JP2002287281A - Silver halide photographic sensitive material, processing method and x-ray image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material for X-ray mammography having high contrast, superior diagnostic ability and good scratch and fingerprint resistances and to provide a processing method for the material and an X-ray image forming method using those. SOLUTION: In the silver halide photographic sensitive material having at least one photosensitive silver halide emulsion layer on one face of the base, a colloidal layer on the side of the silver halide emulsion layer remoter from the base and a backing layer on the other face of the base, >=50% of the total projected area of silver halide grains contained in the at least one silver halide emulsion layer is occupied by flat platy silver halide grains containing a specified sensitizing dye, doped with ions of a heavy metal such as Rh and having an aspect ratio of 3-30 and a specified polymer is contained in the colloidal layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material having a light-sensitive silver halide emulsion layer on one side of a support and a backing layer on the other side. In particular, the present invention relates 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] As a means of increasing contrast, a method of doping silver halide grains with a metal ion such as rhodium, ruthenium, rhenium, osmium or a metal complex ion has conventionally been known. Most of these technologies are for obtaining ultra-high contrast characteristics as a photosensitive material for printing, and have a large content of rhodium salt, but by reducing rhodium salt,
It is possible to adjust the gradation suitable for mammography, which is the object of the present invention. For example, JP-A-6-102
No. 613 describes 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. However, photosensitive materials using silver halide particles doped with metal ions such as rhodium, ruthenium, rhenium and osmium or metal complex ions are liable to scratch, and desensitization due to the attachment of fingerprints (so-called fingerprint marks). It was found that it was easy to occur. In mammography, as described above, it is important for diagnosis to read low-density fine dot-like, streak-like, glass-like, etc. images as calcified images. Outbreaks can lead to misdiagnosis.

On the other hand, tabular silver halide grains are known to easily obtain high sensitivity and have high covering power, and have been used in a wide variety of photosensitive materials due to their excellent properties. However, it was found that when tabular silver halide grains were doped with a rhodium salt or the like in order to increase the gradation, the scratch resistance and the 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 rhodium, ruthenium, osmium and iridium, in which rhodium and the like are desensitizers. It describes that by using particles having the same particle size in mixture, gradation can be formed in a wide exposure range, and processing fluctuation and gradation preservation 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, none of these publications disclose the scratch resistance and fingerprint mark resistance required of the photosensitive material for mammography which is the object of the present invention.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide high contrast, excellent diagnostic performance, abrasion resistance,
An object of the present invention is to provide a silver halide photographic light-sensitive material for X-ray mammography having excellent fingerprint trace resistance, a processing method thereof, and an X-ray image forming method using the same.

[0008]

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

(1) At least one photosensitive silver halide emulsion layer on one side of a support, and a non-photosensitive colloid layer on the side of the silver halide emulsion layer farther from the support, and on the opposite side In the silver halide photographic light-sensitive material having a backing layer on the surface of the silver halide emulsion, silver halide grains contained in at least one of the silver halide emulsion layers account for at least 50% of the total projected area of Rh, Ru, Re, and Os. Are tabular silver halide grains having an aspect ratio of 3 or more and 30 or less doped with at least one metal ion, and containing a compound represented by the general formula (1) and the general formula (2); And a silver halide photographic material, wherein the non-photosensitive colloid layer contains a polymer represented by the general formula (3).

(2) 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. 2. The silver halide photographic material as described in 1 above.

(3) The silver halide photographic light-sensitive material as described in (1) or (2) above, wherein the tabular silver halide grains have a coefficient of variation in volume particle size of 0.10 or less.

(4) The silver halide photographic light-sensitive material according to any one of the above (1) to (3), which is substantially free of hydroquinones, is a compound represented by the above general formula (4), and nitroindazole. And developing using a developer having a bromine ion concentration of at least 10 g / l in terms of potassium bromide.

(5) The method for processing a silver halide photographic light-sensitive material as described in (4) above, wherein the developer is a solution in which a solid developer is dissolved.

(6) The method for processing a silver halide photographic material as described in (5) above, wherein the solid developer is a tablet.

(7) The surface having the silver halide emulsion layer of the silver halide photographic light-sensitive material according to any one of the above items 1 to 3, is adhered to the surface having the phosphor layer of the X-ray fluorescent intensifying screen. After irradiating X-rays that have passed through the subject, it is developed with an automatic processor,
An X-ray image forming method comprising forming an X-ray image by fixing, washing, and drying.

(8) The X-ray image forming method as described in (7) above, wherein the phosphor of the X-ray fluorescent intensifying screen is terbium-activated gadolinium oxysulfide.

(9) When developing with an automatic developing machine,
9. The method for forming an X-ray image according to the above item 7 or 8, wherein the method for processing a silver halide photographic light-sensitive material according to any one of the above items is used.

(10) The method of forming an X-ray image as described in any one of (7) to (9) above, wherein X-rays having a tube voltage of 40 kVp or less are used.

(11) The silver halide photographic material as described in any one of (1) to (3) above, which is for X-ray mammography.

(12) The method for processing a silver halide photographic material as described in any one of (4) to (6) above, which is for X-ray mammography.

(13) The X-ray image forming method as described in any one of (7) to (10) above, which is for X-ray mammography.

Hereinafter, the present invention will be described in detail. The silver halide grains used in the present invention have an aspect ratio of 3 or more and 3 or more.
0 or less tabular silver halide grains. 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 in Photographi.
she Korrespondenz, Vol. 99, p. 99,
It is described in detail in 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 of the area-converted particle diameter to 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 silver halide grains is a value defined by the following equation 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.

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

Coefficient of variation of areal grain size = (standard deviation of areal grain size / average of areal grain size) The silver halide emulsion relating to the present invention is obtained by mixing all of the silver halide grains contained in the silver halide emulsion. 50% of projected area
The above are preferably tabular silver halide grains having an average aspect ratio of 3.0 to 30 (hereinafter also simply referred to as aspect ratio), and 50% or more of the total projected area has an aspect ratio of 4 to 20. The silver halide grains are more preferably tabular silver halide grains, and particularly preferably tabular silver halide grains having an aspect ratio of 5 to 15. 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 such that the main plane of the tabular grains contained therein 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 silver halide emulsion is preferably silver iodobromide having an average silver iodide content of 2 mol% or less, more preferably an average silver iodide content of 1 mol% or less. Molar% or less is particularly preferred. 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 prepared at 1.33 × 10 ⁻² Pa
-155 ° C. in an ultra-high vacuum of (1 × 10 ⁻⁴ torr) or less
After cooling to below, MgKa was irradiated as a probe X-ray at an X-ray source current of 40 mA, and Ag3d5 / 2, Br3d,
It measures about I3d3 / 2 electron. 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.

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 (the 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 mol.
The range of ^-8 is more preferable.

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 general formula [ML ₆ ] ^p -wherein, M represents a metal ion selected from Rh, Ru, Re, and Os, L represents a bridging ligand, and p represents 0, 1, 2, 3, or 4. Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate,
Terrocyanate, each ligand of azide and aquo, nitrosyl, thionitrosyl and the like, preferably aquo,
And 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.

[0039] 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) Cl (CN) 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: ## s (NS) Cl (SCN) 4 ] ^2- These metal complexes preferably used as a salt of a complex of potassium, sodium, ammonium salts or cesium salts.

The compound which provides 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 and growth , Physical aging,
Although it may be added at any stage before and after chemical sensitization, 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 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.
Compound and active gelatin, sulfur sensitization method, 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.

Next, the general formulas (1) and (2)
The compound represented by is described. The compounds represented by the general formulas (1) and (2) are cyanine dyes, which are a kind of spectral sensitizing dyes, and are most suitable for the image forming method of the present invention by the compounds represented by the general formula (1). Spectral sensitization to the photosensitive wavelength is possible.

In the general formula (1), R ₁ and R ₂ each represent an alkyl group having 1 to 8 carbon atoms (eg, a methyl group,
Ethyl group, n-propyl group, etc., substituted alkyl group (for example, vinylmethyl group, 2-hydroxyethyl group, 4-hydroxybutyl group, 2-acetoxyethyl group, 3-acetoxypropyl group, 2-methoxyethyl group, -Butoxybutyl, 2-carboxyethyl, 3-carboxypropyl, 2- (2-carboxyethoxy) ethyl, p-carboxybenzyl, 2-sulfoethyl,
3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3-sulfopropyl group,
2- (3-sulfopropoquin) ethyl group, 2-acetoxy-3-sulfopropyl group, 3-methoxy-2- (3-
Sulfopropoxy) propyl group, 2- [2- (3-sulfopropoxy) ethoxy] ethyl group, 2-hydroxy-
3- (3′-sulfopropoxy) propyl group, p-sulfophenethyl group, p-sulfobenzyl group, etc., and aralkyl difference (eg, benzyl group, phenylethyl group, etc.). 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 having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, etc.).

R ₄ , R ₅ , R ₆ and R ₇ are each a hydrogen atom,
Preferably, a lower alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group, etc.), a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom), an alkoxy group (eg, a methoxy group) Ethoxy group), hydroxyl group, aryl group (eg, phenyl group, p-sulfophenyl group, etc.), carboxy group, alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxydicarbonyl group, etc.), cyano group, trifluoromethyl group Amino group, lower alkyl-substituted amino group (eg, methylamino group, dimethylamino group, etc.), acylamide group (eg, acetamido group, etc.), acyl group (eg, acetyl group, etc.), acyloxy group (eg, acetoxy group, etc.), alkoxycarbonyl Amino group (for example, ethoxycarbonylamino group, etc. Represents a carboalkoxy group (e.g., carboethoxy group, etc.). R ₄ and R ₅ , and R ₆ and R ₇ are linked to each other to form a naphthooxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3- d] Oxazole).

In the general formula (2), Z ₁ and Z ₂
Represents a non-metallic atomic group necessary for completing the next heterocyclic nucleus.

Thiazole nucleus (this nucleus is a lower alkyl group,
Aryl group, halogen atom, lower alkoxy group, carboxy group, lower alkoxycarbonyl group, aralkyl group,
It may have a group such as a trifluoromethyl group or a hydroxyl group, for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, benzothiazole, 4-chlorobenzothiazole , 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole,
5-bromobenzothiazole, 6-bromobezothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 4-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5 -Ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4- Phenylbenzothiazole, 5-phenylbenzothiazole, naphtho [2,1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1, -d] thiazole, 7-Etokishinafuto [2,1-d] thiazole, 8-methoxynaphth [2,1-d] thiazole, 5-methoxynaphth [2,
1-d] thiazole, 5-methoxynaphtho [2,3-
d] Thiazole and the like).

Thiazoline nucleus (this nucleus may have a group such as a lower alkyl group; for example, thiazoline, 4-methylthiazoline and the like), oxazole nucleus (this nucleus is a lower alkyl group, a halogen atom, an aryl group, a lower alkoxy group) , A trifluoromethyl group, a hydroxyl group, a carboxyl group, or the like; for example, oxazole, 4-methyloxasol, 4-ethyloxazole, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, Bromobenzoxazole, 5-fluorobenzoxazole, 5-
Phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, 6-methoxybenzoxazole Hydroxybenzoxazole,
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 group such as a lower alkyl group, an aryl group, a halogen atom, a lower alkoxy group, a hydroxyl group, etc .;
Methyl selenazole, 4-phenyl selenazole, benzo selenazole, 5-chlorobenzo selenazole, 5-
Methoxybenzo-selenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole, etc.), 3,3-di-lower alkylindolenine A nucleus (this nucleus may have a group such as a cyano group, a lower alkyl group, 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-
Chlorindolenine, etc.), imidazole nucleus (this nucleus may have a group such as a lower alkyl group, an aryl group, a halogen atom, a lower alkoxy group, a cyano group, a trifluoromethyl group, an allyl group; for example, 1-methyl Imidazole, 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 group 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 for R ₁ or R ₂ . Next, the compounds represented by the general formulas (1) and (2) are exemplified, but the compounds used in the present invention are not limited thereto.

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

The amount of the compound represented by the general formula (2) is preferably 0.01 to 1 mmol per 1 mol of the photosensitive silver halide.
More preferably, it is 0.1 mmol to 0.6 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 have been used. Specific examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol, and 2-ethoxyethanol.

In the present invention, the effect is increased by adding the compound as an acidic solution or a dispersion of solid fine particles, as compared with the case where the compound is added 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 dispersed in an aqueous system substantially free of an organic solvent and / or a surfactant.

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, aminostilbene compounds substituted with a nitrogen-containing heterocyclic nucleus group (for example, US Pat.
933,390 and 3,635,721), aromatic organic acid formaldehyde condensate (for example, described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like. Good.

The compound represented by the general formulas (1) and (2) according to the present invention may be added at the time of the chemical ripening step.
Particularly preferably, it can be carried out before the start of chemical ripening, and can be added during the nucleation step of the silver halide emulsion according to the present invention until the end of the desalting step, thereby obtaining a high-sensitivity halogen with excellent spectral sensitizing efficiency. A silver halide emulsion is obtained.

Next, the polymer represented by the general formula (3) will be described. In the formula, Rf represents an alkyl group containing at least one fluorine atom, and has 3 to 1 carbon atoms.
It is preferably 5, more preferably 4 to 10, and particularly preferably 4 to 7.

L ₁ and L ₂ each represent a mere bond or a linking group, and the linking group represents a hetero atom, a carbonyl group, an amide group, or an alkylene group bonded thereto, for example, an oxyalkylene group. As the hetero atom, nitrogen, oxygen and sulfur atoms are preferred.

Xp represents hydrogen, a hydroxy group, an anionic group, a cationic group, or an amphoteric group, and the anionic group is preferably a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Preferred are alkali metal ions, ammonium ions and the like. The cationic group is preferably a quaternary alkylammonium group, and the counter anion is preferably a halide ion, p-toluenesulfonic acid ion or the like.

The amphoteric group is preferably a group in which the above-mentioned cationic group and anionic group are bonded. R ₁₀ and R ₁₁ represent hydrogen or a lower alkyl group such as a methyl group or an ethyl group. m and n each represent a polymerization molar ratio, and m + n = 1.0, preferably 0.3 ≦ m ≦ 0.9, 0.1 ≦ n ≦ 0.
7

In the present invention, a plurality of different monomers containing an Rf group may be copolymerized, or a plurality of different monomers containing an Xp group may be copolymerized. That is, for example, Rf1, Rf2, Rf3, ··· , L 11,
_{L 12, L 13, ···,} R 101, R 102, R 103, ···,
Xp1, Xp2, Xp3, ···, L 21, L 22, L 23,
..., _R111 , _R112 , _R113 , ..., m = m1 + m
, N = n1 + n2 + n3 +..., And a plurality of anionic groups, cationic groups, nonionic groups, and amphoteric groups may be present.

The weight average molecular weight of the polymer in the present invention is 150,000 or less, preferably 5,000 to 100,000. When the molecular weight is larger than the above, the viscosity of the coating solution for the photographic constituent layer is increased and the wet strength of the coating film is decreased, which is not preferable.

Specific examples of the polymer represented by the general formula (3) are shown below, but the polymer which can be used in the present invention is not limited to these.

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The synthesis method of the above-mentioned fluorine-based surfactant is described in JP-A-10-501591 and JP-A-11-5043.
No. 60 and JP-A-2000-263714 can be referred to.

The compound represented by the general formula (3) of the present invention is contained in the hydrophilic colloid layer farther from the support than the silver halide emulsion layer. , Protective layer, intermediate layer, filter layer, etc.
In particular, it is preferably contained in a protective layer furthest from the support. The amount of addition is not limited, but is 0.001 to
1 g / m ² is preferable, and more preferably 0.002 to
0.2 g / m ² .

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 (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.), polystyrene (syndiotactic polystyrene (SPS), etc.) can be used. For photosensitive materials for medical diagnosis, which is the object of the present invention, 160-
A PET support having a thickness of 180 μm is preferred. The support may be colored as long as the transparency is maintained,
Blue coloring of about 0.1 to 0.2 is preferable because it can reduce eye fatigue in transmission image observation by sharksten. In addition, the support is usually subjected to an undercoating treatment in order to provide adhesion between the constituent layer applied 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 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 above-mentioned 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 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. Additive RD17643 RD18716 RD308119 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 28 XVII 1009 XVII The preferred developer for developing the photosensitive material is As, JP-A-4-15641, JP-4-1
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 1-phenyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3 -Pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone and the like, and the compound of the above general formula (4) can be used.

In the general formula (4), R ₁₂ and R ₁₃ are each independently a hydroxyl group, a mercapto group, an amino group (an amino group is an alkyl group having 1 to 10 carbon atoms such as methyl,
Ethyl, n-butyl, hydroxyethyl groups and the like as substituents), acylamino groups (eg, acetylamino, benzoylamino groups), alkylsulfonylamino groups (eg, methanesulfonylamino groups), arylsulfonylamino groups (For example, benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (for example, methoxycarbonylamino group, etc.), and alkylthio group (for example, methylthio, ethylthio group, etc.).

Preferred examples of R ₁₂ and R ₁₃ include a hydroxyl 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 substituted by R ₁₂ and R ₁₃ and a carbonyl carbon; preferable.

Specific examples of Z include -O-, -C
_{(R 14) (R 15)} -, - C (R 16), - C (= O) -,
-N (R ₁₇₎ -, - formed by combining the N =. However, R ₁₄ , R ₁₅ , R ₁₆ , and R ₁₇ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxyl group, a carboxyl group, or a sulfo group can be given as a substituent). And an optionally substituted aryl group having 6 to 15 carbon atoms (an alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, and a sulfo group can be given as a substituent), a hydroxyl group, and 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 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.

Specific examples of the compound represented by the general formula (4) of the present invention include sodium erythorbate and sodium ascorbate as well as JP-A-10-13333.
No. 8, pages 3 to 5 can be mentioned.

In the present invention, a developer containing substantially no hydroquinone and containing a compound of the general formula (4) is preferred. In the present invention, substantially not containing means that the concentration is 0.1 g / l or less. 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 redatonone, 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.

As the silver sludge inhibitor, JP-A-56-1985
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 and 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 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), pp. 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 in the present invention includes a compound represented by the general formula (4) and nitroindazole which are 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 developer 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 may include fixing materials commonly used in the art.

As fixing agents, ammonium thiosulfate,
It is a thiosulfate such as sodium thiosulfate, and ammonium thiosulfate is particularly preferred 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 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. Examples of the fixing accelerator include JP-B-45-35754 and JP-B-5-35754.
Thiourea derivatives described in 8-122535 and 58-122536, and thioethers described in U.S. Pat. No. 4,126,459.

The replenishment of the fixing solution at the time of fixing processing of the photographic material of the present invention is preferably 50 to 150 ml, more preferably 65 to 130 ml per 1 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 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 in which a powdery solid processing agent is granulated and then subjected to a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet.

As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, and spray drying granulation are used. Can be done.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Furthermore, the particle size distribution is
Preferably, 0% or more is within a deviation of ± 100 to 150 μm.

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, 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 effects become 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.
No. 88025, British Patent No. 1,213,808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-10942 and 2-9042.
Nos. 109043, 3-39735 and 3-397
It can be produced by a general method described in the specification such as No. 39. Furthermore, powder processing agents are described, for example, in JP-A-54-13.
No. 3332, British Patent Nos. 725,892 and 72
It can be produced by a general method as described in specifications such as 9,862 and German Patent No. 3,733,861.

[0121] 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 resulting solid,
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 a granule 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 silver halide photographic 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 time of immersion in the washing tank liquid is referred to as “water washing 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 developed, fixed and washed (or stabilized), 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, 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, molybdenum (Mo) is used for the anode of the X-ray generating tube, and the addition of a Mo filter removes continuous X-rays of 20 kVp or more that cause a decrease in contrast due to scattering.
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.

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

A tungstate-based phosphor (CaWO)_FourWhat
Terbium-activated rare earth oxysulfide-based phosphor [Y_TwoO_Two
S: 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
Terbium-activated rare earth oxyhalide-based fluorescence
LaOBr: Tb, GdOBr: Tb, etc.), thulium
Activated rare earth oxyhalide phosphor (LaOBr:
Tm, etc.), barium sulfate based phosphor (BaSO_Four: Eu^{Two +}
Etc.) divalent europium activated alkaline earth metal phosphate
Based phosphor [Ba_Three(PO _Four)_Two: Eu²⁺Etc.)
Lopium activated alkaline earth metal fluoride halide based fluorescence
Body (BaFCl: Eu)²⁺, BaFBr: Eu²⁺Etc.)
Phosphors (CsI: Na, CsI: Tl, etc.), sulfide
Phosphor [ZnS: Ag, (Zn, Cd) S: Ag]
Etc.), hafnium phosphate-based phosphor (HfP_TwoO₇: Cu
However, the phosphor used in the present invention is not limited to these.
Not a thing.

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

The X-ray fluorescent intensifying screen of the present invention is preferably filled with a phosphor having 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 fluorescence 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.

[0132]

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

Example 1 All the emulsions shown below were prepared by using a silver halide emulsion manufacturing apparatus shown in FIG. The volume of the reaction vessel was 32 liters. As an ultrafiltration unit, Asahi Kasei SIP-1013, and as a circulating pump, DAIDOR®
otory 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. 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 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.

(Em1-1 to Em1-5: Preparation of Lower Layer Emulsion) [Nucleation Step] The following gelatin solution B-10 in a reaction vessel
One liquid was kept at 30 ° C., and was stirred at 450 rpm using the mixing and stirring apparatus of FIG.
The pH was adjusted to 1.96 with 1 l of 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 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 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
H was adjusted to 5.8. During this time, the silver potential of the solution (saturated silver-
Measured with silver ion selective electrode using silver chloride electrode as reference electrode)
Was controlled to 14 mV using a 1 mol / l potassium bromide solution.

(G-101) Alkali-treated inert gelatin (average molecular weight 100,000) 139.1 g Compound 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) 10 % by weight methanol solution 4.64ml H ₂ O 3266.0ml [grain growth step -1] after completion of the aging, followed S-102 solution by double jet in a While accelerating the flow rate of X-102 liquid (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 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 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 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 H ₂ O 975.8 ml (X-104) Potassium bromide 470.8 g H ₂ O 959.4 ml The entire area of the grain growth step-1 and the grain growth step-2 was 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, and concentration was performed.

After completion of the growth, desalting and washing are carried out according to a conventional method, gelatin is added and the mixture is 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.

Em1-2 was prepared in the same manner as Em1-1 except that the metal compound shown in Table 1 was added to the potassium bromide solution X-104 solution per mol of the silver halide in the finished emulsion. Em1-5 was 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 shown below.

[Nucleation Step] While maintaining the following gelatin solution B-201 solution 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 0.5 mol / l sulfuric acid. Thereafter, the S-201 solution and the X-201 solution were added at a flow rate of 5.0 ml / sec by using the double jet method to form nuclei.

(B-201) Low molecular weight gelatin (average molecular weight: 20,000) 32.4 g Potassium bromide 9.92 g H ₂ O 129.38.0 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 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
H was adjusted to 5.8. During this time, the silver potential of the solution (saturated silver-
Measured with silver ion selective electrode using silver chloride electrode as reference electrode)
Was controlled to 14 mV using a 1 mol / l potassium bromide solution.

(G-201) Inert gelatin treated with alkali (average molecular weight: 100,000) 139.1 g Compound 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) 10 % by weight methanol solution 4.64ml H ₂ O 3266.0ml [grain growth step -1] after completion of the aging, followed S-202 by double jet in solution and While accelerating the flow rate of X-202 liquid (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 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 potassium bromide aqueous solution, the S-204 solution and the X-204 solution were accelerated while increasing the flow rates (addition at the end and at the start). (The flow rate ratio was 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.

In the same manner as in Em2-1, except that the metal compounds shown in Table 1 were added to the potassium bromide solution X-204 solution per mol of the silver halide in the finished emulsion, Em2-2 to Em2-2 were added. Em2-5 was 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.

(Chemical sensitization and spectral sensitization)
After the emulsions of -1 to 1-5 and Em 2-1 to 2-5 were heated to 60 ° C., adenine and thiocyanate were added 10 minutes after the sensitizing dye (the following compound and amount) was added as a dispersion in the form of solid fine particles. A mixed aqueous solution of ammonium acid, chloroauric acid and sodium thiosulfate and a dispersion of a selenium sensitizer were added, and 30 minutes later, silver iodide fine particles were added, followed by ripening for a total of 2 hours. 4-hydroxy-6 as a stabilizer at the end of ripening
A predetermined amount of methyl-1,3,3a, 7-tetrazaindene was added.

The amount added per mole of silver halide is shown below. Sensitizing dye (compounds of general formulas (1) and (2) described in Table 1) Amount described in Table 1 Adenine 10 mg Ammonium thiocyanate 70 mg Chloroauric acid 10 mg Sodium thiosulfate 5.0 mg Dispersion of selenium sensitizer ( 1.0 mg silver iodide fine particles 0.3 mmol 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 600 mg gelatin 40 g The solid fine particle dispersion of the sensitizing dye is as follows: triphenylphosphine selenide) Prepared by known methods.

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.

A dispersion of the 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. 2. On the other hand photographic gelatin.
8 kg was dissolved in 38 kg of pure water, and 93 g of a 25% by mass 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. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3% by mass or less. Thereafter, the dispersion is diluted with pure water to obtain 8
Finished to 0 kg. A part of the dispersion thus obtained was fractionated and used in the above Examples.

In this manner, as shown in Table 1, Em1
-1 to 1-5 to E1-1 to E1-13,
From M2-1 to 2-5, upper layer emulsions of E2-1 to E2-13 were prepared and used.

[0154]

[Table 1]

(Preparation of Emulsion Layer Coating Solution) Each of the above-obtained emulsions (per mole of silver halide) was added with the following various additives to prepare upper and lower emulsion layer coating solutions, respectively.

1,1-Dimethylol-1-bromo-1-nitromethane 7 mg t-butylcatechol 130 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g sodium polystyrenesulfonate 2.0 g trimethylolpropane 7.0 g nitrophenyl-tri phenyl - phosphonium chloride 20 mg 1,3 sodium-dihydroxybenzene-4-sulfonic acid sodium 400 mg 2-mercaptobenzimidazole-5-sulfonic acid _{10mg n-C 4 H 9 OCH} 2 CH (OH) CH 2 n (CH 2 COOH) ₂ 650 mg (Preparation of coating solution for protective layer on emulsion layer side) Gelatin 0.9 g / m ² Matting agent (PMMA having an average particle size of 4 μm) 30 mg / m ² Hardening agent (CH ₂ = CHSO ₂ CH ₂ CONHCH ₂ −) ₂ The swelling rate will be 150% The addition amount of the modifying compounds in (S-1) 7 mg / m ² Compound (S-2) 40 mg / m ² Formula (3) of the polymer (compound shown in Table 2) Table 2 The amount comparison compound according (S -3) Amount shown in Table 2 A coating solution on the backing layer side was prepared as follows.

(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 (PMMA with an average particle size of 5 μm) 100 mg / m ² Compound (S-1) 7 mg / m ² Compound (S-2) 50 mg / m ² General formula The polymer No. of (3) 36 10 mg / m ² Hardener (CH ₂ = CHSO ₂ CH ₂ CONHCH ₂ −) ₂ Adjusted the amount to be added so that the swelling ratio becomes 150%. Preparation of solid fine particle dispersion dye was carried out as follows. That is, water and the surfactant alkanol X are placed in a ball mill container.
C (manufactured by DuPont), dyes (D-1 to D-3) are added, zirconium oxide beads are put therein, and the container is sealed.
Dispersed in a ball mill for 4 days.

[0158]

Embedded image

[0159]

Embedded image

(Coating) Using these coating solutions, the silver content of the upper emulsion layer was 1.5 g / m ² , the lower emulsion layer was 1.5 g / m ² , and the gelatin content of the emulsion protective layer was on one surface of the support. 0.9g
/ M ² and so as to also the other surface, the antihalation dye layer, the protective layer, using two slide hopper type coaters, glycidyl methacrylate 50 wt%,
A copolymer dispersion liquid obtained by diluting the concentration of a copolymer composed of three kinds of monomers of 10% by mass of methyl acrylate and 40% by mass of butyl methacrylate to 10% by mass was applied as a subbing liquid and dried. 1 minute per minute on both sides of a 175 μm thick blue colored polyethylene terephthalate support
Coating was performed simultaneously at a speed of 20 m, and the coating was dried for 2 minutes and 20 seconds. 1 to 20 were produced. Further, a sample was prepared in which only the upper emulsion layer and the lower emulsion layer were similarly coated. However, in this case, the emulsion protective layer was made of Sample No. The same as 1 was used. Using a sample containing only the upper emulsion and a sample containing only the lower emulsion, the difference in sensitivity between the two emulsions was determined by the following sensitometric method.
In the case of the combination of the lower emulsion and the upper emulsion shown in
log = 0.18 to 0.19.

<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 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-mercaptotetrazole Na salt, 3.0 g of 5-nitroindazole, 1500 g of binder mannitol, and 600 g of D-sorbitol were added, and the mixture was stirred at room temperature in a commercially available stirring granulator. And granulated by adding 125 ml of water over 1 minute, and then drying the granulated material at 40 ° C. for 2 hours with a fluidized drier to almost completely remove the water content of the granulated material. To be 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 structure 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)] 14580 g of ammonium thiosulfate / sodium thiosulfate (90/10 mass ratio) is pulverized in a commercially available bantam mill to an average of 10 µm. To this fine powder, a compound (HOCH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ OH) 1000 g sodium metabisulfite 920 g 5-mercapto-tetrazole 50 g binder pine flow 900 g was added, and the mixture was cooled to room temperature in a commercially available stirring granulator. After mixing for about 3 minutes and granulating by adding 150 ml of water over 1 minute, the granulated material 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. Using the packaging material used in developing tablets (A) and (B) for moisture proofing, 92 pieces of (C) and 28 pieces of (D) (the volume after dissolution would be 5.0 liters) were used as tablets. Was packaged. Development starter formulation (addition amount per liter 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 16.0 g Finishing with pure water 67 ml The automatic developing machine used was TCX-701 (manufactured by Konica Corporation). 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. 5.6 liters of a fixing solution prepared in the same manner was used in TCX-70.
No. 1 was used as a start solution in the fixing processing tank.

In each of the developing and fixing steps, the packaging bag opened by hand is set at the inlet of each solid agent, and the tablets are dropped into the built-in chemical mixer.
(0 ° C) and dissolving with stirring for 25 minutes while stirring and dissolving.
Adjust to 0 liters. 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 liters and the capacity of the spare tank is 5.0 liters. The film is produced in the liquid preparation tank during the running process. A spare tank is provided to supply the replenisher so that the replenisher does not enter the non-replenished state during the stirring and dissolving time (about 25 minutes) even if the replenisher runs out.

Development temperature 34 ° C. (replenishment rate is 100 ml / m
² ) Evaluation was performed at a fixing temperature of 34 ° C. (replenishment rate was 100 ml / m ² ), water at 18 ° C. (5 liter / min), a drying temperature of 55 ° C., and a processing time of 45 seconds.

<Evaluation of Sensitometry> The photosensitive material sample No. Emulsion surface M-100 (manufactured by Konica Corporation) with an emulsion surface of 1 to 20 for mammography.
And the inside of the cassette. High adhesion,
X-ray irradiation was performed after standing still for 10 minutes in order to make it constant. The X-ray generator is manufactured by Toshiba Corporation (ROTANOD)
Using E), 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 was placed at a position 20 cm from the anode. After the development processing, a sensitometric curve was prepared by a distance method, and the sensitivity, fog, and gradation were determined. In addition,
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 sample No. The value of the film of 1 is 100
Was evaluated by relative sensitivity. 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. It was represented by tan θ when the angle between the straight line and the horizontal axis was θ.

<Evaluation of scratch resistance> The unexposed sample film was allowed to stand at 23 ° C and a relative humidity of 40% for 2 hours, and then 9.8k using a commercially available nylon scourer under the same conditions.
After rubbing with a weight of Pa, processing was performed with an automatic developing machine under the above conditions, and the evaluation was made by visual observation.

A: Almost no scratch B: Practically no problem but some scratch C: Scratch occurs to the extent of being noticeable and practically problematic D: Very many scratches <Evaluation of anti-fingerprint resistance> The unexposed sample film was lightly pressed with a finger for 3 seconds under the conditions of room temperature 23 ° C. and relative humidity 50%, and the same as described above. Exposure development processing was carried out so that the density might be about 1.0 by the method. The obtained sample was visually evaluated in the following four stages.

A: There is almost no fingerprint trace B: There is a slight fingerprint trace when viewed closely C: The fingerprint trace is generated to the extent that it is conspicuous D: The fingerprint trace is very strong, which is a practical problem <Diagnosis Efficiency evaluation> The obtained sample was placed in a cassette containing a sample in the same apparatus as in the sensitometry evaluation, and the sample was placed in KYOKK.
An O156 mammo 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 comprehensively ranked as diagnostic ability. Evaluation criteria A: All are clearly visible B: All are sufficiently visible C: Some images are hard to see D: All images are hard to see

[0176]

[Table 2]

From the above results, it can be seen that the silver halide photographic light-sensitive material of the present invention has high contrast, is excellent in diagnostic performance for X-ray mammography, and has good scratch resistance and fingerprint mark resistance.

[0178]

Industrial Applicability According to the present invention, a silver halide photographic material for X-ray mammography, which has high contrast, excellent diagnostic performance, good scratch resistance 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 of an apparatus for producing a silver halide emulsion used in 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 symbol FI Theme coat ゛ (Reference) G03C 1/09 G03C 1/09 1/16 1/16 1/18 1/18 1/76 501 1/76 501 5/26 520 5/26 520 5/30 5/30 5/305 5/305

Claims (13)

[Claims] 1. A support having at least one layer on one surface of a support.
A light-sensitive silver halide emulsion layer; and a support for the silver halide emulsion layer.
It has a non-photosensitive colloid layer on the side farther from the
Silver halide photographic materials with a backing layer on the surface
In at least one of the silver halide emulsion layers.
Silver halide grains account for more than 50% of the total projected area.
At least one metal ion of Rh, Ru, Re, Os
Doped with a flat plate having an aspect ratio of 3 or more and 30 or less.
Silver halide particles, and having the general formula (1) and the general formula
A non-photosensitive roller containing the compound represented by (2);
The polymer represented by the general formula (3) is contained in the id layer.
A silver halide photographic light-sensitive material, characterized in that: Embedded image(In the general formula (1), R₁And R_TwoIs each alkyl
Represents a group. Where R ₁And R_TwoAt least one of the
It is an alkyl group having a ruho group. R_ThreeIs lower alkyl
Represents a group. R_Four, R_Five, R₆, And R₇Is a hydrogen atom,
Lower alkyl group, alkoxy group, halogen atom, hydro
Xy group, aryl group, carboxy group, alkoxycarbo
Nil, cyano, trifluoromethyl, amino,
Silamide group, acyl group, acyloxy group, alkoxyca
Represents a rubonylamino group or a carbalkoxy group. R_FourWhen
R_Five, R₆And R₇Are linked to each other to form a naphthoxazole nucleus
May be formed. )(In the general formula (2), Z₁And Z_TwoAre each thiazo
Nucleus, thiazoline nucleus, oxazole nucleus, selenazole
Nucleus, 3,3-dialkylindolenine nucleus, imidazole
Nucleus, pyridine nucleus, benzimidazole nucleus, benzoxa
Zole nucleus, benzothiazole nucleus, benzoselenazole
Nucleus, naphthoxazole nucleus, naphthothiazole nucleus, naph
Lists the non-metallic atoms required to form the toselenazole nucleus.
You. R₈, R₉Represents an alkyl group having a sulfo group.
You. )(In the general formula (3), Rf is at least one
L represents an alkyl group containing a hydrogen atom;₁, L_TwoIs just
Xp represents hydrogen, hydroxy,
Group, anionic group, cationic group, amphoteric group,
R_Ten, R₁₁Represents hydrogen or a lower alkyl group. m and n are heavy
It represents the total molar ratio and represents m + n = 1.0. ) 2. 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 light-sensitive material according to claim 1, 3. The silver halide photographic light-sensitive material according to claim 1, wherein the coefficient of variation of the volume particle diameter of the tabular silver halide grains is 0.10 or less. 4. 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. A method for processing a silver halide photographic light-sensitive material, wherein the development is carried out using a developer having a bromine ion concentration of at least 10 g / l in terms of potassium bromide. Embedded image (In the general formula (4), R ₁₂ and R ₁₃ each independently represent a hydroxy 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 a substituted or unsubstituted 5
Represents an atom group necessary for forming a 6-membered ring. ) 5. The method for processing a silver halide photographic material according to claim 4, wherein the developer is a solution in which a solid developer is dissolved. 6. The method for processing a silver halide photographic light-sensitive material according to claim 5, wherein the solid developer is a tablet. 7. The surface of the silver halide photographic light-sensitive material according to any one of claims 1 to 3, wherein the surface of the silver halide emulsion layer having the silver halide emulsion layer is in close contact with the surface of the X-ray fluorescent intensifying screen having the phosphor layer. An X-ray image forming method, comprising irradiating an X-ray transmitted through a subject, developing, fixing, washing and drying with an automatic developing machine to form an X-ray image. 8. The X-ray image forming method according to claim 7, wherein the phosphor of the X-ray fluorescent intensifying screen is terbium-activated gadolinium oxysulfide. 9. A method for processing a silver halide photographic light-sensitive material according to any one of claims 4 to 6, wherein the method for processing a silver halide photographic light-sensitive material is used for development with an automatic developing machine. X-ray image forming method. 10. The X-ray image forming method according to claim 7, wherein X-rays having a tube voltage of 40 kVp or less are used. 11. The silver halide photographic material according to claim 1, wherein the material is used for X-ray mammography. 12. The method for processing a silver halide photographic material according to claim 4, wherein the method is for X-ray mammography. 13. The X-ray image forming method according to claim 7, wherein the method is for X-ray mammography.