermined amount of the thus prepared emulsion-4 was taken and subjected to spectral sensitization and chemical sensitization in the same manner as in Example 1 except that the amount of the chalcogen sensitizer shown in Table 4 below was changed. The coating sample No. shown in Table 5 15-28 were prepared.

[0191]

[Table 4]

[0192]

[Table 5]

As is clear from Table 5, the samples of the present invention can obtain high sensitivity with low fog even in emulsions subjected to reduction sensitization.

Example 3 A developing tablet was prepared according to the following procedure.

Procedure (A) 13,000 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 hydrogen carbonate
25 g, glutaraldehyde sulfite adduct 650 g, and polyethylene glycol 6000 1354 g are pulverized and granulated in the same manner as in the operation (A). The amount of water added is 3
After granulation, the mixture is dried at 50 ° C. for 30 minutes to remove the water content of the granules almost completely. 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 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, 6500 aluminum sulfate / 18-hydrate
g, glacial acetic acid 1860 g, sulfuric acid (50 wt%) 928 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water to be added is 100 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. The obtained mixture was compressed and tableted using the same tableting machine as described above, with 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 the processing of the developing solution (start of running), a solution obtained by adding 330 ml of a starter to 16.5 liters of a developing solution prepared by diluting a developing tablet with dilution water was used as a starting solution. 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 the running, the photosensitive 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.

[0205] 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 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> Prepared in Example 2 using the treatment liquid prepared in this manner. Identical sample Was treated and evaluated,
All of the samples of the present invention had good photographic performance.

Example 4 (Preparation of tabular grain emulsion of pure silver chloride) A2 Ossein gelatin 37.5 g KI 0.625 g NaCl 16.5 g Make up to 7500 ml with distilled water B2 1500 g with silver nitrate Make up 2500 ml with distilled water 4 g of C2 KI 140 g of NaCl 684 ml with distilled water D2 375 g of NaCl 1818 ml with distilled water Emulsion-2 was obtained in the same manner as emulsion-1 except that EAg was adjusted to 150 mV using the above-mentioned additives A2 to D2.

When about 3,000 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%. In addition, the total silver amount ratio is 5
At the time of 0%, thiourea dioxide is added at a rate of 1% per mole of silver.
× 10 ^-6 mol was added.

<Sensitization Formulation and Formulation for Preparing Coated Sample> Example 1
The coating sample no. In the same manner as in Samples Nos. 4, 6, and 7, as shown in Table 6, 29, 30, and 31 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-based thermoplastic elastomer Demorac 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 the mixture was 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, 90 g of a soft acrylic resin solid and 50 g of nitrocellulose were separately used as a coating solution for forming an undercoat layer.
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.

Thickness of 250 μm incorporating titanium dioxide
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 with a doctor blade to a thickness of 240 μm and dried, 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.

With respect to the obtained sample, a sample treated with the developing solution containing hydroquinone used as a developing agent and a sample treated with the developing solution containing erythorbic acid as a developing agent used in Example 1 were prepared. 1 The sensitivity was measured in the same manner. Table 6 below shows the sensitivity fluctuation width (%) depending on the difference in the developer.

[0215]

[Table 6]

As can be seen 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.

[0219]

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.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 5/26 520 G03C 5/26 520 5/30 5/30

Claims (5)

[Claims] In a silver halide photographic material having a hydrophilic colloid layer including at least one photosensitive silver halide emulsion layer on a support, the halogenation in the photosensitive silver halide emulsion layer At least 50% of the total projected area of the silver particles is composed of tabular grains having an average aspect ratio of 3 to 15, and the content of the thiocyanate compound present on the surface of the tabular grains is 1 × 10 ^-4 mol per mol of silver. ２2 × 10 ^-3 mol, and the following general formula (1)
A silver halide photographic material comprising at least one compound represented by the formula: In the general formula (1) R-S (M ) x formulas, R represents an atomic group which can be substituted aliphatic group a water-soluble group, aromatic group, heterocyclic group, or combined with each other to form a ring . S (M) x represents a group which can be adsorbed to silver halide, M represents a hydrogen atom, an alkali metal atom or a cationic group, x is 1 or 0, and when x is 0,
M represents a cationic group. 2. The method according to claim 1, wherein the silver halide grains in the photosensitive silver halide emulsion layer have been subjected to reduction sensitization and selenium and / or tellurium sensitization at any time during the silver halide emulsion production process. The silver halide photographic light-sensitive material according to claim 1, wherein: 3. A method for imagewise exposing the silver halide photographic light-sensitive material according to claim 1 or 2, followed by continuous processing in an automatic developing machine, wherein each processing tank is in a processing step of the automatic developing machine. A method for processing a silver halide photographic light-sensitive material, characterized by supplying a solid processing agent to the material. 4. The method for processing a silver halide photographic light-sensitive material according to claim 3, wherein the developing solution contains substantially no dihydroxybenzene-based developing agent, and has the following general formula (2):
A method for processing a silver halide photographic light-sensitive material, comprising processing with a developer containing a compound represented by the formula: Embedded image In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group,
Represents a mercapto group or an alkylthio group. P and Q represent a hydroxy group, a carboxy group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, a methylcapto group, an alkyl group or an aryl group, or P and Q represents an atom group which forms a 5- to 8-membered ring together with the two vinyl carbon atoms to which R ₁ and R ₂ are bonded and the carbon atom to which Y is bonded. Y represents ＝ O or ＮN—R ₃ . R ₃ represents a hydrogen atom, a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group. 5. A method for photographing a silver halide photographic light-sensitive material, comprising sandwiching the silver halide photographic light-sensitive material according to claim 1 or 2 with a high-sensitivity intensifying screen and performing X-ray photography.