JP2001194739A - Silver halide photographic sensitive material, processing method for same and image forming method using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material for X-ray mammography having a high contrast, excellent in diagnostic ability and having good preservability, a processing method for the sensitive material and an X-ray image forming method using those. SOLUTION: In the silver halide photographic sensitive material with a photosensitive silver halide emulsion layer on one face of the support and a backing layer on the other face, flat platy silver halide grains doped with ions of a metal selected from Rh, Ru, Re and Os and having an aspect ratio of 3-30 occupy >=50% of the total projected area of all silver halide grains contained in the photosensitive silver halide emulsion layer and a compound of formula 1, e.g. formula 2 is contained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material for single-sided exposure for medical use.

[0002]

2. Description of the Related Art In recent years, it has been found from the survey of disease trends in Japan that the number of cases of breast cancer has increased, and early detection of breast cancer in health examinations has become an important issue.
Conventionally, breast cancer screening includes visual inspection, palpation, ultrasonic imaging, X
X-ray mammography (mammography) is performed,
In particular, the importance of mammography is increasing due to its diagnostic effectiveness. In X-ray mammography, a source having a low X-ray absorptivity and a low tube voltage (40 KVp or less) is used because the object contrast is originally low. However, the image to be diagnosed is still often a tumor shadow or the like having only a small contrast, and this is particularly difficult to find an early cancer.

Further, microcalcified images having a size of several 100 μm are also important for the diagnosis of breast cancer, and it is necessary to accurately read their morphology. Since the calcified portion has a high X-ray absorption rate, it is represented as a low density point on the image. Therefore, a film having a high gradation in a low density portion is suitable for detecting microcalcification.

[0004] As means for increasing the gradation of the film, a method using an emulsion having a high degree of monodispersity, a method using a high contrast agent, a method of forming a multilayer structure and disposing a low-sensitivity emulsion layer on an upper layer are known. However, excessively increasing the gradation of the film makes the graininess more conspicuous, so that the identification of the low-contrast image often deteriorates. Therefore, a means for adjusting to an appropriate gradation is desired.

[0005] A method of using a water-soluble rhodium compound as a high contrast agent when forming silver halide grains is conventionally known. However, most of these techniques are for obtaining ultra-high contrast characteristics as a photosensitive material for printing, and contain a large amount of rhodium salt.

[0006] By reducing the amount of rhodium salt, it is possible to adjust the gradation suitable for mammography, which is the object of the present invention, but the tendency of the gradation drop during storage increases. Concerning the improvement of the preservability when a rhodium salt is used, for example, a method of adding a nucleic acid degradation product in JP-A-50-23618 and a method of adding dihydroxyaryls or aminophenols in JP-A-52-11029 Is known but not enough.

JP-A-6-102613 discloses a method in which a relatively small amount of a rhodium salt is added to silver iodobromide containing 4 mol or less of silver iodide together with a spectral sensitizing dye before chemical sensitization. Has been described. However, it was also found that this method was not sufficiently effective for tabular silver halide grains having an aspect ratio of 4 or more.

On the other hand, it is known that tabular silver halide grains can easily obtain high sensitivity and have high covering power. Although the tabular grains had these excellent properties, it was found that when doped with a rhodium salt in order to increase the gradation, the gradation decrease during storage was larger. JP-A-2-
No. 2,191,051 describes a color photographic light-sensitive material containing tabular silver halide grains containing a noble metal such as rhodium, ruthenium, osmium, iridium, etc., in which rhodium or the like acts as a desensitizer, It is described that by using particles having the same diameter as a mixture, a gradation can be formed in a wide exposure range, and processing fluctuation and gradation preservability are improved. Japanese Patent Application Laid-Open No. 9-197597 discloses that tabular silver halide grains are doped with at least one of chromium, ruthenium, rhodium, rhenium and osmium, and selenium-sensitized to increase sensitivity and increase fog over time. Have been disclosed. However, it has been found that none of them is sufficient for the storage stability under high gradation conditions required for the photosensitive material for mammography which is the object of the present invention.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic material for X-ray mammography having high contrast, excellent diagnostic performance, and good storage stability, a method of processing the same, and a method for processing the same. An object of the present invention is to provide an X-ray image forming method used.

[0010]

An object of the present invention is to provide a silver halide having at least one light-sensitive silver halide emulsion layer on one side of a support and a backing layer on the other side. In the photographic light-sensitive material, at least one of the light-sensitive silver halide emulsion layers has at least 50% of the total projected area of the contained silver halide grains of Rh, Ru, and R.
e, tabular silver halide grains having an aspect ratio of 3 to 30 doped with at least one metal ion selected from e and Os, and containing at least one compound represented by the general formula (1). A silver halide photographic material having at least one photosensitive silver halide emulsion layer on one side of a support and a backing layer on the other side; In at least one of the silver halide emulsion layers, 50% or more of the total projected area of the silver halide grains contained therein is Rh, Ru, or R.
e, tabular silver halide grains doped with at least one metal ion selected from Os and having an aspect ratio of 3 to 30 and containing at least one compound represented by the general formula (2). A silver halide photographic material having at least one photosensitive silver halide emulsion layer on one side of a support and a backing layer on the opposite side; At least one of the silver emulsion layers has at least 50% of the total projected area of the silver halide grains contained therein as Rh, Ru, or R.
e, tabular silver halide grains doped with at least one metal ion selected from Os and having an aspect ratio of 3 to 30 and containing at least one compound represented by the general formula (3). Silver halide photographic material,
Wherein the doping amount of the metal ion is 1 × 10 ⁻¹⁰ mol or more and less than 1 × 10 ⁻⁷ mol per mol of silver, and the tabular silver halide grains are grown by ultrafiltration in the growth process. A silver halide grain that has been subjected to grain growth while appropriately extracting a salt-containing solution from a reactant solution, and a coefficient of variation of a volume particle size of the tabular silver halide grain is 0.10 or less; Wherein the silver halide photographic light-sensitive material does not substantially contain hydroquinones, contains the compound represented by the general formula (4) and nitroindazole, and has a bromine ion concentration in terms of potassium bromide. A processing method of a silver halide photographic light-sensitive material, which is processed using a developer having a concentration of 10 g / l or more, that the developer is a solution in which a solid developer is dissolved, that the solid developer is a tablet, The surface of the silver halide photographic light-sensitive material having the silver halide emulsion layer is adhered to the surface of the X-ray fluorescent intensifying screen having the phosphor layer and irradiated with X-rays transmitted through the subject,
Thereafter, an image forming method for forming an X-ray image by developing, fixing, washing and drying with an automatic developing machine, and a processing method wherein the phosphor of the X-ray fluorescent intensifying screen is terbium-activated gadolinium oxysulfide. To be used for X-ray mammography.

Hereinafter, the present invention will be described in detail. In the general formula (1), Y is more preferably C = O, C = S or C =
Se, most preferably C = O.

When R ₁ and R ₂ are an aliphatic group, an alkyl group having 1 to 22 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group) , 2-ethylhexyl, decyl, dodecyl, hexadecyl, otatadecyl, cyclohexyl, isopropyl, t-butyl, etc.) or alkenyl having 2 to 22 carbon atoms (eg, allyl, butenyl, etc.) Or an alkynyl group (for example, a propargyl group, a butynyl group, etc.). More preferably, the aliphatic group is an alkyl group having 1 to 8 carbon atoms or an alkenyl or alkynyl group having 3 to 5 carbon atoms. These groups may or may not have a substituent.

Preferred aromatic groups for R ₁ and R ₂ are those having 6 to 20 carbon atoms, and include phenyl and naphthyl groups. More preferably, it has 6 carbon atoms.
It has 10 to 10. These groups can have substituents.

The heterocyclic group represented by R ₁ and R ₂ is nitrogen,
It is a 3- to 15-membered ring containing at least one atom selected from oxygen, sulfur, selenium and tellurium. More preferably, the heterocyclic group is a 5- or 6-membered ring containing at least one atom selected from nitrogen, oxygen and sulfur. As the heterocyclic group, a pyrrolidine ring, a piperidine ring, a pyridine ring, a tetrahydrofuran ring, a thiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a benzothiazole ring, a benzoxazole ring, a benzimidazole ring,
Examples thereof include a selenazole ring, a benzoselenazole ring, a tellurazole ring, a triazole ring, a benzotriazole ring, a tetrazole ring, an oxadiazole ring, and a thiadiazole ring.

Preferably, R ₁ and R ₂ together form a ring or polycyclic system. The ring or polycyclic system formed by R ₁ and R ₂ may be an alicyclic group or the above-mentioned aromatic group or heterocyclic group. Preferably, R ₁ and R ₂ together form a 5- or 6-membered ring, preferably an aromatic ring.

Examples of the substituent of R ₁ and R ₂ include an alkyl group (for example, methyl group, ethyl group, propyl group), an alkoxy group (for example, methoxy group, ethoxy group, propyloxy group), and an aryl group (for example, phenyl group). Group, naphthyl group), hydroxy group, halogen atom, aryloxy group (eg, phenoxy group), alkylthio group (eg, methylthio group, butylthio group), arylthio group (eg, phenylthio group), acyl group (eg, acetyl group, propionyl group, Butyryl group), sulfonyl group (eg, methylsulfonyl group, phenylsulfonyl group), acylamino group, sulfonylamino group, acyloxy group (eg, acetoxy group, benzoxy group), carboxyl group, cyano group, sulfo group and amino group. . Preferred substituents are a lower alkyl group and a lower alkoxy group.

The compounds represented by the general formula (1) are exemplified below.

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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As a method for synthesizing the compound represented by the general formula (1), OPPI Briefs 24, No. 4,48
8 (1992), US Pat. No. 5,003,097. Some of these compounds are commercially available. The amount of the compound of the general formula (1) to be used is 1 × 10 ^-7 to 1 × 10 ^-1 mol per mol of silver. Preferably, it is 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver, more preferably, 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol per mol of silver.

The compound of the present invention can be dissolved in the most common organic solvents except methanol, and acetonitrile and acetone are preferably used. Further, it can be added to the emulsion as a dispersion using an appropriate high boiling point solvent or as a solid dispersion. The compound may be added to the photographic light-sensitive material in any layer as long as it is a hydrophilic colloid layer on the side of the support on which the silver halide emulsion layer is present, such as an emulsion layer, a protective layer, and a crossover layer. It may be added to the cut (COC) layer, the undercoat layer or the intermediate layer.
Particularly preferred is an emulsion layer.

As a method for synthesizing the compound represented by the general formula (2) of the present invention, for example, Beilsteins Handb
uch der Organischen Chemi
e, Chem. Ber. Ann. Chem. J. A
m. Chem. Soc. Etc. can be referred to.

The compound represented by the general formula (2) of the present invention is
To be contained in a silver halide photographic light-sensitive material,
What is necessary is just to add to the silver halide emulsion coating solution,
Process from emulsion grain formation to coating.
You may. The addition amount was 5 × 10 5 per mol of silver halide.
^-FiveMol ~ 1 x 10^-1Mole, preferably 1 × 10 ^-Four
Mol ~ 1 x 10^-2Is a mole. Incidentally, the general formula of the present invention
The compound represented by (2) is added only to the emulsion layer.
To the hydrophilic colloid layer where the emulsion layer is present
Although it can be used, it is preferably an emulsion layer.

Next, specific examples of the compound represented by the above general formula (2) according to the present invention will be described, but the present invention is not limited thereto.

[0030]

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[0031]

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In the compound represented by the general formula (3), R
₆ is preferably an alkyl group having up to 16 carbon atoms as an alkyl group, a phenyl group as an aryl group, an imidazole, oxazole, thiazole, triazole, tetrazole, oxydiazole, thiadiazole, benzimidazole, benzoxazole as a heterocyclic group. ,
Represents benzothiazole, pyridine, pyrimidine, triazine, quinoline, quinazoline, purine. The alkyl group, the aryl group, and the heterocyclic group may be substituted with other substituents. Examples of the substituent include alkyl, aryl, halogen, cyano, nitro, hydroxy, mercapto, amino, carboxy, sulfo, and sulfamyl. , Pyridyl, propynylthio, alkylthio and the like.

The compounds represented by formula (3) are exemplified below.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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As a method for synthesizing these compounds, the methods described in JP-A-49-107537 and JP-A-58-90634 can be referred to.

In the present invention, in order to incorporate these compounds into a silver halide photographic light-sensitive material, a light-sensitive silver halide emulsion layer and / or a hydrophilic colloid layer adjacent thereto are preferably used. This is a coating solution for an emulsion layer.

The compound may be added at any time from the formation of the silver halide emulsion grains to the coating.

As the addition method, water, lower alcohol,
A method of dissolving and adding in tetrahydrofuran, acetone, ethyl acetate, dimethylformamide or a mixed solvent thereof, or a method of adding as a solid dispersion can be used.

The addition amount is preferably from 1 × 10 ⁻⁵ mol to 1 × 10 ⁻² mol, and particularly preferably from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻³ mol, per mol of silver halide.

The silver halide grains used in the present invention are tabular silver halide grains having an aspect ratio of 3 to 30. Tabular silver halide grains are crystallographically classified as twins. Twins are crystals having one or more twin planes in one grain. Classification of twin morphology in silver halide grains is based on a report by Klein and Moiser in "Photographhishhe Korrespon."
denz, Vol. 99, p. 99, and Vol. 100, p. 57. The tabular silver halide grains related to the present invention have one or two or more twin planes parallel to each other in the grains, and these twin planes are planes forming the surface of the tabular grains. Exists almost parallel to a plane having the largest area (also referred to as a main plane). The most preferable form in the present invention is a case having two parallel twin planes.

In the present invention, the aspect ratio refers to the ratio between the area-converted particle diameter and the particle thickness (aspect ratio = equivalent diameter / thickness). Here, the area-converted particle size means the diameter of a circle having an area equal to the area when the particle is projected perpendicular to the main plane. On the other hand, the volume-converted particle size is
It refers to the diameter of a sphere having the same volume as the individual silver halide grains. Grain thickness is the thickness of a grain in a direction perpendicular to the major plane and generally corresponds to the distance between the two major planes.

The average equivalent circle diameter of the tabular silver halide grains of the present invention is preferably from 0.1 to 10.0 μm, more preferably from 0.2 to 5.0 μm, and particularly preferably from 0.3 to 2.0 μm.
m is preferred. The average grain thickness of the tabular silver halide grains of the present invention is preferably from 0.01 to 0.3 μm, more preferably from 0.05 to 0.25 μm, particularly preferably from 0.07 to 0.25 μm.
0.2 μm is preferred.

The projected area and thickness of the particles for calculating the area-converted particle diameter and the volume-converted particle diameter can be obtained by the following methods.
A sample was prepared by coating a latex ball having a known particle size as an internal standard on a support and silver halide particles such that the main plane was oriented parallel to the substrate, and shadowing was performed by carbon deposition from a certain angle. Thereafter, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area and thickness of each particle are determined using an image processing device or the like. In this case, the projected area of the particle can be calculated from the projected area of the internal standard, and the thickness of the particle can be calculated from the length of the internal standard and the shadow of the particle. In the present invention, the average value of the aspect ratio, the area-converted particle size, the grain thickness, and the volume-converted particle size is arbitrarily set to 500 by using the above-mentioned replica method for the silver halide grains contained in the silver halide emulsion.
A value obtained by measuring more than one piece and calculating as an arithmetic average thereof.

In the present invention, the coefficient of variation of the volume diameter of the silver halide grains is defined as the coefficient of variation of the volume diameter = (standard deviation of volume diameter / average value of volume diameter) using the value obtained from the above measurement. ). The coefficient of variation of the silver halide grains relating to the present invention is preferably 0.2 or less, more preferably 0.10 or less.

Similarly, the coefficient of variation of the area size of silver halide grains can be determined from the above measurement. Here, the variation coefficient of the area particle size is a value defined by a variation coefficient of the area particle size = (standard deviation of the area particle size / average value of the area particle size). The variation coefficient of the area grain size of the silver halide grains related to the present invention is preferably 0.2 or less, more preferably 0.10 or less.

In the silver halide emulsion relating to the present invention, the average value of the aspect ratio (hereinafter, also simply referred to as aspect ratio) of at least 50% of the total projected area of the silver halide grains contained in the silver halide emulsion is 3. It is preferably a tabular silver halide grain having an aspect ratio of from 4 to 20 and more preferably 50% or more of the total projected area is a tabular silver halide grain having an aspect ratio of from 4 to 20.
To 15 tabular silver halide grains. Further, it is preferred that 80% or more of the total projected area of the silver halide grains contained in the silver halide emulsion is tabular silver halide grains related to the present invention.

The tabular silver halide grains related to the present invention have one or two or more twin planes parallel to each other in the grains, but 50% of the tabular silver halide grains related to the present invention. The above are preferably tabular grains having two twin planes parallel to each other in the grains, and more preferably 80% or more. These twin planes can be observed with a transmission electron microscope. The specific method is as follows. First, a silver halide emulsion is applied on a substrate so that the main plane of the contained tabular grains is oriented substantially parallel to the substrate to prepare a sample. This is continuously cut perpendicular to the substrate using a diamond cutter to obtain a continuous thin section having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the existence and position of the twin plane can be confirmed.

The composition of the silver halide grains in the present invention is preferably silver iodobromide, silver bromide, silver chlorobromide, or silver chloroiodobromide. In particular, the average silver iodide content of the silver halide emulsion is preferably 2 mol% or less, and silver iodobromide is preferred.
Further, the average silver iodide content is preferably at most 1 mol%, particularly preferably at most 0.5 mol%. The composition of the silver halide grains can be determined by a composition analysis method such as an EPMA method and an X-ray diffraction method.

The average silver iodide content of the surface phase of the silver halide grains related to the present invention is preferably 3 mol% or less, more preferably 0.1 mol% or more and 2 mol% or less. , 0.2 mol% or more and 1 mol% or less are more preferable. Here, the average silver iodide content of the surface phase of the silver halide grains is a value obtained by using the XPS method or the ISS method. For example, the surface silver iodide content by the XPS method can be obtained as follows. The sample was 1.33 × 10 ^-2 Pa
After cooling to -155 ° C. or less in the following ultra-high vacuum, MgKa is irradiated as a probe X-ray at an X-ray source current of 40 mA, and Ag3d5 / 2, Br3d, and I3d3 / 2 electrons are measured. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the composition such as the silver iodide content of the silver halide surface phase is determined from these intensity ratios.

In the silver halide emulsion relating to the present invention, the silver iodide content between silver halide grains is preferably more uniform. That is, the coefficient of variation of the silver iodide content in the silver halide emulsion is preferably 30% or less, and more preferably 20% or less. Here, the coefficient of variation is a value obtained by dividing the standard deviation of the silver iodide content by the average value of the silver iodide content and multiplying by 100, and the silver halide grains contained in the silver halide emulsion. Refers to a value obtained by arbitrarily measuring 500 or more.

Further, it is preferable to use a production method in which an aqueous solution containing a salt is appropriately extracted from the reaction solution using an ultrafiltration device. For example, it is preferable to control the average intergranular distance in the growth process of silver halide grains to 0.60 times or more and 1.00 times or less of the average intergranular distance at the start of growth, and more preferably 0.60 times to 0.80 times. It is more preferable to control as follows. Specifically, the value of the average interparticle distance is set to 3.2 μm.
m, preferably 2.8 μm or less, more preferably 0.90 μm or more and 2.0 μm or less.
It is particularly preferable to control it to m or less.

As a preparation form of the silver halide emulsion related to the present invention, a method known in the art can be appropriately applied. For example, a so-called controlled double jet method or controlled triple jet method for controlling pAg of a reaction solution at the time of forming silver halide grains can be used. In addition, a silver halide solvent can be used if necessary. Examples of useful silver halide solvents include ammonia, thioethers, and thioureas. Regarding thioethers, U.S. Pat.
No. 71,151, No. 3,790,387, No. 3,
No. 574,626 can be referred to. The method for preparing the grains is not particularly limited, and an ammonia method, a neutral method using no ammonia, an acidic method, and the like can be used.From the viewpoint of suppressing fog during silver halide grain formation, it is preferable. It is preferable to form particles in an environment where the pH (logarithm of the reciprocal of the hydrogen ion concentration) is 5.5 or less, more preferably 4.5 or less.

In the present invention, the metal ions doped into the tabular silver halide grains include Rh (rhodium), Ru (ruthenium), Re (rhenium), and Os.
(Osmium). One or more of the same or different metal complexes may be used in combination.

These metal ions are used as a single salt or a metal complex. As the simple salt, halide (chloride, bromide, etc.), nitrate, sulfate and perchlorate are preferably used, and as the metal complex, 6-coordinate, 5-coordinate, 4
A coordination or two-coordination complex can be used, and the complex may be a mononuclear complex or a polynuclear complex. The preferred content is 1 × 10 ^-10 mol to 1 × 10 ^-7 mol per mol of silver.
The molar range is preferably 5 × 10 ^-10 mol to 1 × 10
A range of ^-8 mol is more preferred.

In the present invention, the metal complex is preferably a six-coordinate complex or a complex ion represented by the following general formula.

In the formula [ML ₆ ] ^m , M is a metal ion selected from Rh, Ru, Re, and Os, L is a bridging ligand, and m is 0, -1, -2, -3 or -4. Represents Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand,
Nitrosyl, thionitrosyl and the like can be mentioned, and preferred are aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Specific examples are shown below, but the present invention is not limited to these examples. 1: [RhCl _6] ^3- 2: [RhCl ₅ (H ₂ O)] ^2- 3: [Rh (NO) ₂ Cl _4] ^- 4: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 5 : [Rh (NS) Cl _5] ^2- 6: [RuCl _6] ^3- 7: [RuBr _6] ^3- 8: [Ru (NO) Cl _5] ^2- 9: [Ru (NO) (H ₂ O ) Cl _4] ^- 10: [Ru (NS) Cl _5] ^2- 11: [RuBr ₄ (H ₂ O)] ^2- 12: [Ru (NO) CN _5] ^2- 13: [ReCl _6] ^3- 14: [Re (NO) Cl _5] ^2- 15: [Re (NO) CN _5] ^2- 16: [Re (NO) ClCN _4] ^2- 17: [Re (NO) Cl _5] ^- 18: [ _{Re (NS) Cl 4 (SeCN} ) ] ^2- 19: [OsCl _6] ^3- 20: [Os (NO) Cl _5] ^2- 21: _{[Os (NS) Cl 4 (TeCN} ) ] ^2- 22: [ Os (NS) Cl (S N) _4] ^2- These metal complexes preferably used as a salt of a complex of potassium, sodium, ammonium salts or cesium salts.

The compound providing these metal ions or complex ions is preferably added during silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation and growth , Physical aging,
It may be added at any stage before and after chemical sensitization, but it is particularly preferable to add at the stage of nucleation, growth, and physical ripening.
Further, it is preferably added at the stage of nucleation and growth.

In the addition, it may be added in several divided portions, may be added uniformly in the silver halide grains, or may be added to the silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683
As described in Japanese Patent Application Laid-Open No. H10-284, etc., the particles can be contained in the particles with a distribution.

These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). Or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or a silver salt solution and a halide solution are simultaneously mixed. A method of preparing silver halide grains by a method of simultaneous mixing of three liquids, a method of charging a required amount of an aqueous solution of a metal compound into a reaction vessel during grain formation, or a method of mixing silver halides. There is a method in which another silver halide grain doped with metal ions or complex ions in advance during the preparation is added and dissolved. In particular, an aqueous solution of a metal compound or a metal compound and NaC
1, a method of adding an aqueous solution in which KCl is dissolved together to a water-soluble halide solution is preferable. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

The silver halide emulsion relating to the present invention contains a dispersion medium together with silver halide grains. The dispersion medium is a compound having a protective colloid property for silver halide grains, and is preferably present from the nucleation step to the end of grain growth. Dispersion media that can be preferably used in the present invention include gelatin and protective colloid polymers. As gelatin, usually, alkali-treated gelatin or acid-treated gelatin having a molecular weight of about 100,000, or a molecular weight of 5,000 to
About 30,000 low molecular gelatin or oxidized gelatin can be preferably used. In particular, at the time of nucleation, oxidized gelatin, low molecular weight gelatin, and oxidized low molecular weight gelatin can be suitably used.

In the silver halide emulsion of the present invention, Research Disclosure No. 308119
(Hereinafter abbreviated as RD308119) can be used.

The silver halide grains used in the present invention include
Chemical sensitization can be performed by a method commonly used.
come. Chemical ripening, that is, the conditions of the chemical sensitization process, for example
There are no particular restrictions on pH, pAg, temperature, time, etc.
Can be performed under conditions commonly used in the industry.
You. Chemical sensitization involves the use of sulfur-containing compounds that can react with silver ions.
Sulfur sensitization method using compound and active gelatin, selenium compound
Selenium sensitization using tellurium sensitization using tellurium compound
Sensitization method, reduction sensitization method using reducing substances, gold and other precious metals
There are noble metal sensitization methods that use metals, and these methods are simply
They may be used alone or in combination. Above all, selenium increased
Sensitization, tellurium sensitization, reduction sensitization, etc. are preferably used.
In particular, a selenium sensitization method is preferably used. The above selection
Colloidal selenium gold is useful as a sensitizer.
Genus, isoselenocyanates (for example, allyl isose
Lenocyanates), selenoureas (eg, N, N-
Dimethylselenourea, N, N, N'-triethylseleno
Urea, etc.), selenoketones (eg, selenoacetone,
Selenoacetophenone, etc.), selenoamides (for example,
Selenoacetamide, N, N-dimethylselenobenzure
Mide), selenocarboxylic acids and selenoesters
(For example, 2-selenopropionic acid, methyl-3-sele
Nobtilate etc.), selenophosphates (for example,
Tri-p-triselenophosphate, etc.), selenide
(Diethyl selenide, diethyl diselenide,
Phenylphosphine selenide).
come. Particularly preferred selenium sensitizers are selenoureas and selenium sensitizers.
Noamides and selenium ketones. Selenium sensitizer
The amount of selenium compound to be used, silver halide grains,
In general, it depends on the conditions of chemical ripening.
10 per mole^-8Mole-10 ^-FourIt is better to use about mole
No. The method of addition depends on the properties of the selenium compound used.
Depending on the water or methanol, ethanol, ethyl acetate
Dissolved in a single or mixed solvent of organic solvents such as
Or a method of premixing with a gelatin solution and adding
Or disclosed in Japanese Unexamined Patent Publication No.
Method, that is, a mixed solution with an organic solvent-soluble polymer
May be added in the form of an emulsified dispersion.

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

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

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

In the present invention, a more useful sensitizing dye is a trimethine cyanine dye which gives spectral sensitivity to green light, and is described in detail in JP-A-7-28184, pp. 2-12. Oxacarbocyanine dyes or benzimidazolocarbocyanine dyes.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. In addition, the emulsion layer may contain, in addition to the sensitizing dye, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect. For example, a substituted aminostilbene compound which is a nitrogen-containing heterocyclic nucleus group (for example, US Pat.
Nos. 933,390 and 3,635,721), formaldehyde condensates of aromatic organic acids (for example, those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like. Is also good.

US Pat. Nos. 3,615,613;
615,641, 3,617,295, 3,6
The combinations described in JP-A-35,721 and the like are particularly useful. The sensitizing dye may be added during or during each step of nucleation, growth, desalting, and chemical sensitization, or after chemical sensitization.

Next, the layer constitution in the silver halide photographic light-sensitive material of the present invention will be described. The silver halide photographic material of the present invention is a silver halide photographic material having at least one photosensitive silver halide emulsion layer on one surface of a support and having a backing layer on the opposite surface. A transparent plastic base is used as the support. For example, cellulose triacetate, polyester (PET, PE
N or the like) or polystyrene (SPS or the like). For photosensitive materials for medical diagnosis, which is the object of the present invention, 160-180
A PET base with a thickness of μm is preferred. The support may be colored as long as the transparency is maintained.
Blue coloring of about 0.2 is preferable because eye fatigue in observation of a transmission image by sharksten can be reduced. The support is usually subjected to a subbing treatment in order to provide adhesion between the constituent layer coated on the support and the support.

The constituent layers on the side having the photosensitive silver halide emulsion layer include a conductive layer (antistatic layer), an intermediate layer, a filter dye layer, a protective layer and the like in addition to the photosensitive silver halide emulsion layer. Is also good. As the thickness of the protective layer when dried,
0.4 to 1.0 μm is preferred, and more preferably 0.5 to 0.8
μm is preferred. As an additive to be added to the protective layer, those described in Research Disclosure (RD) described later can be used.

The light-sensitive silver halide emulsion layer may be a single layer or a multi-layer, but one of the objects of the present invention is to provide a mammographic light-sensitive material having a multilayer structure in order to obtain a high contrast. It is preferred that the sensitivity be lower than the emulsion sensitivity of the lower layer. The contrast is preferably in the range of 3.6 or more and 4.7 or less. In this case, the sensitivity of the lower emulsion is 0.1 to 0.1 as a relative logarithmic sensitivity to the adjacent upper emulsion.
0.4 preferably high sensitivity, more preferably 0.15
It is preferably 0.3. The dry film thickness of the photosensitive silver halide emulsion layer is preferably from 2 to 4.6 μm as a total of all the photosensitive silver halide emulsion layers, and the ratio of the film thickness between the respective emulsion layers may be arbitrary. As additives to be added to the silver halide emulsion layer, those described in Research Disclosure (RD) described later can be used.

The total thickness of the photosensitive silver halide emulsion layer when dried is preferably 5 μm or less, more preferably 3.5 μm or less.

The layer structure on the backing layer side includes an antihalation dye layer, a protective layer, and the like. In addition to these layers, a conductive layer (antistatic layer), an intermediate layer, and other dye layers may be included. . The antihalation dye layer preferably contains the aforementioned dye in a solid dispersion state. As the binder, gelatin, polymer latex and those described in RD below can be used. The total thickness of the backing layer when dried is preferably 5 μm or less, and more preferably 3.5 μm or less.

As the additives to be added to these layers, those described in Research Disclosure (RD) described later can be used.

In the photographic light-sensitive material of the present invention, an appropriate amount of a hardener is added in advance in the coating step of the photographic material so as to be suitable for rapid processing, and the swelling ratio in the development-fixing-washing step is adjusted. Thus, it is preferable to reduce the water content in the photosensitive material before the start of drying. The silver halide light-sensitive material of the present invention preferably has a swelling ratio of 100 to 200% during the development processing. The swelling ratio is obtained by calculating the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, dividing the difference by the film thickness before processing and multiplying by 100.

The silver halide light-sensitive material according to the present invention includes:
Various photographic additives can be used. Known additives include, for example, Research Disclosure No.
No. 17643 (December 1978); 18716
(November 1979) and the same No. 308119 (19
(December 1989). The types of compounds and the locations described in these three research disclosures are listed below.

Additives RD-17643 RD-18716 RD-308119 page classification page classification page classification chemical sensitizer 23 III 648 upper right 996 III sensitizing dye 23 IV 648-649 996-8 IVA desensitizing dye 23 IV 998 IVB dye 25-6 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right Fogging inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 26-7 XI 650 right 1005-6 XI Antistatic agent 27 XII 650 right 1006-7 XIII Plasticizer 27 XII 650 right 1006 XII sliding agent 27 XII matting agent 28 XVI 650 right 1008-9 XVI binder 26 XXII 1003-4 IX Support Body 28 XVII 1009 XVII Preferred developer for developing the light-sensitive material of the present invention JP-A-4-15641, JP-A-4-4-1 as a developing agent
No. 6841 and the like, for example, dihydroxybenzene, for example, hydroquinone, paraaminophenols, for example, p-
Examples of 3-pyrazolidones such as aminophenol, N-methyl-p-aminophenol and 2,4-diaminophenol include, for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3 -Pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone, and the compound of the above general formula (4) can be used.

In the general formula (4), R ₈ and R ₉ are each independently a hydroxy group, a mercapto group or an amino group (an amino group is an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl,
n-butyl, hydroxyethyl group and the like as substituents), acylamino group (eg, acetylamino, benzoylamino group, etc.), alkylsulfonylamino group (eg, methanesulfonylamino group, etc.), arylsulfonylamino group (eg, A benzenesulfonylamino group, a p-toluenesulfonylamino group, an alkoxycarbonylamino group (eg, a methoxycarbonylamino group), and an alkylthio group (eg, a methylthio, ethylthio group).

Preferable examples of R ₈ and R ₉ include a hydroxy group, an amino group, an alkylsulfonylamino group and an arylsulfonylamino group. Z is preferably composed of a carbon atom, an oxygen atom or a nitrogen atom, and forms a 5- to 6-membered ring together with the two vinyl carbons and the carbonyl carbon substituted by R ₈ and R ₉ ; preferable.

Specific examples of Z include -O-, -C
_{(R 10) (R 11)} -, - C (R 12), - C (= O) -,
-N (R ₁₃₎ -, - formed by combining the N =. However, R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy group, a carboxy group, or a sulfo group can be given as a substituent). Represents an aryl group having 6 to 15 carbon atoms which may be substituted (an alkyl group, a halogen atom, a hydroxy group, a carboxy group or a sulfo group can be mentioned as a substituent), a hydroxy group or a carboxy group. This 5
A saturated or unsaturated condensed ring may be formed in the 6-membered ring. Examples of the 5- to 6-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. Preferred examples of the 5- or 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring and a uracil ring.

Hereinafter, specific examples of the compound represented by formula (4) of the present invention are shown, but the present invention is not limited to these.

[0089]

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[0090]

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[0091]

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Preferred is a developer containing substantially no hydroquinones and containing the compound of the general formula (4). In the present invention, "substantially not containing" means 0.1 g /
It indicates that the concentration is not more than L. It is particularly preferable to use a combination of the compound represented by formula (4) and 3-pyrazolidones.

The preservative may include sulfites, for example, potassium sulfite, sodium sulfite, reductones, for example, piperidinohexose redataton, etc.
These are preferably used in an amount of 0.2 to 1 mol / L, more preferably 0.3 to 0.6 mol / L. Also, addition of a large amount of ascorbic acids leads to processing stability.

As the alkaline agent, sodium hydroxide,
PH adjusters such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate and potassium tertiary phosphate are included. Further, buffers such as borate described in JP-A-61-28708 and saccharose, acetoxime, 5-sulfosalicylic acid, phosphate and carbonate described in JP-A-60-93439 may be used. The content of these agents raises the pH of the developer to 8.5 to 11.5, preferably to pH 9.
Choose to be 5-10.5.

The dissolution aid may contain diethylene glycol, triethylene glycols and esters thereof, and the sensitizer may contain, for example, a development accelerator such as a quaternary ammonium salt, a surfactant and the like.

The silver sludge inhibitor is described in JP-A-56-1981.
No. 106244, silver stain inhibitor, JP-A-3-518
The sulfides and disulfide compounds described in JP-A No. 44, and the cysteine derivatives or triazine compounds described in JP-A-5-289255 are preferably used.

As organic inhibitors, azole organic antifoggants such as indazole, imidazole, benzimidazole, triazole, benztriazole, tetrazole, thiadiazole, mercaptoazole (eg, 1-phenyl-5-mercapto) Although a tetrazole) compound or the like is used, it is particularly preferable to use nitroindazole (5-nitroindazole, 6-nitroindazole). The preferable addition amount of nitroindazole is 0.002 to 0.2 g / L.
And particularly preferably 0.01 to 0.1 g / L.

As the inorganic inhibitor, sodium bromide, potassium bromide, potassium iodide and the like can be contained. in particular,
The bromine ion concentration is preferably 10 g / L or more in terms of potassium bromide.

In addition, L. F. A. Mason, "Photographic Processing Chemistry", Focal Press (1966), pages 226-229, U.S. Pat. Nos. 2,193,015 and 2,592,364.
And those described in JP-A-48-64933. As a chelating agent for concealing calcium ions mixed in tap water used in the treatment liquid, a chelating agent having a chelate stabilization constant with iron of 8 or more described in JP-A-1-193853 as an organic chelating agent is preferably used. Can be Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate.

As the developing hardener, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used.

The development processing method of the present invention includes a compound represented by the general formula (4) and nitroindazole which is substantially free of hydroquinones and whose bromine ion concentration is converted to potassium bromide. It is particularly preferable to use a developer having a concentration of 10 g / L or more, and a high-gradation and stable image which is the object of the present invention can be obtained.

The replenishment of the developing solution during the development processing of the light-sensitive material of the present invention is preferably 50 to 150 ml, more preferably 65 to 130 ml, per m ² of the light-sensitive material.

Preferred fixing solutions can include fixing materials commonly used in the art.

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

The pH of the fixing solution is 3.8 or more, preferably 4.2 or more. In the present invention, the fixing solution may form an acidic film. In this case, an aluminum compound is preferably used as a hardener. For example, it is preferable to add in the form of aluminum sulfate, aluminum chloride, potash and the like.

The fixing solution may further contain a preservative such as sulfite or bisulfite, a pH buffer such as acetic acid or boric acid, a mineral acid (sulfuric acid, nitric acid) or an organic acid (citric acid, oxalic acid, etc.), if desired. Various acids such as malic acid), hydrochloric acid and the like, pH adjusters such as metal hydroxides (potassium hydroxide and sodium hydroxide), and chelating agents having water softening ability can be contained.

As the fixing accelerator, for example, Japanese Patent Publication No.
No. 35754, No. 58-122535, No. 58-12
Thiourea derivatives described in US Pat.
Thioether described in US Pat. No. 6,459.

The replenishment of the fixing solution during the fixing processing of the light-sensitive material of the present invention is preferably from 50 to 150 ml, more preferably from 65 to 130 ml, per m ² of the light-sensitive material.

As the treatment method of the present invention, a method using a solid treating agent is preferable. To solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is sprayed on the surface of the temporarily molded photographic processing agent. Any means such as forming a coating layer can be adopted (see JP-A-4-29136 and JP-A-4-29136).
-85535, 4-85536, 4-8553
No. 3, 4-85534 and 4-172341).

A preferred tablet production method is a method of granulating a powdery solid processing agent and then performing 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 known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing 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.

The particle size distribution is preferably such that 60% or more of the granulated particles have 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 pressurizing and compression can take any shape, but from the viewpoint of productivity, handleability, or the problem of dust when used on the user side, a cylindrical, so-called tablet is used. preferable.

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

The method for producing a tablet processing agent is described in, for example, JP-A-51-61837, JP-A-54-155038, and JP-A-52-55038.
-88025, British Patent 1,213,808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-109042 and 2-1.
No. 09043, No. 3-39735 and No. 3-3993
It can be produced by a general method described in the specification such as No. 9. Furthermore, powder processing agents are described, for example, in JP-A-54-13.
3332, British Patent Nos. 725,892 and 729,
No. 862 and German Patent No. 3,733,861 and the like.

[0115] The bulk density of the solid processing agent, and in view of its solubility, if a tablet from the viewpoint of the effect of the object of the present invention 1.0g / cm ³ ~2.5g / cm ³ is preferably 1. 0g
/ Cm ³ in terms of the strength of the solid obtained,
If it is less than 2.5 g / cm ³ , it is more preferable in terms of solubility of the obtained solid. When the solid processing agent is granules or powder, the bulk density is preferably 0.40 to 0.95 g / cm ³ .

The automatic developing machine used in the present invention is preferably a known roller-type automatic developing machine. When processing the silver halide photographic light-sensitive material of the present invention, the total processing time (dry to dry) is 1 using an automatic processor.
The treatment is preferably performed in 0 to 45 seconds, and more preferably in 15 to 30 seconds. Here, the time from when the tip of the photosensitive material to be processed is immersed in the developing tank liquid of the automatic developing machine to when it comes into contact with the fixing tank liquid in the next process is referred to as “development time”. "Fixing time" refers to the time until contact with the washing tank liquid (stabilizing liquid)
When the immersion time in the rinsing tank liquid is referred to as “rinsing time” and the time in the drying zone of the automatic processor is referred to as “drying time”, the developing time is 3 to 15 seconds (further 3 to 10 seconds).
Developing temperature 25-50 ° C (further 30-40 ° C), fixing time 2-12 seconds (further 2-10 seconds), fixing temperature 20-5
0 ° C (further 30-40 ° C), water washing (stabilization) time 2 ~
15 seconds (further 2 to 8 seconds), water washing (stabilization) temperature 0 to 5
0 ° C (further 15 to 40 ° C), drying time 3 to 12 seconds (further 3 to 8 seconds), drying temperature 35 to 100 ° C (further 40 ° C).
-80 ° C) is preferred. The silver halide photographic light-sensitive material of the present invention is subjected to development, fixing and washing with water (or stabilization), dried with a squeeze roller and then dried.

As the X-ray generator in the image forming method of the present invention, a commercially available X-ray generator can be used. In particular, as an X-ray generator for mammography, a device having an X-ray generating tube having a voltage sensitivity of 40 kVp or less is commercially available. As a dedicated device for mammography, molybdenum (Mo) is used as the anode of the X-ray generating tube, and by adding a Mo filter, continuous X-rays of 20 KVp or more that cause a decrease in contrast due to scattering are removed.
Devices that generate X-rays that are close to a single color including X-rays have become mainstream. Also, there is known an apparatus in which a Rh filter is combined with a rhodium (Rh) anode or a tungsten (W) anode in order to obtain contrast in a breast with a high X-ray absorption and a high breast density or a thick breast. The focal spot size of the anode tends to be miniaturized, and an apparatus having a diameter of 0.1 to 0.3 mm is generally used.

Used for the X-ray fluorescent intensifying screen according to the present invention
Preferred phosphors include tungstate phosphors
(CaWO_Four, MgWO_Four, CaWO_Four: Pb, etc.)
Rb-activated rare earth oxysulfide phosphor [Y_TwoO_TwoS: T
b, Gd_TwoO_TwoS: Tb, La_TwoO_TwoS: Tb, (Y, G
d)_TwoO_TwoS: Tb, Tm, etc.], terbium-activated rare earth phosphorus
Phosphate-based phosphor (YPO_Four: Tb, GdPO_Four: Tb, La
PO_Four: Tb, etc.), terbium-activated rare earth oxyhalogen
Phosphors (LaOBr: Tb, LaOBr: T
b. Tm, LaOCl: Tb, LaOCl: Tb. Tm
GdOBr: Tb, GdOCr: Tb, etc.)
Active rare earth oxyhalide phosphor (LaOBr: T
m, LaOCl: Tm, etc.), barium sulfate-based phosphor [B
aSO_Four: Pb, BaSO_Four: Eu²⁺, (Ba, Sr) S
O_Four: Eu²⁺Etc.] divalent eurobium activated alkaline earth
Metal phosphate phosphors [Ba_Three(PO_Four)_Two: Eu²⁺,
(Ba, Sr)_Three, (PO_Four)_Two: Eu²⁺Etc.)
-Activated alkaline earth metal fluoride halide
Optical body [BaFCl: Eu²⁺, BaFBr: Eu²⁺, Ba
FCl: Eu²⁺. Tb, BaFBr: Eu²⁺. Tb, B
aF_Two, BaCl_Two, XBaSO _Four, KCl: Eu²⁺,
(Ba, Mg) F_Two, BaCl_Two, KCl: Eu²⁺etc〕,
Iodide phosphors (CsI: Na, CsI: Tl, Na
I, KI: Tl, etc.) sulfide-based phosphor [ZnS: Ag,
(Zn, Cd) S: Ag, (Zn, Cd) S: Cu,
(Zn, Cd) S: Cu, Al, etc.], hafnium phosphate-based
Phosphor (HfP_TwoO₇: Cu etc.). But book
The phosphor used in the present invention is not limited to these.
No.

Of these, terbium-activated gadolinium oxysulfide (Gd ₂ O ₂ S: Tb) is particularly preferred as the phosphor.

The average particle diameter of each phosphor layer constituting each phosphor layer is represented by R, and the particle diameter distribution is represented by σ.
It is preferable that each layer satisfy the relationship of 0 <σ / R ≦ 0.5. Preferably, 0 <
It is desirable to satisfy the relationship of σ / R ≦ 0.3, and more preferably to satisfy the relationship of 0 <σ / R ≦ 0.15 in each layer. Here, the average particle size R is the number average, the particle size distribution σ
Indicates standard deviation.

The filling rate of the phosphor in the phosphor layer of the X-ray fluorescent intensifying screen according to the present invention is 68% or more, preferably 70% or more, more preferably 72% or more.
As a method of increasing the filling rate, a method of using a thermoplastic elastomer as a binder and performing a compression treatment to reduce the porosity in the phosphor layer is known. The thickness of the phosphor layer is 135
It is not less than μm, but preferably not less than 150 μm and not more than 250 μm.

It is preferable that the X-ray fluorescent intensifying screen of the present invention is filled with a phosphor in a gradient particle size structure. In particular, it is preferable to apply phosphor particles having a large particle diameter to the surface protective layer side and to apply phosphor particles having a small particle diameter to the support side. Those with a particle size of 10 to 30 μm
Is preferable.

The X-ray fluorescent intensifying screen used in the combination of the present invention has an X-ray absorption of 45% or more, preferably 50% or more, by increasing the filling rate of the phosphor particles. The X-ray absorption amount is obtained as follows. That is, the intrinsic filtration is 2.2 m of aluminum with three-phase power supply.
X-rays generated from a tungsten target operated at 80 kVp from an X-ray generator equivalent to m are transmitted through an aluminum plate having a thickness of 3 mm and a purity of 99% or more, and fixed at a position 200 cm from the tungsten anode of the target tube. The X-ray fluorescence intensifying screen was reached, and then measured at 50 cm from the phosphor layer of the X-ray fluorescence intensifying screen using an ionizing dosimeter to determine the amount of X-ray absorption. As a reference, the X-ray dose at the above measurement position measured without passing through the fluorescent intensifying screen was used.

Preferred binders used in the X-ray fluorescent intensifying screen according to the present invention include thermoplastic elastomers. Specifically, polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, ethylene vinyl acetate, polyvinyl chloride, natural rubber,
At least one type of thermoplastic elastomer selected from the group consisting of fluororubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber and silicone rubber is exemplified.

[0125]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these embodiments.

Example 1 All the emulsions shown below were prepared in a reaction vessel having a volume of 32 L. As an ultrafiltration unit, Asahi Kasei SIP-1013, and as a circulating pump, DAIDOR®
otory Pump was used. The volume of the emulsion circulation part in the ultrafiltration step was 1.2 L, and the emulsion was circulated at a constant flow rate of 15 L / min. Thus, the residence time of the reactant solution was 4.8 seconds, and the volume of the emulsion circulation portion of the ultrafiltration step was 3.8% of the volume of the reaction vessel. The control of the distance between particles in the particle growth process was performed by appropriately controlling the permeation flux in the ultrafiltration step. Specifically, the adjustment is performed by adjusting the flow control valve 19 in FIG.
The reaction solution in the reaction vessel is circulated to the ultrafiltration device and concentrated over the entire area of the particle growth step-1 and the particle growth step-2 so that the average distance between the particles at the start of the particle growth step-1 is maintained. Was carried out.

(Em1-1 to Em1-5: Preparation of Lower Layer Emulsion) [Nucleation Step] The following gelatin solution B-10 in a reaction vessel
1 was maintained at 30 ° C., and the pH was adjusted to 1.96 with 1 mol / L sulfuric acid while stirring at 450 rpm using the mixing and stirring apparatus of FIG. Thereafter, the S-101 solution and the X-101 solution were 5.0 m long using a double jet method.
Nucleation was performed by addition at a flow rate of 1 / sec.

(B-101) Low molecular weight gelatin (average molecular weight: 20,000) 32.4 g Potassium bromide 9.92 g H ₂ O 12938.0 ml (S-101) Silver nitrate 50.43 g H ₂ O 225.9 ml (X- 101) 35.33 g of potassium bromide 224.7 ml of H ₂ O [Aging step] After the completion of the above addition, the following G-101 solution was added, and the temperature was raised to 60 ° C. over 30 minutes. After heating, 60
The stirring was maintained for 20 minutes while maintaining the temperature. Subsequently, the pH was adjusted to 9.5 by adding a 28% aqueous ammonia solution, and the mixture was maintained for 7 minutes. A 1 mol / L nitric acid aqueous solution was added thereto and the pH was adjusted.
Was adjusted to 5.8. During this time, the silver potential of the solution (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled at 14 mV using a 1N potassium bromide solution.

(G-101) Alkali-treated inert gelatin (average molecular weight 100,000) 139.1 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n 4.64 ml of a 10% by mass methanol solution of H (m + n = 9.77) [compound A] 3266.0 ml of H ₂ O [particle growth step-1] After completion of the ripening, the S-102 solution was subsequently prepared by using a double jet method. And X-102 solution while accelerating the flow rate (the ratio of the addition flow rate at the end to the addition at the start is about 12 times)
Added in 38 minutes. After completion of the addition, the G-102 solution was added, and the stirring rotation speed was adjusted to 550 rpm. Then, the S-103 solution and the X-103 solution were successively accelerated while increasing the flow rates (the addition flow rates at the end and at the start). (Roughly twice the ratio) was added in 40 minutes. During this time, the silver potential of the solution was controlled at 14 mV using a 1 mol / L potassium bromide solution.

(S-102) Silver nitrate 639.8 g H ₂ O 2866.2 ml (X-102) Potassium bromide 448.3 g H ₂ O 2850.7 ml (G-102) Alkali-treated inert gelatin (average molecular weight 100,000) ) 203.4 g the 10 wt% methanol [compound a] solution _{6.20ml H 2 O 1867.0ml (S-} 103) Silver nitrate _{989.8g H 2 O 1437.2ml (X-} 103) potassium bromide 679.6g 9.5 g of potassium iodide 1412.0 ml of H ₂ O [Grain growth step-2] After the completion of the addition, the temperature of the solution in the reaction vessel was lowered to 40 ° C. over 20 minutes. afterwards,
After adjusting the silver potential in the reaction vessel to −18 mV using a 3.5 mol / L aqueous potassium bromide solution, the S-104 solution and the X-104 solution were accelerated in flow rate (at the end and at the start). (The ratio of the addition flow rate was 1.2 times).

[0131] Over the entire area of the (S-104) Silver nitrate _{672.0g H 2 O 975.8ml (X-} 104) Potassium bromide 470.8g H ₂ O 959.4ml grain growth step -1 and particle growth step-2, The reaction solution in the reaction vessel was circulated to the ultrafiltration device to carry out concentration, so that the average interparticle distance at the start of the particle growth step 1 was maintained.

After completion of the growth, desalting and washing are carried out according to a conventional method, and gelatin is added and dispersed well.
H was adjusted to 5.8 and pAg to 8.1. The resulting emulsion had an average grain thickness of 0.18 μm and an average grain diameter of 1.13.
The particles were hexagonal tabular grains having a size of μm, an average aspect ratio of 6.3, and a coefficient of variation in volume particle size of 0.08. This emulsion was
It was set to -1.

In the same manner as in Em1-1, except that the metal compounds shown in Table 1 were added to the potassium bromide solution X-104 per mole of the silver halide in the finished emulsion, in the same manner as in Em1-1.
Em1-2 to Em1-5 were obtained. The average particle thickness, the average particle diameter, the average aspect ratio, and the variation coefficient of the volume particle diameter were all the same as Em1-1.

(Em2-1 to Em2-5: Preparation of Upper Layer Emulsion) Em2-1 was prepared using the same apparatus and method as Em1-1 as follows.

[Nucleation Step] While maintaining the following gelatin solution B-201 in the reaction vessel at 30 ° C. and stirring at 450 rpm using the mixing and stirring apparatus of FIG. The pH was adjusted to 1.96 with sulfuric acid. Then, the S-201 liquid and X-201 were prepared using the double jet method.
The solution was added at a flow rate of 5.0 ml / sec to perform nucleation.

(B-201) Low molecular weight gelatin (average molecular weight: 20,000) 32.4 g Potassium bromide 9.92 g H ₂ O 12938.0 ml (S-201) Silver nitrate 50.43 g H ₂ O 225.9 ml (X- 201) Potassium bromide 35.33 g H ₂ O 224.7 ml [Aging step] After the above addition was completed, the following G-201 solution was added, and the temperature was raised to 60 ° C. over 30 minutes. After heating, 60
The stirring was maintained for 20 minutes while maintaining the temperature. Subsequently, the pH was adjusted to 9.5 by adding a 28% aqueous ammonia solution, and the mixture was maintained for 7 minutes. A 1 mol / L nitric acid aqueous solution was added thereto and the pH was adjusted.
Was adjusted to 5.8. During this time, the silver potential of the solution (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled at 14 mV using a 1 mol / L potassium bromide solution.

(G-201) Alkali-treated inert gelatin (average molecular weight 100,000) 139.1 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n 4.64 ml of a 10% by mass methanol solution of H (m + n = 9.77) 3266.0 ml of H ₂ O [Particle growing step-1] After completion of ripening, the S-202 solution and X-202 were subsequently subjected to double jet method. While accelerating the flow rate of the liquid (the ratio of the addition flow rate at the end to the start is about 12 times)
Added in 38 minutes. After the addition was completed, the G-202 solution was added and the stirring speed was adjusted to 550 rpm, and then the S-203 solution and the X-203 solution were accelerated while increasing the flow rates (the addition flow rates at the end and at the start). (The ratio is about 1.4 times). During this time, the silver potential of the solution was controlled at 19 mV using a 1 mol / L potassium bromide solution.

(S-202) Silver nitrate 639.8 g H ₂ O 2866.2 ml (X-202) Potassium bromide 448.3 g H ₂ O 2850.7 ml (G-202) Alkali-treated inert gelatin (average molecular weight 100,000) 203.4 g 10% by mass methanol solution of the [Compound A] 6.20 ml H ₂ O 1867.0 ml (S-203) silver nitrate 389.8 g H ₂ O 566 ml (X-203) potassium bromide 267.6 g iodide 5.6 g of potassium 566 ml of H ₂ O [Particle growth step-2] After the addition was completed, the temperature of the solution in the reaction vessel was lowered to 40 ° C over 20 minutes. afterwards,
After adjusting the silver potential in the reaction vessel to −18 mV using a 3.5 mol / L aqueous solution of potassium bromide, the S-204 solution and the X-204 solution were accelerated while increasing the flow rates (at the end and at the start). (The ratio of the addition flow rate is 1.1 times).

(S-204) Silver nitrate 308 g H ₂ O 447 ml (X-204) Potassium bromide 215.8 g H ₂ O 439.7 ml The grain growth step is performed over the entire area of the grain growth step-1 and the grain growth step-2. The reaction solution in the reaction vessel was circulated to the ultrafiltration device so as to maintain the average interparticle distance at the start of 1 and concentration was performed.

After completion of the growth, desalting and washing are carried out according to a conventional method, and gelatin is added and dispersed well.
H was adjusted to 5.8 and pAg to 8.1. The resulting emulsion had an average grain thickness of 0.16 μm and an average grain diameter of 0.92
The particles were hexagonal tabular grains having a size of μm, an average aspect ratio of 5.8, and a coefficient of variation in volume particle size of 0.09. Em2
It was set to -1.

E-2 was prepared in the same manner as in Em2-1 except that the metal compound shown in Table 1 was added to the potassium bromide solution X-204 per mole of the silver halide in the finished emulsion.
m2-2 to Em2-5 were obtained. The average particle thickness, average particle diameter, average aspect ratio, and variation coefficient of volume particle diameter were all the same as Em2-1.

[0142]

[Table 1]

(Chemical sensitization and spectral sensitization)
After the emulsions of -1 to 1-5 and Em2-1 to 2-5 were heated to 60 ° C., 10 minutes after the addition of the spectral sensitizing dye (the following compound and amount) as a dispersion of solid fine particles, adenine was added. ,
A mixed aqueous solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate and a dispersion of triphenylphosphine selenide were added, and 30 minutes later, silver iodide fine particles were added, followed by ripening for a total of 2 hours. At the end of ripening, 4-hydroxy-6-methyl-1,3,3a,
A predetermined amount of 7-tetrazaindene was added. The amount added per mole of silver halide is shown below.

5,5-dichloro-9-ethyl-3,3'-di- (sulfopropyl) -oxacarbocyanine sodium salt anhydrous 300 mg 5,5-di- (butoxycarbonyl) -1,1'-diethyl -3,3'-Di- (4-sulfobutyl) -benzimidazolocarbocyanine sodium salt anhydride 30 mg adenine 10 mg ammonium thiocyanate 70 mg chloroauric acid 10 mg sodium thiosulfate 5.0 mg triphenylphosphine selenide 1.0 mg iodine Fine silver halide particles 0.3 mmol 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 500 mg Gelatin 40 g A solid fine particle dispersion of a spectral sensitizing dye was prepared by a known method.

That is, the predetermined amount of the spectral sensitizing dye was previously
It was obtained by adding to water adjusted to ° C. and stirring with a high-speed stirring (dissolver) at 3,500 rpm for 30 to 120 minutes.

The dispersion of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., and the mixture was stirred and completely dissolved. 3.8 kg of photographic gelatin on the other hand
Was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at a dispersion blade peripheral speed of 40 m / sec at 50 ° C. for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was reduced to 0.3.
Ethyl acetate was removed while stirring until the amount became less than wt%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. A part of the dispersion thus obtained was fractionated and used in the above Examples.

(Preparation of Emulsion Layer Coating Solution) The following various additives were added to each of the above-obtained emulsions (per mole of silver halide).

1,1-Dimethylol-1-bromo-1-nitromethane 7 mg t-butyl-catechol 130 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g sodium polystyrenesulfonate 2.0 g trimethylolpropane 7.0 g nitrophenyl- Triphenyl-phosphonium chloride 20 mg Sodium 1,3-dihydroxybenzene-4-sulfonate 400 mg 2-Sodium 2-mercaptobenzimidazole-5-sulfonate 10 mg nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH ) ₂ 650 mg Compound of general formula (1) (described in Tables 2 and 3) Table listed amount Compound of general formula (2) (described in Tables 2 and 3) Table listed amount Compound of general formula (3) (Tables 2 and 3) 3) Amount shown in table (Preparation of coating solution for protective layer on emulsion layer side) Tin 0.9 g / m ² Matting agent (PMMA with an average particle size of 3 μm) 30 mg / m ² Hardening agent (CH ₂ = CHSO ₂ CH ₂ CONHCH ₂ −) ₂ Adjust the amount of addition so that the swelling ratio is 150% Compound (S-1) 7 mg / m ² Compound (S-2) 40 mg / m ² Compound (S-3) 5 mg / m ² Backing layer (Preparation of antihalation dye layer solution) Gelatin 2.1 g / m ² dye ( D-1) 35 mg / m ² dye (D-2) 35 mg / m ² dye (D-3) 35 mg / m ² (Preparation of coating solution for protective layer) Gelatin 0.9 g / m ² Matting agent (average particle size 5 μm) PMMA) 100 mg / m ² Compound (S-1) 7 mg / m ² Compound (S-2) 50 mg / m ² Compound (S-3) 6 mg / m ² Hardener (CH ₂ ＣＨCHSO ₂ CH ₂ CONHCH ₂₎ −) ₂ Addition amount so that the swelling ratio is 150% Preparation of Solid Fine Particle Dispersion Dye was prepared as follows. That is, water and the surfactant alkanol X are placed in a ball mill container.
C (manufactured by DuPont) was added, dye (AH) was added, zirconium oxide beads were added, the container was sealed, and the mixture was dispersed in a ball mill for 4 days.

[0149]

[Table 2]

[0150]

[Table 3]

[0151]

Embedded image

(Coating) Using these coating solutions, a support was prepared.
On one side of the emulsion, the silver content was 1.5 g / m 2 ^Two, Under the emulsion
1.5 g / m of layer^TwoEmulsion protective layer gelatin amount 0.9g / m^Two
Also on the other side, anti-halation
Dye layer, intermediate layer, protective layer, two slide hopper type
Using a coater, glycidyl methacrylate 50 mass
%, Methyl acrylate 10% by mass, butyl methacrylate
40% by mass of a copolymer composed of three types of monomers.
Copolymer content obtained by diluting to a concentration of 10% by mass
175μm-thick blue color which was applied and dried using the sprinkled liquid as a subbing liquid
Each side of the colored polyethylene terephthalate support
Coating at a speed of 120m for 2 minutes and drying in 2 minutes and 20 seconds
After drying, a sample was prepared. In addition, only the upper emulsion layer and the lower emulsion layer
A sample was prepared by coating only the same. However, in this case
In this case, the compounds of the general formulas (1) to (3) were not added.
Using a sample containing only the upper emulsion and a sample containing only the lower emulsion,
Table 1 shows the results obtained by determining the difference in sensitivity of the agents by the method described below.
The sensitivity is expressed as a relative sensitivity when Em1-1 is set to 100.
Was.

<Preparation of solid developer> [Granulated product (A)] 1050 g of sodium metabisulfite,
450 g of 1-phenyl-3-pyrazolidone, 7200 g of sodium erysorbate monohydrate, 810 g of binder D-sorbit, N-acetyl-DL-penicillamine 7
g and glutaraldehyde bisulfite adduct 300 g in a commercially available stirring granulator at room temperature for about 3 minutes.
Of water is added over 1 minute, and the granulated material is dried at 50 ° C. for 2 hours with a fluidized-bed drier to almost completely remove water from the granulated material.

[Granulated product (B)] Potassium carbonate 9500
g and 6.0 g of potassium iodide are each pulverized in a commercially available bantam mill to an average of 10 μm. These fine powder, DTPA-Na 170 g, sodium sulfite 425
g, 5-mercapto- (1H) -tetrazolylacetic acid Na
8.3 g of salt, 40 g of 1- (3-sulfophenyl) -5-tetrazole-Na salt, 3.0 of 5-nitroindazole
g, binder mannitol 1500 g, D-sorbit 6
After mixing for about 3 minutes at room temperature in a commercially available stirring granulator and adding 125 ml of water over 1 minute to granulate, the granulated product is dried at 40 ° C. in a fluidized dryer at 40 ° C. for 2 minutes. After drying for a time, the water content of the granules is almost completely removed.

The granulated product (A) thus obtained was added with 1
1.0% of the total mass of sodium octanesulfonate,
Methyl-β-cyclodextrin was added at 3% of the total mass, 25%.
C., and added and mixed in a room conditioned at 40% RH or less. Further, the granulated product (B) contains sodium 1-octanesulfonate at 1.2% of the total mass and methyl-β-cyclodextrin at the total mass. In a room conditioned at 25 ° C. and 40% RH or less, and mixed with Kikusui Seisakusho's Tough Press Collect 1
527HU was subjected to compression tableting using a modified tableting machine to produce each of the developed tablets (A) and (B). The filling amount per tablet was (A) 8.45 g and (B) 12.4 g. (A) 60 pieces, (B) 50 pieces (volume after dissolution is 5.
The tablets were sealed and packaged using a packaging material having the following layer constitution for moisture prevention.

The packaging material is biaxially stretched nylon (ONY)
15 μm thickness / aluminum oxide deposited PET 12 μm thickness /
A bag made of a laminate material consisting of biaxially oriented polypropylene (OPP) 25 μm thick / low-density polyethylene (LLDP) 40 μm thick. The effective surface area on the side (inside) of the packaging material in contact with the tablets was 1300 cm ² . .

<Preparation of solid fixing agent> [Granulated product (C)] In a commercially available bantam mill, 14580 g of ammonium thiosulfate / sodium thiosulfate (90/10 mass ratio) is ground to an average of 10 µm. The compound HO—CH ₂ CH ₂ —S—CH ₂ CH ₂ —SC is added to this fine powder.
H ₂ CH ₂ -OH1000g, sodium metabisulfite 9
After adding 20 g, 50 g of 5-mercapto-tetrazole and 900 g of binder pine flow, mixing in a commercially available stirring granulator at room temperature for about 3 minutes, and granulating by adding 150 ml of water over 1 minute. The granulated product is dried at 40 ° C. in a fluidized bed drier to remove water almost completely.

[Granulated product (D)] 250 g of boric acid, 1500 g of aluminum sulfate octahydrate, 1150 g of succinic acid, 2 tartaric acid
50g, Mannit 208g, D-Sorbit 100g
, And mixed in a commercially available stirring granulator at room temperature for about 3 minutes, and granulated by adding 150 ml of water over 1 minute, and then drying the granulated material at 40 ° C. in a fluidized bed drier. To remove water almost completely.

The granulated product (C) thus obtained, 1400 g of sodium acetate and sodium 1-hexanesulfonate in a room conditioned at 2.5% of the total mass, 25 ° C. and 40% RH or less. 1400 g of sodium acetate was added to the granulated product (D), and sodium 1-hexanesulfonate was further added to 3.0% of the total mass at 25 ° C and 40% R.
The mixture was added and mixed in a room humidified below H, and compression tableting was performed with a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho to produce fixing tablets (C) and (D). The filling amount per tablet is (C) 10.5 g, (D)
8.95 g. Ninety-two tablets (C) and twenty-eight (D) (the amount after dissolving to a volume of 5.0 L) were prepared using the packaging material used in developing tablets (A) and (B) for moisture proofing. Enclosed and packaged.

Development Starter Formulation (Amount Added to 1 L of Developer) N-acetyl-DL-penicillamine 0.11 g Diethylene glycol 48.5 g 5-mercapto- (1H) -tetrazolylacetic acid Na 0.12 g Acetic acid 90% 11.5 g KBr 16 Finished with 0.0 g pure water 67 ml TCX-701 (manufactured by Konica Corporation) was used as an automatic developing machine. At the start, 7.8 L of a developing solution in which a developing tablet was dissolved was added to the developing solution in the developing tank, and a starter was added to fill the developing tank as a starting solution to start processing. The amount of the starter added was 67 ml / 1 L of the developing solution, and the capacity of the developing tank was 7.
An amount corresponding to 8 L was added. As a fixing solution, 5.6 L of the fixing solution prepared in the same manner was put into a fixing processing tank of TCX-701 to be used as a starting solution.

In each of the developing and fixing steps, each of the packaging bags was opened by hand at the inlet of each solid agent, and the tablets were dropped into the built-in chemical mixer.
(0 ° C) and dissolving with stirring for 25 minutes while stirring and dissolving.
Adjust to 0L. This was used as a developing and fixing replenisher.

The pH when the developer was dissolved was 10.15,
The pH when the starter was added was 9.90. The dissolution pH of the fixing solution was 4.25.

The built-in chemical mixer is divided into a liquid preparation tank and a spare tank tank. The capacity of the liquid preparation tank is 5.0 L, and the capacity of the spare tank is 5.0 L. The film was produced in the liquid preparation tank during running processing of the film. A spare tank is provided so that the replenisher is supplied so that the replenisher does not enter the non-replenished state during the stirring and dissolving time (about 25 minutes) even when the replenisher runs out.

Development temperature 34 ° C. (replenishment rate is 100 ml / m
² ) Fixing temperature 34 ° C. (replenishment rate is 100 ml / m ² ), water 18 ° C. (5 L / min), drying temperature 55 ° C., processing time 4
Evaluation was performed in 5 seconds.

<Evaluation of Sensitometry> Using the obtained sample, the emulsion surface was changed to an X-ray fluorescent intensifying screen M for mammography.
-100 (manufactured by Konica Corporation) in close contact with the phosphor layer surface in the cassette. 1 for high and constant adhesion
After standing for 0 minutes, X-ray irradiation was performed. The X-ray generator used was ROTANODE manufactured by Toshiba Corporation, and the tube voltage was 27
Irradiation was performed at KVp and a tube current of 100 mA (focal size 0.4 mm) for 0.5 seconds. At this time, an acrylic plate having a thickness of 2 cm was placed at a position 20 cm from the anode. After the development, a sensitometric curve was prepared by the distance method, and the sensitivity, fog, and gradation were determined. The value of sensitivity is fog +
Sample No. was determined as the reciprocal of the X-ray dose required to obtain a concentration of 1.0. The relative sensitivity was evaluated with the value of the film No. 1 as 100. As for the gradation, the logarithm of the X-ray exposure amount is plotted on the horizontal axis, the optical density is plotted on the vertical axis, and the point of fog + 0.25 and the point of fog + 2.0 are connected on a characteristic curve on coordinates where the unit length is equal. Tanθ when the angle between the straight line and the horizontal axis is θ
It was expressed by.

<Evaluation of Storage Property>
(Relative humidity) The humidity was controlled at 47% for 2 hours, and then sealed in a light-shielding moisture-proof bag and subjected to a storage stability test.

(Test conditions) 1. Natural leave: 3 days 2. Natural leave: 6 months High humidity storage: 40 ° C, RH80 without placing in a light-proof and moisture-proof bag
% For 3 days The samples placed under these storage conditions were subjected to the sensitometric evaluation described above.

<Evaluation of Diagnostic Performance> Using the obtained sample, a KYOKO156 mammo phantom (manufactured by Kasei Optonics Co., Ltd.) was brought into close contact with a cassette in which the sample was placed using the same apparatus as used for sensitometric evaluation, and photographed. The tumor image, microcalcification image, and fiber image were visually evaluated and ranked comprehensively as diagnostic ability.

Evaluation Criteria A: All look clear B: All look good C: Some images are hard to see D: All images are hard to see The above results are shown in Tables 4 and 5.

[0170]

[Table 4]

[0171]

[Table 5]

[0172]

As is clear from the examples, the X of the present invention
According to the silver halide photographic light-sensitive material for X-ray mammography, image contrast is high, diagnostic performance is excellent, and storage stability is good.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a silver halide emulsion manufacturing apparatus applicable to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Reaction container 2 Stirring mechanism 3 Dispersion medium 4 Silver addition line 5 Halide addition line 6 Dispersion medium addition line 7 Addition line 8 Liquid take-out line 9 Liquid return line 10 Permeate discharge line 11 Permeate return line 12 Ultrafiltration unit 13 Circulation Pump 14 Flow meter 15, 16, 17 Pressure gauge 18 Pressure adjusting valve 19 Flow adjusting valve 20 Silver addition valve 21 Halide addition valve 22 Liquid extraction valve 23, 24, 25 Valve 26 Ultrafiltration permeate 27 Permeate receiver 28 Scale 29,30 Silver halide fine grain emulsion addition line 31,32 Fine grain addition valve

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) G03C 1/76 502 G03C 1/76 502 5/17 5/17 5/26 520 5/26 520 5/305 5/305

Claims (16)

[Claims] 1. A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on one side of a support and a backing layer on the other side of the support. At least one of the emulsion layers has at least 50% of the total projected area of the silver halide grains contained therein Rh,
A tabular silver halide grain having an aspect ratio of 3 to 30 doped with at least one metal ion selected from Ru, Re, and Os, and at least one compound represented by the general formula (1): A silver halide photographic light-sensitive material characterized by containing: Embedded image (Where Y is C = O, C = S, C = Se, CH ₂ , CH ₂
Represents CH ₂ , wherein R ₁ and R ₂ are each independently an aliphatic group, an aromatic group, or a heterocyclic group, or R ₁ and R ₂ are bonded to each other to form a 5-membered or 6-membered ring or a polycyclic ring; Represents the group of atoms necessary to form a system. ) 2. A support having at least one layer on one side of a support.
Has a light-sensitive silver halide emulsion layer and a backing
Silver halide photographic light-sensitive material having a
At least one of the light-sensitive silver halide emulsion layers is contained.
At least 50% of the total projected area of the silver halide grains is Rh,
At least one metal selected from Ru, Re, and Os;
ON-doped flat plate with aspect ratio of 3 to 30
A silver halide grain represented by the general formula (2)
(C) containing at least one compound.
Silver halide photographic material. Embedded image(Where R_ThreeRepresents an oxygen atom, NOH, or NH group;_FourIs
R_ThreeIs an oxygen atom, a hydroxylamino group (NHO
H) or an amino group, R_ThreeIs hydrogen when NOH or NH
Atom, hydroxyl group, alkyl having 2 or less carbon atoms
Group, hydroxyalkyl group having 2 or less carbon atoms, carbon
Represents an alkoxy group having 2 or less atoms. R _FiveIs hydrogen field
Child, halogen atom, acyl group, amino group, acylamino
Group, nitro group, cyano group, alkyl having 4 or less carbon atoms
Group, alkoxy group, hydroxyl group, carboxyl group
Or a salt thereof, a sulfo group or a salt thereof. n is 0-2
Represents an integer. ) 3. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on one side of a support and a backing layer on the other side of the support. At least one of the emulsion layers has at least 50% of the total projected area of the silver halide grains contained therein Rh,
Tabular silver halide grains having an aspect ratio of 3 to 30 doped with at least one metal ion selected from Ru, Re and Os, and containing at least one compound represented by the general formula (3) A silver halide photographic material. Embedded image (Wherein, R ₆ represents an alkyl group, an aryl group, or a heterocyclic group, A represents —NR ₇ — or —S—, and R ₇ represents hydrogen or a lower alkyl group having 1 to 5 carbon atoms. Represents.) 4. The method according to claim 1, wherein the doping amount of the metal ion is 1 × 10 ⁻¹⁰ mol or more and less than 1 × 10 ⁻⁷ mol per 1 mol of silver. Silver halide photographic material. 5. The method according to claim 1, wherein the tabular silver halide grains are silver halide grains grown by ultrafiltration while appropriately extracting a salt-containing solution from a reaction solution during the growth process. The silver halide photographic material according to any one of claims 1 to 4. 6. The silver halide photographic light-sensitive material according to claim 1, wherein a coefficient of variation of a volume particle diameter of the tabular silver halide grains is 0.10 or less. material. 7. The silver halide photographic light-sensitive material according to claim 1, which is substantially free of hydroquinones and contains a compound represented by the general formula (4) and nitroindazole. And processing using a developer having a bromine ion concentration of 10 g / l or more in terms of potassium bromide. Embedded image (Wherein, R ₈ and R ₉ are each independently a hydroxy group, a mercapto group, a substituted or unsubstituted amino group, an acylamino group,
Represents an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonyl group or an alkylthio group. Z represents an atomic group necessary for forming a substituted or unsubstituted 5- or 6-membered ring. ) 8. The method for processing a silver halide photographic material according to claim 7, wherein the developer is a solution in which a solid developer is dissolved. 9. The method for processing a silver halide photographic light-sensitive material according to claim 8, wherein the solid developer is a tablet. 10. A surface of a silver halide photographic light-sensitive material according to any one of claims 1 to 6, wherein a surface of the X-ray fluorescent intensifying screen having a phosphor layer is in close contact with a surface of the silver halide emulsion layer having the emulsion layer. An image forming method comprising irradiating an X-ray transmitted through a subject, and thereafter developing, fixing, washing with water and drying with an automatic developing machine to form an X-ray image. 11. The image forming method according to claim 10, wherein the phosphor of the X-ray fluorescent intensifying screen is terbium-activated gadolinium oxysulfide. 12. The method for forming an image of a silver halide photographic material according to claim 10, wherein the image is developed by the processing method according to claim 7. Description: 13. The image forming method according to claim 10, wherein a tube voltage of the X-ray is 40 kVp or less. 14. The silver halide photographic material according to claim 1, which is used for X-ray mammography. 15. The method for processing a silver halide photographic material according to claim 7, wherein the method is for X-ray mammography. 16. The image forming method according to claim 10, wherein the method is for X-ray mammography.