JP2002131861A - Silver halide photographic sensitive material and method of processing the same and method of forming image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material for X-ray mammography having good contrast and fingerprint stain resistance and excellent in diagnostic ability and having good scratch resistance, provide a method of processing the same, and also provide a method of forming a X-ray image using those. SOLUTION: The silver halide photographic sensitive material has on one surface of a substrate at least one layer of photosensitive silver halide emulsion layer and a non-photosensitive colloidal layer on the silver halide emulsion layer and a backing layer on the other surface. At least one of the silver halide emulsion layers contains, in >=50% of the total projected area, flat platy silver halide grains doped with ions of at least one metal selected from Rh, Ru, Re, and Os and having aspect ratio of 3-30 and containing a compound represented by the general formulas (I), (II), and (3) chemical formulas (1), (2) and (3).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a silver halide photographic material having a photosensitive silver halide emulsion layer on one side of a support and a backing layer on the opposite side (hereinafter, referred to as "photosensitive material").
More specifically, the present invention relates to a silver halide photographic light-sensitive material for single-sided exposure for medical use.

[0002]

2. Description of the Related Art In recent years, from a survey of disease trends in Japan, it has been found 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, for breast cancer screening, visual inspection, palpation, ultrasonic image diagnosis, X-ray mammography (mammography), and the like have been performed. In particular, the importance of mammography is increasing due to its diagnostic effectiveness.

[0003] 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 contrast of the subject is originally low. Nevertheless, the image to be diagnosed is often a tumor shadow or the like having only a small contrast, and there is a difficulty in finding an early-stage cancer in particular.

[0004] 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. Because the calcified part has high X-ray absorption,
It is represented on the image as a low density point. Therefore, a film having a high gradation in a low density portion is suitable for detecting microcalcification.

[0005] 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.

[0006] As a means for enhancing contrast, silver halide
A method of doping a metal ion or a metal complex ion such as h (rhodium), Ru (ruthenium), Re (rhenium), and Os (osmium) is conventionally known. Most of these techniques are for obtaining ultra-high contrast characteristics as a photosensitive material for printing, and have a large content of Rh salt. However, by reducing the amount of Rh salt, it is suitable for mammography which is the object of the present invention. It is possible to adjust to gradation. For example, JP-A-6-102613 describes a method in which a relatively small amount of a Rh salt is added to silver iodobromide containing 4 mol or less of silver iodide together with a spectral sensitizing dye before chemical sensitization. ing. However, Rh, Ru, Re, Os
It has been found that a photosensitive material using silver halide particles doped with a metal ion or a metal complex ion tends to cause abrasion and desensitization (so-called fingerprint trace) due to the attachment of a fingerprint.

In mammography, as described above, it is important for diagnosis to read a low-density fine dot-like, streak-like or glass-like image as a calcified image. The occurrence of fingerprints and fingerprints may lead to misdiagnosis.

On the other hand, tabular silver halide grains are known to easily obtain high sensitivity and have high covering power, and are used in a wide variety of photosensitive materials because of their excellent properties. However, it was found that when tabular silver halide grains were doped with Rh salt or the like in order to increase the gradation, the scratch resistance and fingerprint trace resistance deteriorated more. Japanese Patent Application Laid-Open No. 2-219051 describes a color photographic light-sensitive material containing tabular silver halide grains containing a noble metal such as Rh, Ru, Os and Ir (iridium). It is described that by acting as a desensitizer and mixing particles having the same particle size, a gradation can be formed in a wide exposure range, and processing fluctuation and gradation preservability are improved. JP-A-9-197597 discloses that tabular silver halide grains contain Cr (chromium), Ru,
A technique has been disclosed in which at least one of Rh, Re, and Os is doped and selenium is sensitized to improve sensitivity increase and fog increase during storage over time. However,
None of the publications disclose the scratch resistance and fingerprint trace resistance required of 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 which has high contrast, excellent diagnostic performance, and good scratch and fingerprint resistance. An object of the present invention is to provide a processing method and an X-ray image forming method using the processing method.

[0010]

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

The support has at least one light-sensitive silver halide emulsion layer on one surface, a light-insensitive colloid layer above the silver halide emulsion layer, and a backing layer on the opposite surface. In the silver halide photographic light-sensitive material, (1) at least one of the silver halide emulsion layers is doped with at least one metal ion selected from Rh, Ru, Re, and Os for 50% or more of the total projected area. It is a tabular silver halide grain having an aspect ratio of 3 to 30, and is represented by the general formula (I), the general formula (II), or the general formula (III). A silver halide photographic material containing a compound. (2) At least one of the silver halide emulsion layers is a flat plate having an aspect ratio of 3 to 30 in which at least 50% of the total projected area is doped with at least one metal ion selected from Rh, Ru, Re, and Os. A silver halide photographic light-sensitive material which is a silver halide grain and contains a compound represented by the above formula (I), (II) or (IV). (3) The tabular silver halide grains are silver halide grains grown by an ultrafiltration method while appropriately extracting a salt-containing solution from a reaction solution during the growth process (1) or (2). The silver halide photographic light-sensitive material described in (1). (4) The silver halide photographic material as described in (1), (2) or (3), wherein a coefficient of variation of a volume particle size of the tabular silver halide grains is 0.10 or less. (5) The silver halide photographic light-sensitive material according to any one of (1) to (4), which is substantially free of hydroquinones and is represented by the above formula (V) A method for processing a silver halide photographic material, wherein the processing is performed using a developer containing a compound and nitroindazole. (6) The developer is a solution in which a solid developer is dissolved (5).
The method for processing a silver halide photographic light-sensitive material described in the above. (7) The method for processing a silver halide photographic material according to (6), wherein the solid developer is a tablet. (8) The surface of the silver halide photographic material according to any one of (1) to (4), which has the phosphor layer of the fluorescent intensifying screen, is in close contact with the surface of the silver halide emulsion layer having the silver halide emulsion layer. An image forming method for forming an X-ray image by irradiating X-rays transmitted through a developing device, followed by developing, fixing, washing with water and drying with an automatic developing machine. (9) The image forming method according to (8), wherein the phosphor of the fluorescent intensifying screen is terbium-activated gadolinium oxysulfide. (10) The image forming method according to (8), wherein the development is the processing method according to (5), (6) or (7). (11) The image forming method according to (9), wherein the developing is the processing method according to (5), (6) or (7). (12) X-ray has a tube voltage of 40 kVp or less (8)-
The image forming method according to any one of (11). (13) The silver halide photographic material according to any one of (1) to (4), which is for X-ray mammography. (14) The method for processing a silver halide photographic material according to any one of (5) to (7), which is for X-ray mammography. (15) The image forming method according to any one of (8) to (12), which is for X-ray mammography.

Hereinafter, the present invention will be described in detail. The silver halide grains used in the present invention are tabular silver halide grains having an aspect ratio of 5 to 30 at 50% or more of the total projected area. Tabular silver halide grains are crystallographically classified as twins. Twins are crystals having one or more twin planes in one grain. Classification of the twin morphology in silver halide grains is based on the report by Klein and Moiser, “Pho.
togglefish Korresponden
z, Vol. 99, p. 99, and Vol. 100, p. 57.

In the present invention, the aspect ratio means the ratio of the area-converted particle diameter to the particle thickness (aspect ratio = equivalent circle 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 0.1 to 10.0 μm, more preferably 0.2 to 5.0 μm, and particularly preferably 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 is prepared by applying a latex ball of known particle size as an internal standard on a support and silver halide particles so that the main plane is oriented parallel to the substrate, and shadowing is performed by carbon deposition from a certain angle. After that, 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 can be determined by arbitrarily determining the number of silver halide grains contained in the silver halide emulsion by using the above-mentioned replica method. The value measured as above and obtained as an arithmetic average thereof is referred to.

In the present invention, the coefficient of variation of the volume diameter of silver halide grains is a value defined by the following equation using the value obtained from the above measurement.

Coefficient of variation of volume particle size = (standard deviation of volume particle size / average value of volume particle size) The coefficient of variation of the volume particle size of the silver halide grains according to the present invention is preferably 0.2 or less. 10 or less is more preferable.

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 the following equation.

Coefficient of variation of areal grain size = (standard deviation of areal grain size / average of areal grain size) The variation coefficient of areal grain size of the silver halide grains according to the present invention is preferably 0.2 or less. 10 or less is more preferable.

In the silver halide emulsion according to the present invention, 50% or more of the total projected area of the silver halide grains contained in the silver halide emulsion has an average aspect ratio (hereinafter simply referred to as aspect ratio). It is preferably 5 to 30 tabular grains, more preferably 50% or more of the total projected area is a tabular grain having an aspect ratio of 6 to 20, and particularly preferably a tabular grain having an aspect ratio of 7 to 15. Is preferred. It is preferable that 80% or more of the total projected area of the silver halide grains contained in the silver halide emulsion is the tabular grains according to the present invention.

The tabular silver halide grains according to the present invention are:
The grains have one or two or more twin planes parallel to each other in the grains, and preferably at least 50% of the tabular grains are tabular grains having two twin planes parallel to each other in the grains. , 80% or more.

The silver halide grains preferably have a composition of silver iodobromide or silver chloroiodobromide. In particular, silver iodobromide having an average silver iodide content of 2 mol% or less in the silver halide emulsion is preferable. Further, the average silver iodide content is preferably at most 1 mol%, particularly preferably at most 0.5 mol%.

Further, in the silver halide emulsion according 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 referred to herein 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 the result by 100, and the silver halide contained in the silver halide emulsion. A value obtained by arbitrarily measuring 500 or more particles. The silver iodide content of each silver halide grain can be determined, for example, by analyzing the composition of each grain using an X-ray microanalyzer.

In order to make the silver iodide content between silver halide grains uniform, it is preferable that the grain size distribution of the seed emulsion is narrow, and the degree of supersaturation during the formation of a phase containing silver iodide is reduced. It is preferred to keep it high. Further, it is preferable to form a silver iodide-containing phase by adding silver iodide-containing silver halide fine grains (particularly, silver iodide fine grains). Further, it is preferable to use a production method in which an aqueous solution containing a salt is appropriately extracted from the reactant solution by an ultrafiltration apparatus. For example, the average intergranular distance in the growth process of silver halide grains is determined by the average intergranular distance at the start of growth. Is preferably controlled to 0.60 to 1.00 times, more preferably to 0.60 to 0.80 times. Specifically, the value of the average interparticle distance is set to 3.2.
It is preferably controlled to not more than μm, more preferably to not more than 2.8 μm, particularly preferably to 0.90 to 2.0 μm.

As a preparation form of the silver halide emulsion, 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.

A silver halide solvent can be used if necessary. Examples of useful silver halide solvents include ammonia, thioethers and thioureas. Regarding thioethers, US Pat. No. 3,271,15
No. 1, 3,790,387, 3,574,626
No. etc. can be referred to.

The method of preparing the grains is not particularly limited, and an ammonia method, a neutral method using no ammonia, an acidic method, or the like can be used. The viewpoint that fogging during silver halide grain formation can be suppressed. From, preferably p
It is preferable to form particles in an environment where H 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, Ru,
Re and Os. 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 of metal ions is 1 × 10 ⁻¹⁰ to 1 × per mole of silver.
The range of 10 ⁻⁷ mol is preferred, and 5 × 10 ⁻¹⁰ to 1 × 10.
^-8 mol is more preferred.

The metal complex is preferably a six-coordinate complex or complex ion represented by the following general formula. In the general 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,-, 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 alcohol. Each ligand of
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, potassium salts, such as sodium salts, ammonium salts or cesium salts, preferably used as a salt of the complex.

The compound providing these metal ions or complex ions is preferably added during silver halide grain formation and incorporated into silver halide grains. Preparation of silver halide grains, that is, nucleation, Growth, physical ripening, 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. Is more preferred.

In the addition, the compound may be added in several divided portions, may be added uniformly in the silver halide grains, or may be added uniformly 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 prepared by using water or a suitable organic solvent (alcohols, ethers, glycols,
Ketones, esters and amides). For example, an aqueous solution of a metal compound or an aqueous solution in which a metal compound and sodium chloride and potassium chloride are dissolved together may be added to water-soluble silver during grain formation. A silver halide grain is prepared by adding it to a salt solution or a water-soluble halide solution, or, when a silver salt solution and a halide solution are simultaneously mixed, adding it as a third aqueous solution and simultaneously mixing the three solutions. Method, a method of charging a required amount of an aqueous solution of a metal compound into a reaction vessel during grain formation, or adding another silver halide grain previously doped with a metal ion or complex ion during silver halide preparation. There is a method of dissolving. In particular, a method in which an aqueous solution of a metal compound or an aqueous solution in which a metal compound and sodium chloride and potassium chloride are dissolved together is added 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 according 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.

The dispersion medium which can be preferably used includes:
There are gelatin and protective colloid polymers. As the gelatin, alkali-treated gelatin or acid-treated gelatin having a molecular weight of about 100,000, or low-molecular gelatin or oxidized gelatin having a molecular weight of about 5,000 to 30,000 can be preferably used. In particular, at the time of nucleation, oxidized gelatin, low molecular weight gelatin, or oxidized low molecular weight gelatin can be suitably used.

In the silver halide emulsion of the present invention, Research Disclosure (Research)
Disclosure) 308119 (hereinafter referred to as RD30
(Abbreviated as 8119).

The silver halide grains used in the present invention can be subjected to chemical sensitization by a commonly used method. The conditions of the step of chemical ripening, that is, chemical sensitization, for example, pH, pAg, temperature, time and the like are not particularly limited, and can be performed under conditions generally used in the art. Chemical sensitization includes sulfur sensitization using a compound containing sulfur capable of reacting with silver ions and active gelatin, selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound, reduction using a reducing substance. There are sensitization methods, gold and other noble metal sensitization methods using noble metals, and these methods may be used alone or in combination. Among them, selenium sensitization, tellurium sensitization, reduction sensitization, etc. are preferably used,
In particular, a selenium sensitization method is preferably used.

Examples of useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (such as allyl isoselenocyanate), and selenoureas (N, N
-Dimethylselenourea, N, N, N'-triethylselenourea, etc.), selenoketones (selenoacetone, selenoacetophenone, etc.), selenoamides (selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids, and seleno Esters (such as 2-selenopropionic acid and methyl-3-selenobutyrate), selenophosphates (such as tri-p-triselenophosphate), and selenides (such as diethylselenide, diethyldiselenide, and triphenylphosphineselenide). Can be mentioned. Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenium ketones.

The amount of the selenium sensitizer varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally 10 ^-8 to 10 per mol of silver halide.
^{It is} preferable to use about ^-4 mol. Depending on the properties of the selenium compound to be used, the addition method may be a method in which the compound is dissolved in water or an organic solvent such as methanol, ethanol, ethyl acetate or the like alone or in a mixed solvent, or a method in which the compound is previously mixed with a gelatin solution and added. Or JP-A-4-1407
The method disclosed in No. 39, that is, a method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer may be used.

Next, the compounds represented by formulas (I) and (II) will be described in detail. The compounds represented by the general formulas (I) and (II) are cyanine dyes, which are a kind of spectral sensitizing dyes. The compounds represented by the general formula (I) are suitable for the image forming method of the present invention. It can be spectrally sensitized to the photosensitive wavelength.

In the general formula (I), R ₁ and R ₂ each represent an alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, propyl) or a substituted alkyl group (vinylmethyl, 2-hydroxyethyl, 4-hydroxy Butyl, 2-acetoxyethyl, 3-acetoxypropyl, 2-methoxyethyl,
4-butoxybutyl, 2-carboxyethyl, 3-carboxypropyl, 2- (2-carboxyethoxy) ethyl, p-carboxybenzyl, 2-sulfoethyl, 3-
Sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2-hydroxy-3-sulfopropyl, 2- (3-
Sulfopropoxy) ethyl, 2-acetoxy-3-sulfopropyl, 3-methoxy-2- (3-sulfopropoxy) propyl, 2- [2- (3-sulfopropoxy) ethoxy] ethyl, 2-hydroxy-3- (3'-sulfopropoxy) propyl, p-sulfophenethyl, p-sulfobenzyl and the like, and aralkyl groups (benzyl, phenethyl and the like).

However, at least one of R ₁ and R ₂ is:
It is an alkyl group having a sulfo group. R ₃ has 1 to 4 carbon atoms
Represents a lower alkyl group (e.g., methyl, ethyl).

Each of R ₄ , R ₅ , R ₆ and R ₇ is a hydrogen atom, preferably a lower alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl) and a halogen atom (chlorine, bromine, fluorine, Iodine), alkoxy group (methoxy, ethoxy, etc.), hydroxyl group, monoaryl group (phenyl, p
-Sulfophenyl, etc.), carboxyl group, alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, etc.), cyano group, trifluoromethyl group, amino group, lower alkyl-substituted amino group (methylamino, dimethylamino, etc.), acylamide (acetamide, etc.) ), An acyl group (such as acetyl), an acyloxy group (such as acetoxy), an alkoxycarbonylamino group (such as ethoxycarbonylamino), and a carboalkoxy group (such as carboethoxy). R ₄ and R ₅ , R ₆ and R ₇ are linked to each other to form a naphthooxazole nucleus (naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,
3-d] oxazole and the like.

In the general formula (II), Z ₁ and Z ₂ each represent a group of nonmetallic atoms necessary for completing the following heterocyclic nucleus.

Thiazole nucleus (this nucleus has a substituent such as a lower alkyl group, a monoaryl group, a halogen atom, a lower alkoxy group, a carboxyl group, a lower alkoxycarbonyl group, a monoaralkyl group, a trifluoromethyl group, a hydroxyl group, etc. May be specifically, thiazole, 4-methylthiazole, 4-phenylthiazole,
4,5-dimethylthiazole, 4,5-diphenylthiazole, benzothiazole, 4 (5,6 or 7) -chlorobenzothiazole, 4 (5 or 6) -methylbenzothiazole, 5-bromobenzothiazole, 6-bromo Besozothiazole, 5-iodobenzothiazole, 4 (or 5) -methoxybenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-
Ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5
-Trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole,
(Or 5) -phenylbenzothiazole, naphtho [2,
1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] Thiazole, 8-methoxynaphtho [2,
1-d] thiazole, 5-methoxynaphtho [2,1-
d] thiazole, 5-methoxynaphtho [2,3-d] thiazole and the like, and a thiazoline nucleus (this nucleus may have a substituent such as a lower alkyl group.
Methylthiazoline, etc.), an oxazole nucleus (the nucleus is a lower alkyl group, a halogen atom, a monoaryl group, a lower alkoxy group, a trifluoromethyl group, a hydroxyl group,
It may have a substituent such as a carboxyl group, for example, oxazole, 4-methyloxazole, 4-ethyloxazole, benzoxazole, 5 (or 6) -chlorobenzoxazole, 5 (or 6) -methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5 (or 6) -methoxybenzoxazole, 5-
Trifluoromethylbenzoxazole, 5 (or 6)
-Hydroxybenzoxazole, 5-carboxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho [2,1-d] oxazole, naphtho [1,2-d Oxazole, naphtho [2,3-d] oxazole and the like). Selenazole nucleus (this nucleus may have a substituent such as a lower alkyl group, a monoaryl group, a halogen atom, a lower alkoxy group, a hydroxyl group, and the like; for example, 4-methyl selenazole, 4-phenyl selenazole, benzo selena Zole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole and the like ), 3,3-
Di-lower alkyl indolenine nucleus (this nucleus is a cyano group,
It may have a substituent such as a lower alkyl group or a halogen atom, for example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3- Dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine,
3,3-dimethyl-5-chloroindolenine, etc., imidazole nucleus (this nucleus is a substituent such as a lower alkyl group, a monoaryl group, a halogen atom, a lower alkoxy group, a cyano group, a trifluoromethyl group, an allyl group, etc.) For example, 1-methylimidazole, 1-ethylimidazole, 1-methyl-4-phenylimidazole, 1-
Ethyl-4-phenylimidazole, 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole, 1-ethyl-5
-Chlorobenzimidazole, 1-methyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-allyl-5-methoxybenzimidazole, 1-methyl-5-cyanobenzimidazole, 1 -Ethyl-5-cyanobenzimidazole, 1-methyl-5-fluorobenzimidazole, 1
-Ethyl-5-fluorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1-
Ethyl-5-trifluoromethylbenzimidazole,
1-ethylnaphtho [1,2-d] imidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-phenylimidazole, 1-phenylbenzimidazole, 1-phenyl- 5-chlorobenzimidazole, 1-phenyl-
5,6-dichlorobenzimidazole, 1-phenyl-
5-methoxybenzimidazole, 1-phenyl-5-
Cyanobenzimidazole, 1-phenylnaphtho [1,
2-d] Imidazole and the like). A pyridine nucleus (this nucleus may have a substituent such as a lower alkyl group, for example, pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine and the like).

R ₈ and R ₉ each represent an alkyl group as defined above for R ₁ or R ₂ . Next, the general formulas (I) and (II)
The sensitizing dye represented by the following formula is exemplified, but the present invention is not limited thereto.

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The amount of the compound represented by the general formula (I) is preferably 0.1 to 4 mmol per 1 mol of the photosensitive silver halide. More preferably, it is 0.3 to 3 mmol.

The amount of the compound represented by the formula (II) is preferably 0.1 to 5 mmol per 1 mol of the photosensitive silver halide. More preferably, it is 0.1 to 2 mmol.

As the solvent for these compounds, conventionally used water-miscible organic solvents can be used. For example, alcohols, ketones, nitriles, alkoxy alcohols and the like are used. Specific examples include methanol, ethanol, propyl alcohol, i-propyl alcohol, ethylene glycol, propylene glycol, 1,
3-propanediol, acetone, acetonitrile, 2
-Methoxyethanol, 2-ethoxyethanol and the like.

In the present invention, the effect is increased by adding the compound as an acidic solution or a dispersion of solid fine particles, rather than adding the compound as a solution of an organic solvent. In particular, it is preferably added in the form of a solid fine particle dispersion substantially insoluble in water, which is dispersed in an aqueous system substantially free of an organic solvent and / or a surfactant.

Each of these sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. In addition to the sensitizing dye, the emulsion layer may contain a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, a substituted aminostilbene compound which is a nitrogen-containing heterocyclic group (US Pat. No. 2,932)
3,390 and 3,635,721), aromatic organic acid formaldehyde condensate (described in US Pat. No. 3,743,510), cadmium salt,
An azaindene compound may be contained.

The sensitizing dye according to the present invention can be added during the chemical ripening step, particularly preferably before the start of the chemical ripening, or from the nucleation step of the silver halide emulsion to the end of the desalting step. , A high-sensitivity silver halide emulsion having excellent spectral sensitization efficiency can be obtained.

Next, the compound represented by formula (III) will be described in detail. In general formula (III), the adsorption accelerating group to silver halide represented by X _1, a group having a thioamide moiety (thioureido, thiourethane, dithiocarbamate ester, 4-thiazoline-2-thione, 4
-Imidazoline-2-thione, 2-thiohydantoin,
Rhodanine, thiobarbituric acid, tetrazoline-5
Thione, 1,2,4-triazoline-3-thione, 1,
3,4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2
-Thione, benzoxazoline-2-thione, benzothiazoline-2-thione, etc.), mercapto group (methylthio, ethylthio, phenylthio, etc.), group having disulfide, 5- or 6-membered nitrogen-containing heterocyclic group (benzotriazolyl) , Triazolyl, tetrazolyl, indazolyl, benzimidazolyl, imidazolyl, benzothiazolyl,
Thiazolyl, benzoxazolyl, oxazolyl, triazinyl and the like).

Examples of the divalent group represented by L ₁ include an alkylene group, an arylene group, a heteroarylene group, an ether group, a thioether group, an imino group, an ester group, an amide group, and a sulfonyl group. These groups may be combined to form one divalent group.

Examples of the electron donating group represented by R ₁ , R ₂ and R ₃ include an alkyl group, an amino group, a hydroxyamino group, an alkylamino group, a dialkylamino group and an alkoxy group.

Examples of the alkyl group represented by R ₁ , R ₂ and R ₃ include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl and the like. Groups. These alkyl groups further include a halogen atom (chlorine, bromine, fluorine, etc.), an alkoxy group (methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy,
Dodecyloxy), an aryloxy group (phenoxy,
Naphthyloxy), an aryl group (phenyl, naphthyl, etc.), an alkoxycarbonyl group (methoxycarbonyl,
Ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl, etc., aryloxycarbonyl group (phenoxycarbonyl, naphthyloxycarbonyl, etc.), heterocyclic group (2,3 or 4-pyridyl, morpholyl, biperidyl, piperazyl, selenazolyl, sulfolanyl, piperidinyl , Tetrazolyl, thiazolyl, oxazolyl, imidazolyl, thienyl, pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyrimidyl, pyrazolyl, furyl, etc.), amino group (amino, N, N-dimethylamino, anilino, etc.), hydroxyl group, cyano group, sulfo Group, carboxyl group, sulfonamide group (methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc. It may be replaced by, or the like.

The compound of the general formula (III) is preferably contained in a silver halide emulsion layer or a layer adjacent thereto, particularly preferably a silver halide emulsion layer. The amount of addition is 1 × 10 ^{−6 to} 0.1 mol, preferably 1 × 10 ^{−5 to} 0.01 mol, per mol of silver halide. General formula (III)
The compound of formula (I) can be added to a silver halide emulsion according to the usual method of adding a photographic emulsion additive. For example, it can be dissolved in methanol, ethanol, methyl cellosolve, acetone, water, or a mixed solvent thereof and added.
Further, it may be added as a dispersion by a method such as solid dispersion or emulsification dispersion.

The compound of the general formula (III) may be added in any step of the production process of the silver halide emulsion, or after the production of the silver halide emulsion and immediately before the coating process. The preferred timing of addition is from the end of silver halide grain formation to the end of the coating solution preparation step.

Specific examples of the compound of the present invention represented by formula (III) are shown below, but it should not be construed that the invention is limited thereto.

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Next, the compound represented by formula (IV) will be described. In formula (IV), preferred examples of the group for promoting adsorption to silver halide represented by X ₂ include a thioamide group, a mercapto group, a group having a disulfide bond, and a 5- to 6-membered nitrogen-containing heterocyclic group. Is mentioned.

Among the adsorption promoting groups represented by X ₂ , the thioamide group may be a part of a ring structure or may be an acyclic group. Specific examples of the acyclic thioamide group include a thioureido group, a thiourethane group, and a dithiocarbamate group. Specific examples of the cyclic thioamide group include 4-thiazoline-2-thione and 4-imidazoline-2-. Thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione,
1,2,4-triazoline-3-thione, 1,3,4-
Thiadiasolin-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzooxazoline-2-thione, benzothiazoline-2-thione, and the like, which may be further substituted. Good.

Examples of the mercapto group include an aliphatic mercapto group, an aromatic mercapto group and a heterocyclic mercapto group (—SH
When a nitrogen atom is adjacent to the carbon atom to which the group is bonded, it has the same meaning as a cyclic thioamide group having a tautomeric relationship with the nitrogen atom, and specific examples of this group are the same as those listed above.) .

Further, as the 5- or 6-membered nitrogen-containing heterocyclic group,
A 5- to 6-membered nitrogen-containing heterocyclic ring composed of a combination of nitrogen, oxygen, sulfur and carbon is exemplified. Of these, preferred are residues such as benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, and triazine. These groups may be further substituted.

Of the groups represented by X ₂ , preferred are
Cyclic thioamide groups (ie, mercapto-substituted nitrogen-containing heterocycles, specifically 2-mercaptothiadiazolyl, 3-mercapto-1,2,4-triazolyl, 5-mercaptotetrazolyl, 2-mercapto-1,3 , 4-oxadiazolyl, 2-mercaptobenzoxazolyl, etc.) or a nitrogen-containing heterocyclic group (benzotriazolyl, benzimidazolyl, indazolyl, etc.).

The divalent linking group represented by L ₂ is an atom or an atomic group containing at least one of carbon, nitrogen, oxygen and sulfur. Specifically, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-,
-NH -, - N =, - CO -, - SO 2 - ( these groups may also have a substituent) is made of a single, or combination of such.

Examples of the substituent of the substituted or unsubstituted amino group represented by R ₁₃ and R ₁₄ include an alkyl group, an aryl group, an acyl group, a sulfonyl group, an oxycarbonyl group, a carbamoyl group, a sulfamoyl group, a hydroxyl group, And a heterocyclic group. The number of substituents is preferably one, but when two, they may be different from each other. Further, two substituents may be linked to each other to form a nitrogen-containing heterocyclic ring (morpholino, piperidino, pyrrolidino, imidazolyl, etc.).

Specific examples of the group which can be substituted on the benzene ring represented by R ₁₅ include a halogen atom (fluorine, chlorine, bromine), an alkyl group (preferably having 1 to 20 carbon atoms) and an aryl group (preferably Represents an alkoxy group (preferably having 1 to 20 carbon atoms), an aryloxy group (preferably having 6 to 20 carbon atoms), an alkylthio group (preferably having 1 to 20 carbon atoms). ), An arylthio group (preferably having 6 to 20 carbon atoms), an acyl group (preferably having 2 to 20 carbon atoms), an acylamino group (preferably an alkanoylamino group having 1 to 20 carbon atoms, Benzoylamino group having 20), nitro group, cyano group, oxycarbonyl group (preferably alkoxycarbonyl group having 1 to 20 carbon atoms, aryloxycarbo having 6 to 20 carbon atoms) Carboxyl group, sulfo group, hydroxyl group, ureido group (preferably alkyl ureido group having 1 to 20 carbon atoms, aryl ureide group having 6 to 20 carbon atoms), sulfonamide group (preferably having 1 to 20 carbon atoms). Alkylsulfonamide group, arylsulfonamide group having 6 to 20 carbon atoms), sulfamoyl group (preferably alkylsulfamoyl group having 1 to 20 carbon atoms, arylsulfamoyl group having 6 to 20 carbon atoms), carbamoyl group (Preferably having 1 to 2 carbon atoms)
0, an alkylcarbamoyl group, an arylcarbamoyl group having 6 to 20 carbon atoms), an acyloxy group (preferably an alkanoyloxy group having 2 to 20 carbon atoms, a benzoyloxy group having 7 to 20 carbon atoms), an amino group (unsubstituted amino group) , Preferably an alkyl group having 1 to 20 carbon atoms or 6 to 2 carbon atoms.
Secondary or tertiary amino group substituted with 0 aryl group),
A carbonate group (preferably an alkyl carbonate group having 2 to 20 carbon atoms, an aryl carbonate group having 7 to 20 carbon atoms), a sulfonyl group (preferably an alkyl sulfonyl group having 1 to 20 carbon atoms, Arylsulfonyl group), sulfinyl group (preferably having 1 to 20 carbon atoms)
Alkylsulfinyl group, arylsulfinyl group having 6 to 20 carbon atoms) and heterocyclic group (pyridyl, imidazolyl, furyl, and the like), and when there are two or more substituents, they may be the same or different. These groups may be further substituted.

Next, specific examples of the compound of the present invention represented by the general formula (IV) are shown, but it should not be construed that the invention is limited thereto.

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The compound of the formula (IV) is preferably contained in a silver halide emulsion layer or a layer adjacent thereto, particularly preferably a silver halide emulsion layer. The amount of addition is 1 × 10 ^{−6 to} 0.1 mol, preferably 1 × 10 ^{−5 to} 0.01 mol, per mol of silver halide.

The method of adding the compound to a silver halide emulsion may be in accordance with the usual method of adding a photographic emulsion additive. For example, it can be dissolved in methanol, ethanol, methyl cellosolve, acetone, water, or a mixed solvent thereof and added. Further, it may be added as a dispersion by a method such as solid dispersion or emulsification dispersion.

The compound may be added in any step of the production of the silver halide emulsion or in any step after the production of the silver halide emulsion and immediately before the coating step. The preferred timing of addition is from the end of silver halide grain formation to the end of the coating solution preparation step.

Next, the layer structure in the photographic light-sensitive material of the present invention will be described. The photographic light-sensitive material of the present invention has at least one light-sensitive silver halide emulsion layer on one surface of a support and has a backing layer on the opposite surface. Use a clear plastic base. For example, cellulose triacetate (TAC), polyester (polyethylene terephthalate PET, polyethylene naphthalate PEN, etc.), polystyrene (SPS, etc.) and the like are used. For photosensitive materials for medical diagnosis, which is the object of the present invention, 160-1
A PET base having a thickness of 80 μm is preferred.

The support may be colored in a range where the transparency is maintained. The coloring of the support in blue to about 0.1 to 0.2 can reduce eye fatigue in observation of a transmission image by Sharksten. preferable. Further, in order to provide adhesion between the constituent layer coated on the support and the support, the support is
Normally, the underwriting process is performed.

The constituent layer on the side having the photosensitive silver halide emulsion layer may include, in addition to the photosensitive silver halide emulsion layer, a conductive layer (antistatic layer), an intermediate layer, a filter dye layer, a protective layer and the like. Good. The dry thickness of the protective layer is 0.
It is preferably from 4 to 1.0 μm, more preferably from 0.5 to 0.8 μm
Is preferred. As additives to be added to the protective layer, those described in Research Disclosure (RD) described later can be used.

In the silver halide emulsion layer, additives described in RD below can be used.

The total thickness of the photosensitive silver halide emulsion layer when dried is preferably 5 μm or less, and 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 dye in a solid dispersed 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 (RD) below 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 light-sensitive material so as to be suitable for rapid processing, and the swelling ratio in the development-fixing-washing step is adjusted. By doing so, it is preferable to reduce the water content in the photosensitive material before the start of drying.

The swelling ratio of the light-sensitive material of the present invention during the development processing is preferably 100 to 200%. Here, the swelling ratio is obtained by calculating the difference between the film thickness after swelling in each processing solution and the film thickness before the development processing, and dividing this by the film thickness before the processing.
Say what is 00 times.

The photographic material of the present invention may contain various photographic additives (chemical sensitizers, sensitizing dyes, desensitizing dyes, dyes, development accelerators, antifoggants / stabilizers, brighteners, hardeners). , A surfactant, an antistatic agent, a plasticizer, a slipping agent, a matting agent, a binder, a support, etc.). Known additives include, for example, RD17643 (December 1978),
Page 23, section III to page 28, section XVII, RD18716 (197
Nov. 2009), pages 648 to 651, RD308119.
(December 1989), page 996, section III to page 1012 XXI
Those described in the section can be used.

Preferred developers for developing the light-sensitive material of the present invention include JP-A-4-15641 as a developing agent.
Dihydroxybenzenes such as hydroquinone; aminophenols such as p-aminophenol, N-methyl-p-aminophenol and 2,4-diaminophenol; 3-pyrazolidones such as 1 -Phenyl-3-pyrazolidone, 1-
In addition to phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone and the like, the compound of the above formula (V) can be used.

In the general formula (V), R ₁₆ and R ₁₇ are each independently a hydroxyl group, a mercapto group, or an amino group (an amino group is an alkyl group having 1 to 10 carbon atoms and is a methyl, ethyl, butyl, hydroxyethyl group) And the like as a substituent), an acylamino group (acetylamino,
Benzoylamino), alkylsulfonylamino group (methanesulfonylamino, etc.), arylsulfonylamino group (benzenesulfonylamino, p-toluenesulfonylamino, etc.), alkoxycarbonylamino group (methoxycarbonylamino, etc.), alkylthio group (methylthio, ethylthio Etc.).

Preferred examples of R ₁ and R ₂ include a hydroxyl group, an amino group, an alkylsulfonylamino group,
An arylsulfonylamino group can be mentioned.

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 carbonyl carbon and the two vinyl carbons substituted by R ₁₆ and R ₁₇ ; Particularly, a reductone ring is preferable. Specific examples of Z are, -O -, - C (R 18) (R 19) -, - C (R 20),
-C (= O) -, - N (R 21) -, - formed by combining the N =. However, R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxyl group, a carboxyl group,
A sulfo group), an optionally substituted aryl group having 6 to 15 carbon atoms (an alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group can be mentioned as a substituent), a hydroxyl group, Represents a carboxyl group. Further, a saturated or unsaturated condensed ring may be formed on the 5- or 6-membered ring. Examples of the 5- to 6-membered ring include rings such as dihydrofuranone, dihydropyrone, pyranone, cyclopentenone, cyclohexenone, pyrrolinone, pyrazolinone, pyridone, azacyclohexenone, and uracil. Examples include rings of tenone, cyclohexenone, pyrazolinone, azacyclohexenone, and uracil.

As the compound represented by the general formula (V),
In addition to sodium erythorbate and sodium ascorbate, compounds described in JP-A-10-133338, pp. 3-5 can be mentioned.

In the present invention, a developer containing substantially no hydroquinone and containing a compound of the formula (V) is preferred. "Substantially free of hydroquinones" means that the concentration is 0.1 g / liter or less. It is particularly preferable to use the compound represented by the general formula (V) in combination with a 3-pyrazolidone.

Preservatives may include sulphites, such as potassium sulphite, sodium sulphite; reductones, such as piperidinohexose reductone, preferably 0.2 to 1 mol / l, It is more preferable to use 0.3 to 0.6 mol / liter.

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 chemicals can be adjusted so that the pH of the developer is 8.5 to 11.5, preferably pH 9.5 to 1
Choose 0.5.

As a solubilizing agent, diethylene glycol, triethylene glycols and esters thereof can be contained, and as a sensitizer, a development accelerator such as a quaternary ammonium salt, a surfactant and the like can be contained.

The silver sludge inhibitor is described in JP-A-56-1981.
106244, JP-A-3-51844, 5-28
The compound described in No. 9255 is preferably used.

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

As the inorganic inhibitors, sodium bromide, potassium bromide, potassium iodide and the like can be contained.

In addition, L. F. A. Mason, "Photographic Processing Chemistry", Focal Press (1966), pp. 226-229, U.S. Pat. Nos. 2,193,015 and 2,592,364.
And those described in JP-A-48-64933. Examples of chelating agents for concealing calcium ions in tap water used in the treatment liquid include JP-A-1-19385.
The compound described in No. 3 is preferably used.

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

As the developing method in the present invention, it is preferable to use a developing solution containing substantially no hydroquinones and containing the compound represented by the general formula (V) and nitroindazole. And a stable image with high gradation can be obtained.

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

Preferred fixing solutions can include fixing materials commonly used in the art. Examples of the fixing agent include thiosulfates such as ammonium thiosulfate and sodium thiosulfate, and ammonium thiosulfate is particularly preferable in view of the 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 be one that forms an acidic hardening film. In this case, an aluminum compound is preferably used as a hardener. In addition, fixing solutions include preservatives, pH buffers, various acids and metal hydroxides.
An H adjuster or a water softener can be included.

Examples of the fixing accelerator include, for example,
No. 35754, No. 58-122535, No. 58-12
No. 2536 and U.S. Pat. No. 4,126,459.

The replenishment of the fixing solution during the fixing processing of the photographic material is preferably 50 to 150 ml, more preferably 65 to 130 ml per m ² of the photographic 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 a fine or granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is sprayed on the surface of the temporarily formed photographic processing agent. (See Japanese Patent Application Laid-Open Nos. 4-29136 and 4-8).
No. 5533, No. 4085534, No. 4-85535
Nos. 4-85536 and 4-172341).

A preferred tablet production method is a method in which a powdered solid processing agent is granulated and then subjected to a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet.

The granulation method for tablet formation is to use a known method such as tumbling granulation, extrusion granulation, compression granulation, 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. Further, the particle size distribution is
% Is preferably within a deviation of ± 100 to 150 μm.

When the obtained granules are compressed under pressure, known compressors such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine and a briquetting machine can be used. . The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity and handling, or from the problem of dust when used on the user side, a cylindrical type, so-called tablet Is preferred.

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

A method for producing a tablet processing agent is described in, for example,
Nos. 1-61837, 54-155038 and 52-
88025 and British Patent 1,213,808.

[0125] The bulk density of the solid processing agent is determined as follows from the viewpoint of its solubility and the effects of the object of the present invention.
Preferably 0~2.5g / cm ^3, in terms of the strength of the resulting solids greater than 1.0g / cm ^3, 2.5g / cm
^{A value of} less than ³ is more preferable from the viewpoint of the solubility of the obtained solid. When the solid processing agent is granules or powder, the bulk density is preferably from 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 light-sensitive material of the present invention, the total processing time (D
(ryto dry) is preferably processed in 10 to 45 seconds, more preferably in 15 to 30 seconds. Here, the time from the time when the tip of the photosensitive material to be processed is immersed in the developing tank liquid of the automatic developing machine to the time 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 solution (stabilizing solution), "Washing time" refers to the time of immersion in the washing tank solution, and "Drying time" refers to the time in the drying zone of the automatic processor. , The developing time is 3 to 15 seconds (further 3 to 10 seconds), the developing temperature is 25 to 50 ° C. (furthermore, 30 to 50 seconds).
40 ° C.), fixing time 2 to 12 seconds (further 2 to 10 seconds),
Fixing temperature: 20-50 ° C. (further 30-40 ° C.), water washing (stabilization) time: 2-15 seconds (further 2-8 seconds), water washing (stabilization) temperature: 0-50 ° C. (further 15-40 ° C.) ° C), drying time 3-12 seconds (further 3-8 seconds), drying temperature 35-
100 ° C (more preferably 40 to 80 ° C) is preferred.

The photosensitive material is developed, fixed and washed (or stabilized), dried with a squeeze roller after squeezing out water.

As an X-ray generator in the image forming method of the present invention, a commercially available X-ray generator can be used. Particularly, as an X-ray generator for mammography, an apparatus having a tube voltage of an X-ray generator tube of 40 kVp or less is commercially available. As a dedicated device for mammography,
Apparatus that removes continuous X-rays of 20 kVp or more that causes a decrease in contrast due to scattering by using Mo for the anode of the X-ray generating tube and further adds a Mo filter, and generates X-rays close to a single color including characteristic X-rays Is the mainstream. Further, there is also known an apparatus in which an Rh anode or a W (tungsten) anode is combined with an Rh filter in order to obtain a contrast in a breast having a high X-ray absorption and a high breast density or a thick breast. The focal size of the anode tends to be miniaturized.
Devices of 1 to 0.3 mm are common.

Preferred phosphors used for the X-ray fluorescent intensifying screen according to the present invention include the following.

A tungstate-based phosphor (CaWO)
_FourTerbium-activated rare earth oxysulfide-based phosphor [Y_TwoO
_TwoS: Tb, Gd_TwoO_TwoS: Tb, La_TwoO_TwoS: Tb,
(Y, Gd)_TwoO_TwoS: Tb, etc.], terbium-activated rare earth
Phosphate phosphor (YPO_Four: Tb, GdPO_Four: Tb
Etc.), Terbium-activated rare earth oxyhalide-based fluorescence
Body (LaOBr: Tb, GdOBr: Tb, etc.)
Activated rare earth oxyhalide phosphor (LaOB)
r: Tm, etc.), barium sulfate-based phosphor (BaSO_Four: E
u^{Two +}Etc.) divalent europium activated alkaline earth metal phosphorus
Phosphate-based phosphor [Ba_Three(PO _Four)_Two: Eu²⁺Etc.)
Europium activated alkaline earth metal fluoride halide system
Phosphor (BaFCl: Eu)²⁺, BaFBr: Eu
²⁺Etc.), iodide-based phosphors (CsI: Na, CsI: Tl
Etc.), sulfide-based phosphor [ZnS: Ag, (Zn, Cd)
S: Ag etc.], hafnium phosphate-based phosphor (HfP_TwoO₇:
Cu etc.).

However, the phosphor used in the present invention is not limited to these. Of these, terbium-activated gadolinium oxysulfide (Gd ₂ O
₂ S: Tb) are preferred in which the phosphor.

The average particle diameter of each layer of the phosphor particles 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. More preferably, 0 in each layer.
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 135μ
m or more, but preferably 150 to 250 μm.

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

The X-ray fluorescent intensifying screen used in the combination of the present invention has an X-ray absorptivity of 4 by increasing the filling rate of the phosphor particles.
It is at least 5%, but preferably at least 50%.
Incidentally, the X-ray absorption amount is obtained as follows. That is, 3
X-rays generated from a tungsten target operated at 80 kVp from an X-ray generator equivalent to 2.2 mm of aluminum with an intrinsic power of 2.2 mm and a purity of 99 mm with a thickness of 3 mm with phase power supply
% Or more through an aluminum plate 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 a position 50 cm after 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 for the X-ray fluorescent intensifying screen include thermoplastic elastomers. Specifically, polystyrene, polyolefin, polyurethane,
Polyester, polyamide, polybutadiene, ethylene-vinyl acetate, polyvinyl chloride, natural rubber, fluorine rubber,
Examples include at least one thermoplastic elastomer selected from the group consisting of polyisoprene, chlorinated polyethylene, styrene-butadiene rubber, and silicone rubber.

[0137]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these embodiments. Unless otherwise specified, “%” in the examples represents “% by mass”.

Example 1 All the emulsions shown below were prepared in a reaction vessel having a volume of 32 liters. As an ultrafiltration unit, Asahi Kasei SIP-1013, and as a circulating pump, DAID
O Rotary Pump was used. The volume of the emulsion circulation portion of the ultrafiltration step was 1.2 liters, and the emulsion was circulated at a constant flow rate of 15 liters / minute. Therefore, the residence time of the reactant solution was 4.8 seconds, and the volume of the emulsion circulation portion in 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 was circulated to the ultrafiltration device so as to maintain the average interparticle distance at the start of the particle growth step-1 over the entire region of the above, and concentration was performed.

(Preparation of emulsion Em1) [Nucleation step] The following gelatin solution B-10 in a reaction vessel
1 at 30 ° C. and 0.5 mol / L while stirring at 450 rpm using the mixing and stirring apparatus of FIG.
The pH was adjusted to 1.96 with sulfuric acid. Thereafter, the S-101 solution and the X-101 solution were added at a flow rate of 5.0 ml / sec by using the double jet method to form nuclei. (B-101) Low molecular weight gelatin (average molecular weight: 20,000) 32.4 g Potassium bromide 9.92 g Water 12938.0 ml (S-101) Silver nitrate 50.43 g Water 225.9 ml (X-101) Potassium bromide 35. 33 g water 224.7 ml [Aging step] After the addition was completed, 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 at 20 ° C. for 20 minutes. 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 is added thereto and p
H 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 measured for 10 m using a 1 mol / L potassium bromide solution.
V. (G-101) Alkali-treated inert gelatin (average molecular weight 100,000) 139.1 g 10% methanol solution of compound A 3.20 ml water 3266.0 ml A: HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O]
_19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) [Grain growth step-1] After ripening, the flow rates of the S-102 solution and the X-102 solution are accelerated by using a double jet method. While (the ratio of the addition flow rate at the end and the start time is about 12 times)
Added in 38 minutes. After the addition is completed, the G-102 solution is added, the stirring speed is adjusted to 550 rpm, and subsequently the S-103 solution and the X-103 solution are accelerated while increasing the flow rates (the addition flow rate 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 10 mV using a 1 mol / L potassium bromide solution. (S-102) silver nitrate 639.8 g water 2866.2 ml (X-102) potassium bromide 448.3 g water 2850.7 ml (G-102) alkali-treated inert gelatin (average molecular weight 100,000) 203.4 g of compound A 10% methanol solution 6.20 ml water 1867.0 ml (S-103) silver nitrate 989.8 g water 1437.2 ml (X-103) potassium bromide 679.6 g silver iodide fine grain emulsion (* below) 0.057 mol water 1412 0.0 ml [Particle growth step-2] After the completion of the addition, the solution temperature in the reaction vessel was lowered to 40 ° C over 20 minutes. afterwards,
After adjusting the silver potential in the reaction vessel to −22 mV using a 3.5 mol / L potassium bromide aqueous solution, the S-104 solution and the X-104 solution were accelerated while increasing the flow rates (addition at the end and at the start). (The flow rate ratio was 1.2 times). (S-104) Silver nitrate 672.0 g Water 975.8 ml (X-104) Potassium bromide 470.8 g Water 959.4 ml After completion of the above growth, a desalting and washing treatment was performed according to a conventional method.
Add gelatin and disperse well.
8. The pAg was adjusted to 8.1.

The obtained emulsion Em1 had an average grain thickness of 0.1 mm.
It was a hexagonal tabular particle having a particle diameter of 16 μm, an average particle diameter of 1.20 μm, an average aspect ratio of 7.5, and a volume coefficient of variation of 0.09. The standard deviation of the intergranular silver iodide content of this emulsion was 19%.

* Preparation of silver iodide fine grain emulsion A 2000 ml aqueous solution containing 36 g of gelatin was stirred at 40 ° C. After adjusting the silver potential to -150 mV with respect to the saturated calomel electrode using an aqueous KI solution, silver nitrate (178
g) An aqueous solution and a potassium iodide (174 g) aqueous solution were added over 13 minutes while accelerating the flow rate by a double jet method. After desalting, gelatin was added at 50 ° C. to pH 6.8,
Adjusted to pAg9. This silver iodide fine grain emulsion had an average equivalent circle diameter of 0.05 μm.

(Preparation of Emulsions Em2 to Em5) A solution of silver halide 1 in the finished emulsion was added to a potassium bromide solution X-104.
Em2 to Em5 were obtained in the same manner as in Em1, except that the metal compounds shown in Table 1 were added per mol in the amount shown in Table 1.
The variation coefficient of the average particle thickness, the average particle diameter, the average aspect ratio, and the volume particle size were all the same as Em1.

(Chemical sensitization and spectral sensitization)
After adjusting m1 to Em5 to 60 ° C., the sensitizing dye (compounds and amounts shown in Table 1) was added as a dispersion in the form of solid fine particles. After 10 minutes, an aqueous solution of adenine, ammonium thiocyanate, chloroauric acid, sodium thiosulfate, and a dispersion of triphenylphosphine selenide were added, followed by 3 more minutes.
After 0 minute, silver iodide fine grains were added and ripening was performed for a total of 2 hours. At the end of ripening, the stabilizer (ST-1) and a predetermined amount of gelatin were added.

ST-1: 4-hydroxy-6-methyl-
The amount added per mole of 1,3,3a, 7-tetrazaindene silver halide is shown below.

Sensitizing dyes (compounds of general formulas (I) and (II) described in Table 1) Amounts described in Table 1 Adenine 10 mg Ammonium thiocyanate 60 mg Chloroauric acid 10 mg Sodium thiosulfate 4.0 mg Triphenylphosphine selenide 1. 0 mg silver iodide fine grain emulsion (same as above) 0.1 mmol Stabilizer (ST-1) 600 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 is
It was obtained by adding to water adjusted to 7 ° 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, triphenylphosphine selenide 12
0 g was added into 30 kg of ethyl acetate at 50 ° C. and completely dissolved by stirring. On the other hand, 3.8 kg of photographic gelatin
Was dissolved in 38 kg of pure water, and 93 g of a 25% aqueous solution of sodium dodecylbenzenesulfonate was added. Then, these two liquids were mixed and dispersed at 50 ° C. for 30 minutes at 50 ° C. at a peripheral speed of the dispersion blade of 40 m / sec by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3% or less. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg.
A part of the dispersion thus obtained was fractionated and used in the above Examples.

Sensitized emulsions E1 to E thus obtained
Table 1 shows the contents of No. 10.

[0148]

[Table 1]

(Preparation of Emulsion Layer Coating Solution) The following various additives were added to each emulsion obtained above (per mole of AgX).

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 5.0 g resorcin-4 - sodium sulfonate 400 mg 2-mercapto-5-sulfonic acid _{10mg C 4 H 9 OCH 2 CH} (OH) CH 2 N (CH 2 COOH) 2 650mg compound of general formula (III) (described in Table 2) Table 2 described amount Compound of general formula (IV) (described in Table 2) Table 2 described amount (Preparation of coating solution for protective layer on emulsion layer side) Hereinafter, all are shown in terms of weight per 1 m ² after coating.

Gelatin 0.9 g Matting agent (PMMA having an average particle size of 4 μm) 30 mg Hardening agent (CH ₂ = CHSO ₂ CH ₂ CONHCH ₂ −) ₂ Addition amount is adjusted so that the swelling ratio becomes 150%. -1) 7 mg Compound (S-2) 40 mg Compound (S-3) 5 mg Backing layer (Preparation of antihalation dye layer solution) Gelatin 2.1 g Dye (D-1) 35 mg Dye (D-2) 35 mg Dye (D -3) 35 mg (Preparation of coating solution for protective layer) Gelatin 0.9 g Matting agent (PMMA having an average particle diameter of 5 μm) 100 mg Compound (S-1) 7 mg Compound (S-2) 50 mg Compound (S-3) 6 mg Hard film Agent (CH ₂ = CHSO ₂ CH ₂ CONHCH _2- ) ₂ Adjust the amount of addition so that the swelling ratio becomes 150% S-1: Dihexyl sodium sulfosuccinate _{S-3: C 8 F 17} SO 2 N (C 3 H 7) (CH 2 CH 2 O) 15
H PMMA: polymethyl methacrylate

[0152]

Embedded image

(Coating of Light-Sensitive Material Sample) Using these coating solutions, a silver amount of 3.0 g / m ² was applied to one surface of the support.
Emulsion protective layer so that the amount of gelatin was 0.9 g / m ² ,
On the other side, an antihalation dye layer and a protective layer were coated with a glycidyl methacrylate / methyl acrylate / butyl methacrylate copolymer (50/10/40%) at a concentration of 10% using two slide hopper coaters. % Of a copolymer dispersion obtained by diluting to a concentration of 0.1% by weight and applied to both sides of a blue-colored polyethylene terephthalate support having a thickness of 175 μm and applied and dried as a subbing liquid at a rate of 12 / min.
Coating was performed simultaneously at a speed of 0 m, and drying was performed for 2 minutes and 20 seconds to prepare photosensitive material samples 1 to 28.

(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 in a fluidized bed drier to remove almost completely the water content of the granulated material. [Granulated material (B)] 9500 g of potassium carbonate and 6.0 g of potassium iodide were each averaged in a commercially available bantam mill at an average of 10 g.
Grind to μm. These fine powders and DTPA-N
a 170 g, sodium sulfite 425 g, 5-mercapto- (1H) -tetrazolylacetic acid Na salt 8.3 g, 1-
(3-Sulfophenyl) -5-mercaptotetrazole Na salt (40 g), 5-nitroindazole (3.0 g), binder mannitol (1500 g), and D-sorbitol (600 g) were added and mixed at room temperature for about 3 minutes in a commercially available stirring granulator. , 1
After granulating by adding 25 ml of water over 1 minute, the granulated product is dried at 40 ° C. for 2 hours with a fluidized drier to remove the moisture of the granulated product almost completely.

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 amount to be 0 liter) was sealed in a moisture-proof bag in which polyethylene terephthalate was vapor-deposited with aluminum.

Development starter formulation (addition amount per liter of developer) N-acetyl-DL-penicillamine 0.11 g diethylene glycol 48.5 g sodium 5-mercapto-1H-tetrazolyl acetate 0.12 g 90% acetic acid 11.5 g potassium bromide 9.0 g Make up to 67 ml with pure water.

As the automatic developing machine, TCX-701 (manufactured by Konica) was used. At the start, 7.8 liters of the developing solution in which the 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 starter was added in an amount of 67 ml / liter of the developing solution, which was equivalent to the capacity of the developing tank of 7.8 liter.

The fixing solution is TC-DF701 (manufactured by Konica).
Was prepared and placed in a fixing tank of TCX-701 to be used as a starting solution.

As the developing replenisher and fixing replenisher, the above-mentioned developer and fixing agent were used. P when the developer is dissolved
H was 10.15, and the pH when the starter was added was 9.
90. The dissolution pH of the fixing solution was 4.25.

Development temperature 34 ° C. (replenishment rate is 100 ml / m
² ) Fixing temperature: 34 ° C. (replenishment rate: 100 ml / m ² ), water: 18 ° C. (5 l / min), drying temperature: 55 ° C., processing time: 45 seconds, and the following evaluations were made.

<< Evaluation of Sensitometry >> A sample film was prepared by setting the emulsion surface to an X-ray fluorescent intensifying screen M-1 for mammography.
00 (made by Konica Corp.) and the inside of the cassette. X-ray irradiation was performed after standing for 10 minutes in order to keep the adhesion high and constant. As an X-ray generator, a product of Toshiba Corporation (ROTANODE) was used, and irradiation was performed at a tube voltage of 27 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 is
cm. After the development processing, a sensitometry curve was prepared by a distance method, and the sensitivity, fog, and gradation were determined. The value of the sensitivity was determined as the reciprocal of the X-ray dose required to obtain a density of fog + 1.0, and the relative sensitivity was evaluated with the value of the film of Sample 1 as 100. The gradation is expressed as fog + 0.25 in a characteristic curve on coordinates where the logarithm of the X-ray exposure amount is plotted on the horizontal axis and the optical density is plotted on the vertical axis, and the unit length is made equal.
And a line connecting the point of fog +2.0 and the angle formed by the horizontal axis is represented by tan θ when θ is θ.

<< Evaluation of Scratch Resistance >> An unexposed film sample was allowed to stand at 23 ° C. and RH (relative humidity) of 40% for 2 hours.
After rubbing with a load of g / cm ² , processing was performed with an automatic developing machine under the above conditions, and a four-stage evaluation was performed by visual observation.

A: Almost no scratches B: Some scratches but no problem in practical use C: Scratches appear to the extent that they are noticeable, which is a problem in practical use D: Very large scratches and wide scratches Thick and dense <Evaluation of fingerprint trace resistance> Under conditions of 23 ° C. and RH of 50%, the unexposed sample film was gently pressed with a finger for 3 seconds. Exposure / development processing was carried out so as to be 0.0. The resulting sample was visually inspected for the following 4
It was evaluated on a scale.

A: Almost no fingerprint mark B: Slight fingerprint mark when viewed closely C: Fingerprint mark is generated to the extent that it is conspicuous D: Fingerprint mark is very strong, which is a problem in practical use. Diagnostic Ability Evaluation> A film sample was placed in a cassette containing a sample in the same apparatus as in the sensitometry evaluation, and the film was placed in a KYOKO15.
A 6-mamma phantom (manufactured by Kasei Optonics Co., Ltd.) was closely attached and photographed, and a tumor image, a microcalcification image, and a fiber image were visually evaluated, and a comprehensive diagnostic ability was ranked on a 4-point scale. The evaluation criteria are as follows.

A: All are clearly visible B: All are sufficiently visible C: Some images are hard to see D: All images are hard to see The results are shown in Tables 2 and 3.

[0166]

[Table 2]

[0167]

[Table 3]

The samples of the present invention were excellent in all evaluations.

[0169]

Industrial Applicability According to the present invention, a silver halide photographic material for X-ray mammography, which has high contrast, excellent diagnostic performance, and good scratch and fingerprint resistance, a method for processing the same, and a method for using the same. X-ray image forming method.

[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 particle addition line 31,32 Fine particle addition valve

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) G03C 1/035 G03C 1/035 HM 1/09 1/09 1/16 1/16 1/18 1 / 18 1/29 1/29 5/17 5/17 5/26 520 5/26 520 5/30 5/30 5/305 5/305

Claims (15)

[Claims] 1. A support comprising at least one photosensitive silver halide emulsion layer on one side of a support, a non-photosensitive colloid layer above the silver halide emulsion layer, and a backing layer on the opposite side. Wherein at least one of the silver halide emulsion layers has at least 50% of the total projected area doped with at least one metal ion selected from Rh, Ru, Re, and Os. Ratio 3
Silver halide photographic light-sensitive materials, characterized by comprising tabular silver halide grains of from 1 to 30 and containing compounds represented by the following general formulas (I), (II) and (III): . Embedded image Wherein R ₁ and R ₂ each represent an alkyl group. However, at least one of R ₁ and R ₂ is an alkyl group having a sulfo group. R ₃ represents a lower alkyl group. R ₄ ,
R ₅ , R ₆ and R ₇ are each a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, an aryl group, a carboxyl group, an alkoxycarbonyl group,
Represents a cyano group, a trifluoromethyl group, an amino group, an acylamide group, an acyl group, an acyloxy group, an alkoxycarbonylamino group or a carboalkoxy group. R ₄ and R ₅ , R
₆ and R ₇ may be linked together to form a naphthoxazole nucleus. [Chemical formula 2] [Wherein, Z ₁ and Z ₂ are each a thiazole nucleus, a thiazoline nucleus, an oxazole nucleus, a selenazole nucleus, an imidazole nucleus, a pyridine nucleus, a benzimidazole nucleus, a benzoxazole nucleus, and a benzothiazole nucleus. , A benzoselenazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus, and a nonmetallic atomic group necessary for forming a naphthoselenazole nucleus. R ₈ and R ₉ each represent an alkyl group having a sulfo group. [Chemical formula 3] Wherein, X ₁ represents an adsorption accelerating group to silver halide, L ₁
Represents a divalent linking group, and m represents 0 or 1. R ₁₀ , R
₁₁ and R ₁₂ each represent an electron-donating substituent, which may be the same or different, and may combine with each other to form a ring. ] 2. A support comprising at least one photosensitive silver halide emulsion layer on one side of a support, a non-photosensitive colloid layer above the silver halide emulsion layer, and a backing layer on the opposite side. Wherein at least one of the silver halide emulsion layers has at least 50% of the total projected area doped with at least one metal ion selected from Rh, Ru, Re, and Os. Ratio 3
Silver halide photographic light-sensitive materials, comprising: silver halide grains having a particle size of from 1 to 30, and containing compounds represented by the above general formulas (I), (II) and (IV). material. Embedded image Wherein, X ₂ represents an adsorption promoting group to silver halide, L ₂
Represents a divalent linking group, and n represents 0 or 1. R ₁₃ and R ₁₄ each represent a hydroxyl group or a substituted or unsubstituted amino group, and R ₁₅ represents a hydrogen atom or a group that can be substituted on a benzene ring. ] 3. The silver halide grains according to claim 1, wherein the tabular silver halide grains are grown by ultrafiltration while appropriately extracting a salt-containing solution from a reaction solution during the growth process. The silver halide photographic light-sensitive material according to claim 1 or 2, wherein 4. A silver halide photographic light-sensitive material according to claim 1, wherein the tabular silver halide grains have a coefficient of variation of a volume particle size of 0.10 or less. 5. The silver halide photographic material according to claim 1, which is substantially free of hydroquinones and contains a compound represented by the following formula (V) and nitroindazole. A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed using a developing solution contained therein. Embedded image [Wherein, R ₁₆ and R ₁₇ each represent a hydroxyl group, a mercapto group, a substituted or unsubstituted amino group, an acylamino group, 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. ] 6. The method for processing a silver halide photographic material according to claim 5, wherein the developing solution is a solution in which a solid developer is dissolved. 7. The method for processing a silver halide photographic material according to claim 6, wherein the solid developer is a tablet. 8. The surface of the silver halide photographic light-sensitive material according to claim 1, wherein the surface of the silver halide emulsion layer having the silver halide emulsion layer is in close contact with the surface of the fluorescent intensifying screen having the phosphor layer. After irradiating the transmitted X-rays, developing, fixing,
An image forming method, wherein an X-ray image is formed by washing and drying. 9. The image forming method according to claim 8, wherein the phosphor of the fluorescent intensifying screen is terbium-activated gadolinium oxysulfide. 10. An image forming method according to claim 8, wherein the developing is the processing method according to claim 5, 6, or 7. 11. The image forming method according to claim 9, wherein the developing is the processing method according to claim 5, 6, or 7. 12. The image forming method according to claim 8, wherein the X-ray has a tube voltage of 40 kVp or less. 13. The silver halide photographic material according to claim 1, which is used for X-ray mammography. 14. The method for processing a silver halide photographic material according to claim 5, wherein the method is for X-ray mammography. 15. The image forming method according to claim 8, wherein the method is for X-ray mammography.