JP2000010222A - Silver halide photographic sensitive material and method for treating the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material capable of making the enhancement of sharpness and the reduction of residual color compatible even in the case of developing treatment at a low pH preferable from the environmental point of view, and the method for the treatment. SOLUTION: This silver halide photographic sensitive material has at least one dye capable of being decolored in a development treatment process for reducing crossover light, which is fixed in such state that the dye has an absorption maximum in the wavelength range of 500-600 nm and the optical transmission density at the wavelength of 550 nm shows three times or more of the transmission density at the wavelength of 450 nm, on at least one layer of a photosensitive layer or a non- photosensitive layer provided on at least one side of a transparent support and has photosensitive layers containing spectrally sensitized silver halide particles on the both sides of the transparent support. The photosensitive layer provided on at least one side of the transparent support has such photosensitive property that the logarithm of the ratio of the light exposure of monochromatic light having the wavelength of 450 nm to the light exposure of the monochromatic light having the wavelength of 550 nm giving a fixed developed silver density, is at least 0.8. The photographic sensitive material is treated at a pH not less than 7 but not exceeding 10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material excellent in sharpness of medical X-ray photography and a processing method thereof.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material (hereinafter, abbreviated as light-sensitive material), a photographic emulsion layer and other hydrophilic colloid layers are colored in order to absorb light in a specific wavelength range. I have been. This is because the light scattered when the incident light passes through or after transmission through the photographic emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the photosensitive material on the side opposite to the emulsion layer, and then re-exposed to the photographic emulsion layer. The purpose of the present invention is to prevent the image from being blurred due to the incident light, ie, halation.

As is well known, a medical X-ray sensitive material generally has a photographic emulsion layer on both sides of a transparent support.
The so-called crossover light in which the intensifying screen absorbs X-rays and fluoresces by passing through one emulsion layer adjacent to the intensifying screen and reaching the other emulsion layer is a so-called crossover light in medical X-ray photography. Significantly reduces sharpness. Therefore, a colored layer is provided between the photographic emulsion layer and the support to block crossover light. (Hereinafter, this colored layer is called a crossover shielding layer). These hydrophilic colloid layers to be colored often contain a dye.

[0004] This dye has a spectral absorption according to the purpose of use, and it is necessary that the color be rapidly decolorized in the development process. The dye should be cross-linked so as not to diffuse into the silver halide emulsion layer or other hydrophilic colloid layers. It is required to be sufficiently fixed in the over-shielding layer.

[0005] For the purpose of fixing a dye to a specific layer, many techniques have been disclosed in the prior art.
In No. method using a mordant polymer, JP-A-1-72828
In JP-A No. 195, a method using a dye as solid microcrystalline particles is known.

[0006] On the other hand, as described in "Development of a small medical processing system using isoascorbic acid as a developing agent" described in Photographic Society of Japan, Vol. It has become an important issue to improve the environmental compatibility of processing agents and reduce the amount of waste liquid, especially when ascorbic acid or erythorbic acid, which is extremely excellent in material safety, is used as a developing agent. There is a demand for an excellent light-sensitive material capable of developing even at a low developer pH.

In the prior art, in order to reduce the crossover of the light-sensitive material, a desired low-crossover light-sensitive material can be obtained by increasing the coating amount of the dye.
In the processing with a developing solution, decolorization of the dye becomes insufficient due to the large amount of the dye applied, and the dye remains on the photographic material after the processing, which is a very serious problem in medical diagnosis.

For example, in the method using a mordant polymer described in Japanese Patent Application Laid-Open No. 1-166031, since the dye controls the fixing property in the light-sensitive material and the decoloration rate in the developing solution by pH, the dye has a low pH. In the processing with a developer, the bleaching property is insufficient.

Japanese Patent Application Laid-Open (JP-A) No. 1-172828 is an excellent technique for reducing the crossover of a light-sensitive material to less than 10% using a dye in the form of solid fine particles. Although the absorption maximum wavelength and absorbance in the monomer state are described, the optical properties of solid particulate dyes to reduce crossover, the spectral sensitivity distribution of photographic materials, and rare-earth phosphors as main components The effect of the secondary light emitting component of the intensifying screen on the image quality is not sufficiently described, and it was not possible to obtain a preferable dye decoloring property in a low pH developer treatment in order to easily increase the dye coating amount. .

Japanese Patent Application Laid-Open No. 1-172828 discloses that a fine-particle dye has an optical density of 1.0 at a wavelength corresponding to the peak emulsion sensitivity.
It is preferable that, in the photosensitive material used in combination with the green light-emitting intensifying screen, it is preferable that the particulate dye exhibit at least an optical density of 1.0 or more over a wavelength region of 450 nm to 550 nm. As described above, in order to actually realize them, a large amount of a dye having a relatively large half width is applied in a large amount, so that the bleachability of the dye is disadvantageous in rapid processing. Since the amount of coating is limited in order to achieve compatibility with decolorization, the gain of sharpness must be reduced.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a processing system that exhibits high sharpness and is environmentally friendly by effectively absorbing crossover light using a dye having favorable optical characteristics. It is another object of the present invention to provide a silver halide photographic light-sensitive material having a sufficient processing suitability and a processing method therefor.

[0012]

The above objects are achieved by the present invention described below. (1) On at least one side of the transparent support, at least one dye capable of being decolorized in a development process for reducing crossover light has an absorption maximum at a wavelength of 500 nm or more and 600 nm or less, and at a wavelength of 550 nm. Silver halide grains fixed to at least one photosensitive layer or non-photosensitive layer in a state where the optical transmission density is three times or more the optical transmission density at a wavelength of 450 nm and spectrally sensitized on both sides of the transparent support Having a photosensitive layer containing at least one side of the transparent support, the photosensitive layer having a wavelength of 550 nm that provides a constant developed silver concentration at a wavelength of 550 nm for monochromatic light exposure.
A silver halide photographic material, characterized in that the logarithm of the ratio of the amount of exposure to monochromatic light of 50 nm is at least 0.8. (2) substantially terbium activated gadolinium oxysulfide: using the phosphor is (Gd ₂ O ₂ S Tb), and further absorb at least 500nm or less of the light wavelength of the emission light of the phosphor, 500 nm to The above-mentioned (1), which exhibits a crossover of 0% or more and 12% or less when radiation exposure is performed in combination with a radiation intensifying screen containing a fluorescent dye and / or a fluorescent pigment that emits light at a wavelength range of 600 nm. 3. The silver halide photographic light-sensitive material according to item 1. (3) The silver halide photographic material as described in the above (1) or (2), wherein at least one or more dyes capable of decoloring in the course of development processing for reducing crossover light are in the form of solid fine particles. (4) The silver halide photographic material as described in any one of (1) to (3) above, wherein the spectrally sensitized silver halide grains are tabular grains having an average aspect ratio of 4 to 30. . (5) The halogenation according to any one of (1) to (4), wherein the average amount of iodine contained in the spectrally sensitized silver halide grains is from 0 mol% to 0.4 mol%. Silver photographic photosensitive material. (6) As the average halogen composition of the spectrally sensitized silver halide grains, silver chloride is 10 mol% or more and 100 mol% or more.
The silver halide photographic material according to any one of the above (1) to (5), comprising: (7) A method for processing a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to any one of the above (1) to (6) is developed with a developer having a pH of 7 to less than 10. (8) The method for processing a silver halide photographic material as described in (7) above, wherein the developer uses ascorbic acid and / or erythorbic acid as a developing agent.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the light-sensitive material of the present invention, at least one kind of dye that can be decolorized in a development process for reducing crossover light of a photographic light-sensitive material is fixed in a state of exhibiting an absorption maximum at a wavelength of 500 nm or more and 600 nm or less.

The developing process includes a developing process, a fixing process,
It refers to the three washing steps, and the decolorization of the dye may be any step. In particular, a dye that decolorizes in a developer is preferably used.

The dye thus fixed has an optical transmission density (absorbance) at a wavelength of 550 nm of 450 nm.
In the photosensitive layer on at least one side of the transparent support, the exposure of the monochromatic light having a wavelength of 550 nm to the exposure amount of the monochromatic light having a wavelength of 550 nm, which gives a constant developed silver concentration, as described later. The common logarithm of the quantity ratio is 0.8 or more.

By adopting such a structure, sharpness can be improved and residual color can be reduced even in processing of a low pH developer which is environmentally preferable. On the other hand, even if the absorption maximum is less than 500 nm or more than 600 nm, the effect of reducing the crossover light becomes insufficient, and if the amount of the dye used is increased to make this effect sufficient, the residual color Will occur. on the other hand,
When the above-mentioned optical density ratio is less than 3, in order to obtain sufficient sharpness, there is a problem of a residual color particularly in a low pH developing solution processing. If the above exposure ratio is less than 0.8, the effect of reducing the crossover light cannot be sufficiently obtained.

Further, in the light-sensitive material of the present invention, the dye exhibits an absorption maximum at a wavelength of 500 nm or more and 600 nm or less.
It is preferable that the absorption maximum exists in the wavelength range of m to 580 nm.

In the light-sensitive material of the present invention, one or more dyes that can be decolorized in the development process for reducing crossover light may be used, and the dye in the light-sensitive material of the present invention has a wavelength of 550 nm. The optical transmission density at the wavelength is fixed so as to be three times or more the optical transmission density at the wavelength of 450 nm. In particular, the optical transmission density (absorbance) at a wavelength of 550 nm is more preferably 4 times or more, and most preferably 5 times or more, the optical transmission density at a wavelength of 450 nm. The upper limit is not particularly limited, but is about 20 times.

In the present invention, as a method for fixing a decolorizable dye to a photosensitive layer or a non-photosensitive layer in a developing process for reducing crossover light, see JP-A-3-10.
No. 9535, a method in which a known dye is dissolved in oil and emulsified and dispersed in an oil droplet form, a method described in JP-A-3-5748, in which a dye is adsorbed on an inorganic material surface, and a method described in JP-A-2-298939.
And a method of dispersing a known dye as solid fine particles.

Above all, the absorption spectrum of the dye is preferably one belonging to the associated species of the dye rather than one belonging to the state of the monomer species of the dye.
In that respect, it is preferable that at least one or more dyes are in the form of solid fine particles.

Hereinafter, the dye used as the solid fine particles will be described in detail.

The solid particulate dye preferably used in the present invention is represented by the following general formula [1] or general formula [2].

[0023]

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In the general formulas [1] and [2], D represents a compound having a chromophore, and X has a dissociable proton or a dissociable proton bonded to D directly or via a divalent linking group. Represents a group, and y represents an integer of 1 to 7.

In the general formula [2], S _1, S ₂ and... Sc represent crystallization solvents incorporated in the dye crystals, and even if S ₁ , S ₂ ,. It may be different. p ₁ and p ₂ and..., pc each represent a molar ratio of 0 to 10. p _1, p _2, ··,
Any of pc is not 0, and c representing the number of solvent types is an integer of 1 or more.

In the present invention, the general formula [1]
The dye of [2] can be more preferably used.

Further, in the present invention, a dye represented by the general formula [3] in the general formula [1] or a dye represented by the general formula [4] in the general formula [2] is used. Is more preferred.

[0029]

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[0030]

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In the general formulas [3] and [4], A ₁ represents an acidic nucleus necessary for forming a dye, and A ₂ represents an acidic nucleus required for forming a dye, or an aromatic ring or a heterocyclic ring. L ₁ , L ₂ , L ₃ , L ₄ , L ₅ each represents a methine group or an azomethine group, and m and n are each 0 or 1.

In the general formula [4], S ₁ and S ₂ may be the same or different and each represents a crystallization solvent incorporated in the dye crystal. p ₁ and p ₂ are each 0 to 10
Represents the molar ratio up to

In the present invention, the general formula (3)
The dye of [4] can be more preferably used.

Hereinafter, the general formula [1] or [2] will be described in detail.

The compound having a chromophore represented by D can be selected from many known dye compounds. Examples of these compounds include oxonol dyes, merocyanine dyes, cyanine dyes, arylidene dyes, heteroarylene dyes, azomethine dyes, triphenylmethane dyes, azo dyes, and anthraquinone dyes.
Specific examples include compounds described in JP-A-3-259136, page (5), lower left column, line 14 to page (13), lower left column, last line.

The dissociable proton or the group having a dissociable proton of the dye of the general formula [1] or [2] of the present invention is preferably in a non-dissociated state at the time of dispersion. Examples of these groups include carboxylic acid groups, sulfonamide groups, sulfamoyl groups, sulfonylcarbamoyl groups, carbonylsulfamoyl groups, and enol groups of oxonol dyes. Particularly, a carboxylic acid group and a sulfonamide group are preferable.

The crystallization solvents S _{1 to} S _C will be described later, but the number c of the solvent species is preferably an integer of 1 to 6, more preferably 1, 2, 3 and particularly preferably 1 or 2. preferable. When any of S _{1 to} S _C represents H ₂ O, it is so-called crystallization water.

Next, the general formula [3] or [4] will be described in detail.

The acidic nucleus represented by A ₁ is preferably a methylene group or a cyclic ketomethylene group (including a thioketomethylene group) sandwiched between electron-withdrawing groups. Specific examples are shown below, but the specific examples only show keto bodies or analogs thereof.

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkenyl group or a hydroxyl group, and R ₅ , R ₆ and R ₇ each represent a hydrogen atom Or a substituent. R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ or R ₆
And R ₇ may combine with each other to form a 5- or 6-membered ring.

The substituents represented by R ₅ , R ₆ and R ₇ are not particularly limited as long as they do not substantially dissolve the dye of the general formula [3] in water at pH 5 to pH 7. For example,
Carboxylic acid group, sulfonamide group having 1 to 10 carbon atoms, preferably sulfonamide group having 1 to 6 carbon atoms (for example, methanesulfonamide, benzenesulfonamide, butanesulfonamide), sulfonylcarbamoyl group having 2 to 10 carbon atoms , Preferably a sulfonylcarbamoyl group having 2 to 7 carbon atoms (for example, methanesulfonylcarbamoyl, propanesulfonylcarbamoyl), a carbonylsulfamoyl group having 2 to 10 carbon atoms, preferably a carbonylsulfamoyl group having 2 to 7 carbon atoms ( For example, acetylsulfamoyl, propionylsulfamoyl), having 1 to 1 carbon atoms
An alkyl group having 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, hexyl, 2-hydroxyethyl, 4-carboxybutyl); , Preferably an alkoxy group having 1 to 6 carbon atoms (eg, methoxy, ethoxy, butoxy), a halogen atom (eg, chlorine, bromine, fluorine), an amino group having 0 to 10 carbon atoms, preferably 0 to 6 Amino group (eg, dimethylamino, methylethylamino, diethylamino, ethylbutylamino, carboxyethylamino), having 2 carbon atoms
To 12 ester groups, preferably 2 to 7 carbon atom ester groups (e.g., methoxycarbonyl, ethoxycarbonyl), 1 to 10 carbon atom amide groups, preferably 1 carbon atom
To 6 amide groups (eg, acetylamino, benzamide), a carbamoyl group having 1 to 10 carbon atoms, preferably a carbamoyl group having 1 to 6 carbon atoms (eg, carbamoyl,
Methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, butylcarbamoyl, phenylcarbamoyl), a sulfamoyl group having 0 to 10 carbon atoms, preferably a sulfamoyl group having 0 to 6 carbon atoms (for example, methylsulfamoyl, butylsulfamoyl, phenylsulfamoyl) Famoyl), an aryl group having 6 to 15 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms (for example, phenyl, naphthyl, 4-carboxyphenyl, 3-carboxyphenyl, 3,5-dicarboxyphenyl, 4- Methanesulfonamidophenyl, 4-butanesulfonamidophenyl), an acyl group having 2 to 10 carbon atoms, preferably 2 carbon atoms
To 7 acyl groups (eg, acetyl, benzoyl, propanoyl), a sulfonyl group having 1 to 10 carbon atoms, preferably a sulfonyl group having 1 to 7 carbon atoms (eg, methylsulfonyl, phenylsulfonyl), Ureido group, preferably a ureido group having 1 to 6 carbon atoms (for example,
Ureido, methylureide), a urethane group having 2 to 12 carbon atoms, preferably a urethane group having 2 to 7 carbon atoms (for example,
Examples thereof include methoxycarbonylamino, ethoxycarbonylamino), cyano group, hydroxyl group, nitro group, and heterocyclic group (for example, 5-carboxybenzoxazole ring, pyridine ring, sulfolane ring, and furan ring as a heterocyclic ring). These may be further substituted.

The alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ is an alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, benzyl, phenethyl, propyl, butyl, isobutyl, pentyl, hexyl , Octyl, nonyl) are preferable, and may have a substituent (for example, each group described above).

The aryl group represented by R ₁ , R ₂ , R ₃ and R ₄ is an aryl group having 6 to 10 carbon atoms (for example, phenyl,
Naphthyl) is preferable, and may have a substituent (for example, each group described above).

The heterocyclic ring in the heterocyclic group represented by R ₁ , R ₂ , R ₃ and R ₄ is a 5- or 6-membered heterocyclic ring which may have a condensed ring (for example, an oxazole ring, Oxazole ring, thiazole ring, imidazole ring, pyridine ring, furan ring, benzofuran ring, thiophene ring, sulfolane ring,
A pyrazole ring, a pyrrole ring, an indole ring, a chroman ring, a coumarin ring, a 2H-chromen-2-one ring) are preferable, and may have a substituent (for example, each of the groups described above).

The alkenyl group represented by R ₁ , R ₂ , R ₃ and R ₄ is an alkenyl group having 2 to 10 carbon atoms (eg, vinyl, allyl, 1-propenyl, 2-pentenyl, 1,3
-Butadienyl) is preferred.

R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ or R
Examples of the 5- or 6-membered ring formed by linking ₆ and R ₇ include a pyrrolidine ring, a piperidine ring, a morpholine ring and a benzene ring.

In the formula, A ₂ represents an acidic nucleus or an aromatic or heterocyclic ring. Examples of the acidic nucleus include a methylene group represented by A ₁ and a cyclic ketomethylene group (including a thioketomethylene group). Examples of the aromatic ring include benzene and naphthalene. The heterocyclic ring is preferably a 5- or 6-membered ring, and may have a substituent (for example, each of the groups described above). Further, the substituents may be connected to each other to form a condensed ring. For example, the heterocyclic ring represented by R ₁ can be mentioned. Specific examples of the heterocyclic ring are shown below.

[0058]

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In the formula, R ₈ , R ₉ , R ₁₀ , and R ₁₁ represent a hydrogen atom or a substituent (same as R ₅ ).

The methine groups represented by L ₁ , L ₂ , L ₃ , L ₄ and L ₅ may have a substituent (for example, methyl or ethyl). It may form a 5- or 6-membered ring (for example, a cyclopentene ring, a cyclohexene ring, an isophorone ring). Further, it may be an azomethine group.

In the general formula [3], A ₁ is preferably a substituted or unsubstituted pyrazolone, barbitur, pyridone or pyrazolopyridone nucleus, more preferably pyridone or pyrazolopyridone nucleus. A ₂ is preferably an aromatic ring or a heterocyclic ring, more preferably a substituted benzene, a substituted naphthalene, or a substituted heterocyclic ring.

Specific examples of the dye represented by the general formula [4] are shown below, but the general formula [3] containing no crystallization solvent of the specific example is shown below.
The dyes belonging to the above are also preferably used. Examples of such a dye include Dye B used in Examples. However, in the present invention, a dye containing a crystallization solvent belonging to the general formula [4] is more preferable.

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The dye represented by the general formula [3] or [4] can be produced by a method known to those skilled in the art (for example, a method using an acidic nucleus and ethyl orthoformate, diphenylamidine, 1,1).
(A condensation reaction with a methine source such as 1,3,3-tetramethoxypropane, malonaldehyde dianyl or glutaconaldehyde dianyl, or a formyl compound).

The reaction temperature is 0 to 200 ° C., preferably 20 to 120 ° C., and the reaction time is 5 minutes to 48 hours.
Preferably, 10 minutes to 5 hours are preferable.

As a method of incorporating various solvents into a dye as a crystallization solvent, a powder crystal or a wet cake of the dye obtained by the above method is heated using a protic or aprotic polar or non-polar solvent. Obtained by stirring. The reaction temperature is from 0 to 200
℃, preferably 20 to 120 ℃, the reaction time is 5
Minutes to 20 hours, preferably 30 minutes to 6 hours.
Whether the crystallization solvent has been incorporated can be confirmed by NMR, powder X-ray crystal diffraction, thermal analysis, Karl Fischer titration, and the like. In particular, the powder X-ray diffraction method is a useful measuring means since it can be seen that the crystal structure of the dye changes due to the presence of the crystallization solvent.

According to this method, when a solvent is incorporated into the dye crystal, an X-ray diffraction pattern completely different from that of the dye alone can be obtained, and a different X-ray diffraction pattern differs depending on the type of the solvent. The dyes shown can be obtained.

The aprotic solvent used in the preferred dye is preferably an amide having 6 or less carbon atoms (eg, N, N-dimethylformamide (hereinafter abbreviated as DMF), N, N-dimethylacetamide (hereinafter abbreviated as DMAc). , N-methylpyrrolidone (hereinafter abbreviated as NMP)), sulfoxides having 6 or less carbon atoms (for example, N, N-dimethylsulfoxide (hereinafter abbreviated as DMSO), N, N-diethylsulfoxide), sulfones having 6 or less carbon atoms (Eg, sulfolane), imidazoles having 6 or less carbon atoms (eg,
1,2-dimethylimidazole, 1-ethyl-2-methylimidazole), phosphoric amides or phosphites having 6 or less carbon atoms (for example, hexamethylphosphoric triamide (hereinafter abbreviated as HMPA), hexamethylphosphorous Acid triamide) and ureas having 6 or less carbon atoms (eg, tetramethylurea). Further, tetrahydrofuran, dioxane, toluene, and benzene may be used.

As the protic solvent used in the present invention, alcohols having 10 or less carbon atoms (methanol, ethanol, propanol, isopropanol, butanol,
Ethylene glycol), carboxylic acids having 5 or less carbon atoms (formic acid, acetic acid, propionic acid, etc.), phenols (phenol, m-cresol, p-cresol, etc.), liquid ammonia, water and the like. These solvents may be used alone or as a mixed solvent with another solvent. The solvent used as the mixed solvent may be the aprotic polar solvent described above, or may be any organic solvent such as methanol, acetone, acetonitrile, and ethyl acetate.

Usually, after the dye is produced, the filtered crystals are dried to remove the solvent and then dispersed. In the present invention, the dispersion step is performed without drying after the dye is formed. After the dye is produced, the solvent may be removed by filtration, or the dispersion may be carried out without filtration. The drying step mentioned here includes, for example, a heating step (normal pressure or reduced pressure), a blast drying (room temperature or heating), and a freeze drying. If there is no drying step, the present invention is not limited by any operation steps.

These water and organic solvent may be used in the dyeing reaction, or after the dyeing reaction, the above-mentioned solvent may be used again to incorporate a crystallization solvent.

The above-mentioned method for converting the dye into solid fine particles is carried out by using a known fine means (for example, ball mill, vibrating ball mill, planetary ball mill, sand mill, colloid mill, jet mill, roller mill) in the presence of a dispersing agent. Can be dispersed mechanically.

As the dispersant to be used, known anionic, nonionic and cationic surfactants and polymers can be used, and two or more of them may be used in combination as appropriate.

A commercially available dispersant may be used. For example, Demol N, Demol SNB, Demol EP manufactured by Kao Corporation may be used.

The dispersant is generally mixed with a dye powder or a wet cake before dispersion and sent as a slurry to a disperser. However, the dispersant is mixed with the dye in advance, and then heat-treated or treated with a solvent. To give a dye powder or a wet cake. During the dispersion, as the fine particles are formed, they can be added to the dispersion. Further, it can be added to the dispersion liquid for stabilizing the physical properties after dispersion. In any case, a solvent (eg, water / alcohol) is generally allowed to coexist. Before, during or after dispersion, the pH may be controlled with a suitable pH adjuster.

The prepared dispersion is stored with stirring or stored in a highly viscous state (for example, in a jelly state using gelatin) with a hydrophilic colloid in order to suppress sedimentation of fine particles during storage. You can also do.
It is preferable to add a preservative for the purpose of preventing propagation of various bacteria during storage.

The solid fine particle dispersion of the dye thus prepared has an average particle size of 0.005 μm to 10 μm, preferably 0.01 μm to 3 μm, and particularly preferably 0.05 μm to 3 μm.
It is preferably 0.5 μm.

Here, the characteristics of the dye dispersion in the form of solid fine particles are added.

The absorption spectrum is preferably such that the absorbance at 650 nm or more is low, particularly the absorbance at 550 nm / the absorbance at 650 nm = 5 to 50, and the absorbance at 550 nm / absorbance at 650 nm =
It is preferably from 10 to 50.

In order to obtain these preferable absorbance ratios, the average particle size of the solid fine particle dispersion of the dye is 0.05 to 0.05.
It is preferably 0.5 μm.

The half width of the absorption maximum is 50 nm or more and 15
0 nm or less, preferably 50 nm or more and 1 nm or less.
Most preferably, it is 10 nm or less.

In the present invention, the fact that a decolorizable dye is fixed to a photosensitive layer or a non-photosensitive layer in a development process for reducing crossover light means that a dye is added to a photosensitive material after coating and drying. Refers to a state of being substantially localized only in the layer (does not diffuse to other than the added layer). Whether or not the dye is fixed in a certain layer can be easily specified by observing the cross section of the light-sensitive material with an optical microscope by distinguishing the colored layer from other layers. When a dye is added to two or more adjacent layers, it is fixed to each layer.
This can be confirmed by preparing the photographic materials to which the dyes are added one layer at a time and observing the same as above.

In particular, as the non-photosensitive layer for fixing the dye,
An undercoating hydrophilic colloid layer or another hydrophilic colloid layer coated simultaneously with the silver halide emulsion is preferred, and the layer is preferably located closer to the support than the silver halide emulsion layer. Particularly, the coating amount of gelatin contained in the non-photosensitive layer is 0.05 g to 0.6 g per square meter (1 m ² ) on one side of the support.
The following is preferred. Most preferably, it is 0.05 g or more and 0.4 g or less.

The photosensitive layer for fixing the dye is preferably a silver halide emulsion layer closest to a transparent support (eg, polyesters such as polyethylene terephthalate).

In the present invention, the coating amount of the dye capable of being decolorized in the development process for reducing the crossover light is preferably from 5 mg to 60 mg, more preferably from 10 mg to 50 mg, per square meter of one side of the photographic material.

In the light-sensitive material of the present invention, the ratio of the exposure amount (E450) of the monochromatic light having a wavelength of 450 nm to the exposure amount (E450) of a monochromatic light having a wavelength of 550 nm which gives a fixed developed silver concentration of at least one side of the photosensitive layer (E550) The base 10 logarithm of (E450 / E550) is at least 0.8, and most preferably at least 0.9. At this time, the monochromatic light exposure is performed only from one side of the light-sensitive material, and the photosensitive layer located on the opposite side of the light source with respect to the support of the light-sensitive material is subjected to a film removal treatment after the development treatment and removed, and then the density is measured.

This is extremely important for minimizing the sensitivity of the light-sensitive material to an auxiliary light-emitting component having a wavelength of 500 nm or less of the intensifying screen. In order to reduce crossover, the absorption maximum is reduced to a wavelength of 500 nm or more and 600 nm or less. The effect is exhibited when a dye having an absorption coefficient at a wavelength of 550 nm that is three times or more the absorption coefficient at a wavelength of 450 nm is used.

In the light-sensitive material of the present invention, the ratio of the exposure amount (E450) of monochromatic light at a wavelength of 450 nm to the exposure amount (E550) of monochromatic light at a wavelength of 550 nm, which gives a fixed developed silver concentration of at least one side of the photosensitive layer, In order to specifically achieve that the base 10 logarithm of (E450 / E550) is at least 0.8, the average aspect ratio of the spectrally sensitized silver halide grains is 4 or more and 30 or less. Preferably
Further, it is more preferred that the tabular grains have an average aspect ratio of 6 or more and 30 or less.

At this time, the average aspect ratio refers to a value obtained by averaging the value obtained by dividing the circle-equivalent diameter of the projected area of each arbitrarily selected silver halide grain by the grain thickness, by the number of grains.

In particular, monodisperse hexagonal tabular silver halide grains described in JP-A-63-151618, JP-A-62-115435, and JP-A-6-43605.
Tabular silver halide grains having a thickness average of 0.1 μm or less (preferably 0.01 μm or more) described in JP-A-6-43606 are particularly useful.

It is preferable that the silver halide emulsion in the light-sensitive material of the present invention is not exposed to sub-emission having a wavelength of 500 nm or less emitted from an ortho-intensifying screen, and a specific method will be described below.

In the present invention, the average amount of iodine contained in the spectrally sensitized silver halide grains is preferably from 0 mol% to 0.4 mol%, and particularly preferably from 0 mol% to 0.2 mol%.
Most preferably, it is at most mol%.

In general, it has been considered that the higher the iodine content, the higher the sensitivity of silver halide, which is preferable.
In the present invention, since the intrinsic absorption of silver halide is shifted to the longer wavelength side, 450 n
It is not preferable that the sensitivity of silver halide to light having a wavelength near m increases.

Although there is no particular limitation on the internal structure of the particles of the iodine amount, it is preferable to convert iodine only on the particle surface.

The spectrally sensitized silver halide grains are
The average halogen composition preferably contains silver chloride in an amount of 10 mol% to 100 mol%, more preferably 50 mol% to 100 mol%.

At this time, silver chloride is added in an amount of 10 mol% to 100 mol%.
The silver halide grains contained below are preferably tabular grains having an average aspect ratio of 4 or more and 30 or less, and more preferably tabular grains having an average aspect ratio of 6 or more and 30 or less.

In the present invention, a light-sensitive material using silver halide grains having a high silver chloride content is described in JP-A-9-8.
No. 0666, No. 9-222689, No. 9-28162
No. 0, No. 7-120857, No. 8-76306, No. 8-76308, No. 9-5911 and the like.

The amount of silver coated on one side of the light-sensitive material of the present invention is preferably 0.5 g / m ² or more and 2.0 g / m ² or less, more preferably 1.0 g / m ² or less.
Particularly preferably, it is not less than m ^{2 and not} more than 1.6 g / m ² .

Other compounds which can be used in the light-sensitive material of the present invention are described in JP-A-8-240877.
Nos. 7-128809, 6-332888, 7-28203, 6-67365 and the like.

The light-sensitive material of the present invention uses a rare-earth phosphor which is substantially terbium-activated gadolinium oxysulfide (Gd ₂ O ₂ S: Tb), especially in combination with a conventional ortho-intensifying screen. At least 500 nm or less of the light emitted by the phosphor is absorbed at a wavelength of 500 nm or less.
It is preferable to use a radiation intensifying screen containing a fluorescent dye or a fluorescent pigment exhibiting an emission peak in a wavelength range of ~ 600 nm and the light-sensitive material of the present invention as an assembly, and a crossover when radiation exposure is performed in the combination. It is preferably from 0% to 12%. In particular, the crossover is preferably 2% to 10%, more preferably 2%.
It is most preferably at least 8%. The method of calculating the crossover is in accordance with the definition in JP-A-1-72828.

The radiation intensifying screen of the present invention comprises
As a basic structure, it comprises a support and one or two or more phosphor layers formed thereon. The intensifying screen can have the same configuration as a known radiographic intensifying screen. For example, a light reflecting layer or a light absorbing layer may be provided between a support and a phosphor layer, or a phosphor layer may be provided. It is preferable to provide a surface protective layer on the surface.

Hereinafter, a fluorescent dye or a fluorescent pigment used for a preferable intensifying screen will be described in detail.

The fluorescent dye or fluorescent pigment in the present invention is a substance that absorbs a part of the light emitted from the above-mentioned phosphor and emits light again in the visible region. For example, the above Gd ₂ O ₂
The S: Tb phosphor is a fluorescent dye or a fluorescent pigment that absorbs emitted light other than around 545 nm and re-emits light around 545 nm. The emission peak wavelength of the fluorescent dye or pigment is set in accordance with the spectral sensitivity of the silver halide photographic light-sensitive material. Specifically, at least light having a wavelength of 500 nm or less is absorbed and the wavelength range of 450 to 600 nm is absorbed. It is preferable to use a fluorescent dye or pigment exhibiting an emission peak. The emission peak is more preferably 490 to 600 nm
And particularly preferably in the range of 500 to 570 nm. The half width of the emitted light is preferably 100 nm or less, more preferably 80 nm or less, and particularly preferably 70 nm or less.

By the conversion of the emission wavelength, the sensitivity of the radiographic assembly can be improved, and at the same time, the crossover can be remarkably reduced due to the decrease of the blue emission light.

In the present invention, the fluorescent dye or fluorescent pigment refers to those having an emission quantum yield of 20% or more. Here, the quantum yield is: quantum yield (%) = (number of emitted photons / number of absorbed photons) × 1
It is represented by 00. The higher the quantum yield, the better,
It is preferably at least 40%, more preferably at least 60%.

The fluorescent dye or fluorescent pigment may be an inorganic compound fluorescent substance or an organic compound, and is not particularly limited. However, when it is contained in the phosphor layer, the particle diameter of the phosphor dye or pigment is preferably small in order not to impair the filling rate of the rare earth phosphor, usually in the range of 0 to 2 μm. It is preferably in the range of 0 to 1 µm. Also,
Preferably, it is not present in a solid state in the intensifying screen. Therefore, as a material having such a small particle diameter and a high quantum yield, a fluorescent dye or a fluorescent pigment made of an organic compound is preferably used.

As the fluorescent dye or fluorescent pigment, known dyes or pigments, for example, “Dye Handbook” (315-110)
9, Organic Synthesis Association, published in 1970) and "Color Material Engineering Handbook" (pp. 225-417, edited by The Color Material Association,
1989) can be used. In particular, the dyes described in "Laser Soy" (Mitsuo Maeda, Academic Press, 1984) are preferred. More specifically, Table 26-29
4. The carbocyanine dye described in No. 4, Tab.
phthalocyanine dye described in le11, xanthene dye described in Table 12 on pages 76 to 105, triarylmethane dye described in Table 13 on page 106, 10
Acridine dyes described in Table 14 on pages 7 to 110, fused ring compounds described in Table 18 on pages 137 to 149, coumarin and azacoumarin dyes described in Table 23 on pages 189 to 238, and T on pages 239 to 246.
quinolone and azaquinolone dyes described in Table 25, oxazole and benzoxazole compounds described in Table 26 on pages 247 to 261, and 273 to 27.
Furan and benzofuran compounds described in Table 29 on page 5, pyrazoline compounds described in Table 30 on page 276, phthalimide and naphthalimide compounds described in Table 31 on page 277, Tabl on page 282
The peteridine compound according to e32, Tabl at page 283
Examples include the pyrylium, phosphorine, boradiazinium and pyridine compounds described in e33.

Further, diketopyrrolopyrrole compounds described in JP-A-58-210084 and perylene compounds described in JP-A-7-188178 can be mentioned.

A fluorescent dye or a fluorescent pigment has a maximum (peak) wavelength in the absorption spectrum in the range of 350 to 500 nm and a maximum wavelength in the fluorescence (emission) spectrum of 500 to 500 nm.
Preferably, it is in the range of ~ 600 nm. More preferably, the maximum wavelength of the absorption spectrum is in the range of 400 to 490 nm, and the maximum wavelength of the fluorescence spectrum is 500 to 490 nm.
570 nm, and among the above compounds, such fluorescent dyes or pigments are carbocyanine dyes, xanthene dyes, triarylmethane dyes, acridine dyes, coumarin and azacoumarin dyes, phthalimide and naphthalimide compounds, pyrylium compounds, A diketopyrrolopyrrole compound and a perylene compound.
Particularly preferably, the maximum wavelength of the fluorescence spectrum is 500 to
In the 555 nm range, such fluorescent dyes or pigments are carbocyanine dyes, xanthene dyes, triarylmethane dyes, coumarin dyes, phthalimide and naphthalimide compounds, diketopyrrolopyrrole compounds, and perylene compounds.

It is preferable that these fluorescent dyes or fluorescent pigments have no afterglow. Those having a fluorescence lifetime of 10 ^-2 seconds or less are preferably used. Further, these fluorescent dyes or fluorescent pigments are required to be hardly decomposed by storage time or light or heat.

Hereinafter, specific examples of the fluorescent dye and the fluorescent pigment used in the present invention are shown, but the present invention is not limited to these.

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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[0143]

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A fluorescent dye or a fluorescent pigment, which is one of the characteristic requirements of the present invention, may be contained in any layer of the intensifying screen. It is preferable to include the phosphor layer in the surface protective layer, and particularly preferable is the phosphor layer.

The phosphor layer is prepared by dispersing the phosphor particles and, when the phosphor dye or pigment is contained, the particles in an organic solvent solution containing a binder resin to prepare a dispersion. The dispersion can be formed by directly applying the dispersion onto a support (or an undercoat layer such as a light-reflective layer provided on the support) and drying the dispersion. Alternatively, after applying the dispersion onto a separately prepared temporary support and drying to form a phosphor sheet, the phosphor sheet is peeled off from the temporary support and attached to the support using an adhesive. May be.

The particle size of the phosphor particles is not particularly limited, but is usually in the range of about 1 to 15 μm, preferably about 2 to 1 μm.
The range is 0 μm. It is preferable that the volume filling ratio of the phosphor particles in the phosphor layer is higher, and usually about 60 to 85%.
, Preferably in the range of 65 to 80%,
Particularly preferably, it is in the range of 68 to 75%. (The ratio of the phosphor particles in the phosphor layer is usually at least 80% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight.) The amount of the fluorescent dye or pigment used is usually The amount is in the range of 0.1 to 5000 mg, preferably in the range of 1 to 1000 mg, particularly preferably in the range of 5 to 500 mg per 1 kg of the phosphor. The binder resin, the organic solvent, and various additives that can be optionally used for forming the phosphor layer are described in various known documents. The thickness of the phosphor layer can be arbitrarily set according to the target sensitivity, but is preferably in the range of 70 to 150 μm for the front screen and 80 to 400 μm for the back screen.
m. Note that the X-ray absorption of the phosphor layer is determined by the amount of the phosphor particles applied.

The phosphor layer may be composed of one layer, or may be composed of two or more layers. Preferably it is one to three layers, more preferably one or two layers. For example, as the phosphor layer, a layer composed of phosphor particles having a relatively narrow particle size distribution and different particle sizes may be laminated, and in that case, a layer closer to the support has a smaller particle size. Is also good. Further, a phosphor layer may be formed by mixing phosphor particles having different particle diameters, or a phosphor layer may be formed.
As described on page 3, left column, line 3 to page 4, left column, line 39 of JP-A No. 0, even a phosphor layer having a structure in which the particle size distribution of the phosphor particles is inclined. Good. For example, Gd ₂ O
_In the case of 2S: Tb phosphor, the coefficient of variation of the particle size distribution is usually in the range of 30 to 50%, but monodisperse phosphor particles having a coefficient of variation of 30% or less can also be preferably used.

The support can be appropriately selected from various supports used for known radiographic intensifying screens according to the purpose. For example, a polymer film containing a white pigment such as titanium dioxide or a polymer film containing a black pigment such as carbon black is preferably used.

An undercoat layer such as a light reflecting layer containing a light reflecting material may be provided on the surface of the support (the surface on the side where the phosphor layer is provided). The light reflection layer is a layer made of a polymer binder containing a white pigment such as titanium dioxide. For example, as described in Examples 1 and 2 of JP-A-9-21899, the average particle size is 0.1 to 0.5 μm
It is preferable to provide a light reflecting layer containing 10 to 75% by volume of titanium dioxide in the range of 10 to 100 μm in thickness.

It is preferable to provide a surface protective layer on the surface of the phosphor layer. As the surface protective layer, the light scattering length measured at the main emission wavelength of the phosphor is preferably in the range of 5 to 80 μm, more preferably in the range of 10 to 70 μm, and particularly preferably in the range of 10 to 60 μm. It is.
Here, the light scattering length represents an average distance that light travels straight before being scattered once, and the shorter the scattering length, the higher the light scattering property. Further, the light absorption length representing the average free distance until light is absorbed is arbitrary, but from the viewpoint of the screen sensitivity, it is preferable that there is no absorption by the surface protective layer since the sensitivity decreases little. In order to make up for the insufficient scattering, it is possible to give a slight absorption.

The surface protective layer preferably has a structure in which light scattering particles are dispersed and contained in a resin material. The light refractive index of the light-scattering particles is usually 1.6 or more, preferably 1.9 or more. The particle size of the light-scattering particles is usually in the range of 0.1 to 1.0 μm. Examples of such light scattering particles include magnesium oxide, zinc oxide, zinc sulfide, titanium dioxide, niobium oxide, barium sulfate, lead carbonate, silicon dioxide, polymethyl methacrylate, styrene, and fine particles of melamine. it can. Among these, preferred light scattering particles having a particularly high refractive index are fine particles of zinc oxide, zinc sulfide, titanium dioxide, and lead carbonate, and particularly preferably titanium oxide (particularly anatase type).

The resin material used for forming the surface protective layer is not particularly limited, but polyethylene terephthalate, polyethylene naphthalate, polyamide, aramid, fluororesin, polyester and the like can be preferably used.

The surface protective layer is prepared by dispersing the light-scattering particles in an organic solvent solution containing a resin material (binder resin) to prepare a dispersion, and then depositing the dispersion on the phosphor layer (or It can be formed by applying directly (via any auxiliary layer) and then drying. Alternatively, a separately formed protective layer sheet may be provided on the phosphor layer using an adhesive. The thickness of the surface protective layer is usually 2 to 12
.mu.m, preferably 3.5-10 .mu.m. The surface protective layer may contain a fluorescent dye or pigment by adding particles of the fluorescent dye or fluorescent pigment to this dispersion.

Further, with regard to a preferred method for producing a radiation intensifying screen and materials used therefor, for example, JP-A 9-21899, page 6, left column, line 47 to line 8
5th line on the left column of the page, 17th line on the right column of page 2 to 33rd line on the 3rd page of page 2 of JP-A-6-347598, and 42nd line on the 3rd page left column of the same publication from 4th page left. There is a detailed description in column 22 line, which can be referred to.

Examples of the developing agent for processing the photographic light-sensitive material of the present invention include polyhydroxybenzene compounds represented by hydroquinone and ascorbin conventionally used in processing systems for medical silver halide photographic light-sensitive materials. Acids or erythorbic acids, that is, ascorbic acid or erythorbic acid (a diastereomer of ascorbic acid) and alkali metal salts thereof such as lithium salt, sodium salt and potassium salt are preferably used.

Of these, ascorbic acid or erythorbic acid and alkali metal salts thereof such as lithium salt, sodium salt and potassium salt are preferable.

The amount of the developing agent is usually 0.01 mol / liter to
It is preferably used in an amount of 0.8 mol / l,
It is particularly preferred to use from 0.1 mol / l to 0.4 mol / l. These may be used alone or in combination of two or more.

In the present invention, it is preferable to use an auxiliary developing agent exhibiting superadditivity together with the developing agent.

As an auxiliary developing agent exhibiting superadditivity, 1-
There are phenyl-3-pyrazolidones auxiliary developing agents.

Examples of 1-phenyl-3-pyrazolidones as auxiliary developing agents include 1-phenyl-3-pyrazolidone and 1-phenyl-3-pyrazolidone.
Phenyl-4,4-dimethyl-3-pyrazolidone, 1-
Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3
-Pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-
Examples include dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. Of these, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone is preferred.

In the present invention, when a 1-phenyl-3-pyrazolidone auxiliary developing agent is used in combination with the developing agent, the amount is 0.001 mol / L to 0.1%.
It is preferably used in an amount of mol / l, particularly preferably from 0.005 mol / l to 0.05 mol / l. Even if these are used alone, 2
More than one species may be used in combination.

The developer using the above developing agents is
The pH is preferably from 7 to less than 10, and more preferably from pH 8 to 9.
It is more preferably 5 or less, and even when the pH of the developer is in this range, the light-sensitive material of the present invention shows excellent dye decolorization.

The concentration of sulfite ions in 1 liter of these developing solutions is preferably 0.01 mol or more and 0.6 mol or less, and more preferably 0.05 mol or more and 0.2 mol or less from the viewpoint of environmental compatibility of the waste liquid.
The light-sensitive material of the present invention can be quickly decolorized even at a low molar concentration of sulfite ion.

In the method of processing a photographic light-sensitive material of the present invention, the processing time of Dry to Dry from the time when the light-sensitive material is carried into the developing tank to the end of the drying step may be from 20 seconds to 200 seconds. , 25 seconds or more and 150 seconds or less, more preferably 25 seconds or more and 125 seconds or less.

Further, in the method for processing the photographic light-sensitive material of the present invention, the replenishment amounts of the development and fixing are preferably from 25 ml to 200 ml per square meter (1 m ² ) of the photographic light-sensitive material, more preferably 40 ml
It is more preferably at least 160 ml and at most 60 ml and at most 130 ml.

The light-sensitive material of the present invention has an absolute humidity of 1.4% by weight or less, preferably 1.3 to 1.5%, as an environmental condition after coating and drying.
It is preferable to wind up at 0.6% by weight in a roll shape. Further, when the roll-shaped coated product is processed into a product form, the environmental condition is an absolute humidity of 1.4% by weight or less, preferably 1.3 to 1.5% by weight.
Preferably it is 0.6% by weight.

Further, the photographic material in the product form is sealed and stored in a moisture-proof package until it is opened, and the absolute humidity in the package is 1.4% by weight or less, preferably 1.3% by weight or less. It is preferable that the container is hermetically sealed so as to be 0.6% by weight.

[0168]

The present invention will be specifically described below with reference to examples. Example 1 (Method of preparing dye for crossover cut) Wet cake of Dye C1 used in Comparative Example Synthesis of III-3 of Example 1 of JP-A-6-317877, and heat-treated water-wet cake-like dye obtained in the same manner as III-3-D were used as C1. And

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[0170] 2. Wet cake of dye C2 used in Comparative Example A 1 / A dye described in JP-A-1-72828 was synthesized, and a water wet cake dye was designated as C2.

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[0172] 3. Dye I-46 wet cake used in examples of the present invention Dye A (solid 10 g) and methanol 150
In a mixed solvent of 50 ml of water and 50 ml of water, the mixture was stirred for 2 hours while controlling the temperature at 70 ° C. to produce a wet cake dye I-46 in water.

As a result, the dye crystals contained 2 mol of methanol and 1 mol of water per 1 mol of the dye. As a method of confirming the crystallization solvent, the wet cake was dried at room temperature for measurement, and the presence of methanol in the crystals was confirmed by ¹ H-NMR. The presence of water of crystallization was confirmed by Karl Fischer titration.

It was also confirmed that heating the crystals at 150 ° C. released methanol and water of crystallization in the crystals. From this, the dye solids concentration in the wet cake is 50
% By weight.

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4. Wet cake of dye B used in the present invention Example 10 g of compound b1 and 8 g of compound b2 were added to DMF (N, N-
(Dimethylformamide) solvent to obtain a DMF wet cake dye of Dye B (solid content: 20 g).

According to ¹ H-NMR measurement, this dye did not contain the solvent DMF in the crystals.

The dye solids concentration in the wet cake determined from the dry weight was 50% by weight.

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5. Wet cake of dye I-77 used in Examples of the present invention 10 g of compound b1 and 8 g of compound b2 were added to DMAc (N, N
-Dimethylacetamide) in a solvent to give dye B
A DMAc wet cake dye (solid content: 20 g) was obtained.

According to ¹ H-NMR measurement, this dye was found to be N, N
-Dimethylacetamide was contained in an amount of 2 mol per mol of the dye. Take this wet cake dye for measurement,
When heated, it has an endothermic peak at 160 ° C and DM in the crystal
Ac was completely released. The dye solids concentration in the wet cake determined from the heat-dried weight was 70% by weight.

(Preparation Method of Microcrystal Water Dispersion of Dye for Crossover Cut) Each of the above wet cake-like dyes was treated as a wet cake without drying, and 3.0 g of the dye solid was weighed. Water for dispersing and a 25% by weight solution of Demol SNB (manufactured by Kao Corporation) as a dispersant
After pre-mixing 2.4 g, add the above dye and add a total of 3
The mixture was adjusted with water to 0 g and mixed well to obtain a slurry.

120 g of zirconia beads were prepared, put in a vessel together with the slurry, and 1500 rpm using a 1/16 gallon sand grinder mill (manufactured by Imex Co., Ltd.).
The vessel was dispersed while being cooled with water by rotation.

The average particle size of the zirconia beads is as follows:
Dye B and Dye C2 used were 0.5 mm, and others were 1 mm. Table 1 shows the dispersion time of each dye.

After completion of the dispersion, the solid content of the dye was 5% by weight.
Was added to obtain a dispersion liquid. Each dye dispersion was designated as DP1 to DP5.

The obtained dispersions of the respective dyes are dyes dispersed in the form of microcrystals. Each of the dyes was photographed by an electron microscope using a carbon replica method, and the average particle size was determined from the projected area of 500 arbitrary microcrystals. I asked. The results are shown in Table 1.

Each of the dispersions was diluted to a constant volume, and a light absorption spectrum was obtained by detecting transmitted light of the dispersion. Table 1 shows the absorption maximum wavelength of each dispersion and the absorbance (extinction coefficient) at a wavelength of 550 nm.

[0189]

[Table 1]

Dye Microcrystalline Dispersion DP as Comparative Example
The absorption maximum wavelengths of 1 and DP2 were 510 nm and 490 nm, respectively. DP3, DP4, DP5 used in examples of the present invention
Has a maximum absorption wavelength in the range of 500 nm or more and 600 nm or less, and preferably has a large absorption coefficient at a wavelength of 550 nm. The absorption spectrum of a dispersion of these dyes is shown in FIG.

The performance when each dispersion is applied to a silver halide photographic material (photographic material) will be described below.

(Method for Preparing Coating Solution for Crossover Cut Layer) Each compound was added to the mother liquor so that the following coating amount was obtained. The order of addition of each compound, described material coating amount per surface 1 m ^2. -Dispersion of the dye for crossover cut is shown in Table 2 as solid content-Gelatin 0.30 g-Sodium polystyrene sulfonate (average molecular weight 600,000) 8.9 mg-A-15 mg-Preservative D 1 mg At this time, acetic acid or caustic soda Was used to adjust the pH of the coating solution to 6.0. The coating amount on one side 1 m ² per
It was 0.0cc.

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(Preparation method of tabular silver halide emulsion T1) 6.9 g of potassium bromide, 5 g of ammonium nitrate and 3.5 g of low molecular weight gelatin having a weight average molecular weight of 15,000 were added to 1 liter of water, and the mixture was kept at 45 ° C. 40cc of silver nitrate aqueous solution (4.0g of silver nitrate) and 3.15 of potassium bromide while stirring
g of 45 cc was added over 40 seconds by the double jet method. Next, after 18.6 g of gelatin was added, 40 cc of an aqueous solution of silver nitrate (4.0 g of silver nitrate) was added over 10 minutes while the temperature was raised to 60 ° C. Here, 25 cc of a 1N aqueous solution of caustic soda was added, and the mixture was physically aged at 60 ° C. for 20 minutes, and then 5.0 cc of a 100 wt% acetic acid aqueous solution was added.

Subsequently, 435 cc of an aqueous solution of 158.67 g of silver nitrate
And 400 cc of a 30 wt% potassium bromide solution were added by a control double jet method over 35 minutes while maintaining pAg 8.5 until the entire amount of silver nitrate aqueous solution was added. Next, 17.5 cc of a 2N potassium thiocyanate solution was added. After physical ripening at 60 ° C for 5 minutes, the mixture was mixed with cold water and cooled to 35 ° C.

Thereafter, the soluble salts were removed by the sedimentation method. The temperature was raised again to 40 ° C., and 35 g of deionized / alkali-treated gelatin, 0.175 g of preservative D and 0.35 g of sodium polystyrenesulfonate as a thickener were added, and the solution was adjusted to pH 6.4 and pAg 8.00 with sodium hydroxide and silver nitrate solution. It was adjusted.

In the completed silver halide grains, tabular grains having a (111) plane having an aspect ratio of 2 or more and 30 or less as main planes accounted for 99% of all grains as a total projected area.

The average of the circle-equivalent diameters of the projected areas of all grains is 0.
72 μm, the coefficient of variation was 28%. The average of the thickness of all the particles was 0.12 μm, and the average of the aspect ratio of each particle was 6.4.

The characteristics of the tabular grains are as follows:
% Are circular tabular grains having no sharp corners, and hexagonal tabular grains having a ratio of adjacent sides of 0.5 or more and 2 or less accounted for 20%.

The emulsion prepared as described above was subjected to chemical sensitization while being kept at 56 ° C. while stirring.

First, 0.27 g of sodium ethylthiosulfinate was added to 1 mol of silver halide emulsion, and then 23.5 cc of 1% potassium iodide was added.

Subsequently, 4-hydroxy-6-methyl-1,3,3a, 7-
6.4 cc of tetrazaindene was added, and sensitizing dye-1 was further added.
Was added simultaneously with 768 mg of sensitizing dye-2.

Three minutes later, 5 mg of chloroauric acid and 6.2 cc of 1 wt% potassium thiocyanate were added in advance, and then 1.3 mg of sodium thiosulfate and 1.7 mg of selenium compound 1 were added.
mg was added at the same time. Forty minutes later, 41 mg of mercapto compound M was added as a terminator for chemical sensitization, and the temperature was lowered to 40 ° C.

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(Preparation Method of Coating Solution for Tabular Silver Halide Emulsion T1) Each compound was added so that the following coating amount was obtained. Sided 1 m ² per material application quantity and silver amount 1.3 g, Gelatin 1.1 g-dextran (average molecular weight 39,000) 0.4 mg - Sodium polystyrenesulfonate (average molecular weight 600,000) 35mg · A-2 110mg · A-3 1.7 mg ・ A-4 0.2mg ・ A-5 2.0mg ・ Dye 1 (oil emulsion) 0.33g as dye solid content ・ 1,2-bis (vinylsulfonylacetamide) ethane 60mg At this time, the coating amount of this emulsion layer is one side 1m ² per 31.0cc
Met. The compounds in the above were as follows.

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(Preparation Method of Coating Solution for Surface Protective Layer) Each compound was added so as to have the following coating amount. It sided 1 m ² per material coating amount Gelatin 1.0 g · Sodium polyacrylate (average molecular weight 400,000) 7 mg - Sodium polystyrenesulfonate (average molecular weight 600,000) 1.1 mg · matting agent-1 (average particle size 3.7 .mu.m) solid 70mg as a part ・ A-6 13.8mg ・ A-7 34.5mg ・ A-8 6.8mg ・ A-9 1.2mg ・ A-10 1.4mg ・ A-11 2.1mg ・ Preservative D 0.9mg At this time, a small amount of caustic soda The pH of the coating solution for the surface protective layer was adjusted to 6.8. The coating amount on one side 1 m ² per
It was 0.0cc. The compounds in the above were as follows.

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(Method of Preparing Support) Biaxially stretched thickness
Corona discharge was carried out on a 175 μm polyethylene terephthalate support, and each coating solution containing the following main components was applied to both sides of the support by a wire bar coater in the order of a first undercoat layer and a second undercoat layer.

First Undercoat Layer (Support Side) The amount of the coating solution per square meter on one side of the support was 4.9 cc.
The coating amount per square meter on one side of the support of each additive material is as follows.・ Styrene butadiene copolymer latex (as solid content) 0.31 g ・ 2,4-Dichloro-6-hydroxy-s-triazine sodium 8 mg Drying temperature 190 ° C.

Second undercoat layer The amount of the coating solution per square meter on one side of the support was 7.9 cc.
The coating amount per square meter on one side of the support of each additive material is as follows. Gelatin _{80mg · C 12 H 25 O (} CH 2 CH 2 O) 10 H 1.8mg · preservatives D 0.27 mg-average particle diameter 2.5μm matting agent 2.5mg drying temperature 185 ° C. polymethyl methacrylate

(Coating method of photographic material) A dye layer was formed on the undercoated support prepared as described above, from the support side.
Co-extrusion was carried out simultaneously on both sides so as to form a silver halide emulsion layer and a surface protective layer, and dried.

(Measurement of Swelling Ratio of Photographic Material) First, the photographic material to be measured was aged at 40 ° C. and 60% RH for 7 days.
Next, this photographic material was immersed in distilled water at 21 ° C. for 3 minutes,
This state was frozen and fixed with liquid nitrogen. This photographic material was cut with a microtome so as to be perpendicular to the surface of the photographic material, and then freeze-dried at -90 ° C. The treated product was observed with a scanning electron microscope to determine the swollen film thickness Tw. On the other hand, the film thickness Td in a dry state was also determined by cross-sectional observation using a scanning electron microscope. Tw and Td obtained in this way
Swelling rate (unit%)
And When each photographic material was measured by this method,
The swelling ratio was 165%.

(Measurement of Spectral Sensitivity) Each photographic material was exposed from one side using an equal energy spectrophotometer. Thereafter, a developing treatment was performed, and the film on the side opposite to the exposed surface was removed. As a result of reading the exposure amount that gives a density of 0.5 on the exposed surface side at that time, any photographic material has a wavelength of 55 that gives a constant developed silver concentration.
The logarithm (expressed as 450/550 spectral sensitivity) of the ratio of the exposure amount of the monochromatic light of wavelength 450 nm to the exposure amount of the monochromatic light of 0 nm is 0.95.
Met.

(Method of Manufacturing Intensifying Screen Using Fluorescent Dye) Preparation of Support with Titanium Dioxide-Containing Reflective Layer 500 g of rutile-type titanium dioxide powder (manufactured by Ishihara Sangyo Co., Ltd., trade name: CR95) having an average particle size of 0.28 μm and acrylic binder resin (manufactured by Dainippon Ink and Chemicals, Inc.) 100 g of Chris Coat P1018GS) was added to methyl ethyl ketone and mixed and dispersed. Thick this dispersion
The thickness of the dried polyethylene terephthalate (PET) film is 40
The coating was uniformly coated to a thickness of μm and dried to obtain a support having a reflective layer containing titanium dioxide. The volume filling rate of the titanium dioxide particles in the obtained support with a titanium dioxide-containing reflective layer is as follows:
48%.

[0216] 2. Preparation of Phosphor Sheet 250 g of phosphor particles of terbium-activated gadolinium oxysulfide (Gd ₂ O ₂ S: Tb, Tb activation amount 0.3 mol%) having an average particle diameter described later and a polyurethane-based binder resin (Dainippon Ink Chemical Industry Co., Ltd.) Product name: Pandex T52
65M) 8 g, epoxy binder resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name: Epicoat 1001) 2 g,
Coumarin-6 (Aldrich No. 25 in the text) is used as a fluorescent dye.
15 mg of compound No. 44,263-1) and 0.5 g of isocyanate compound (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) were added to methyl ketone,
Dispersed with a propeller mixer. By this method the average particle size
2.0 μm, 3.0 μm, 6.2 μm, each dispersion containing terbium-activated gadolinium oxysulfide phosphor particles of 7.0 μm, coated and dried on the surface of the temporary support to form a phosphor layer, peeled off the temporary support from this, A phosphor sheet containing phosphor particles of each average particle size was obtained.

[0217] 3. Addition of a front-side phosphor layer A calendar roll treatment is performed using each of the phosphor sheets described above to form a phosphor layer having a multilayer structure with different average particle diameters of the phosphor particles on a support having a titanium dioxide-containing reflective layer. did. Phosphor particles having an average particle size of 7.0 μm were used for the upper layer (layer thickness after calender roll treatment) and phosphor particles having an average particle size of 2.0 μm were used for the lower layer (layer thickness after calender roll treatment). The volume filling ratio of the phosphor particles in the phosphor layer is 70
%Met.

[0218] 4. Attachment of phosphor layer for back side A calendar roll treatment is performed using each of the phosphor sheets described above to form a phosphor layer having a multilayer structure with different average particle diameters of phosphor particles on a support having a reflective layer containing titanium dioxide. did. Phosphor particles having an average particle diameter of 6.2 μm were used for the upper layer (layer thickness after calender roll treatment) and phosphor particles having an average particle diameter of 3.0 μm were used for the lower layer (layer thickness after calender roll treatment: 80 μm). The volume filling ratio of the phosphor particles in the phosphor layer is 70
%Met.

[0219] 5. Preparation of Film for Surface Protective Layer For the surface protective layer of the intensifying screen, anatase-type titanium oxide (trade name: A220, manufactured by Ishihara Sangyo Co., Ltd.) in polyethylene terephthalate (PET) having a thickness of 6 μm.
3% by weight was prepared. The scattering length of this PET film by monochromatic light of 545 nm is 30 μm, and the haze is
It was 50. A polyester-based adhesive was applied to one surface, and a surface protective layer was provided on the phosphor layer by a lamination method.
The front screen containing coumarin-6 as a fluorescent dye thus obtained in the phosphor layer was FG1,
The screen for the back side was BG1.

6. Measurement of Fluorescence Spectrum FIG. 2 shows a fluorescence emission spectrum when the front-side FG1 is irradiated with X-rays (W tube, 40 kVp). For comparison, FIG. 3 shows a spectrum of a front screen manufactured without adding a fluorescent dye, and FIG. 4 shows a spectrum of a front screen manufactured by adding a yellow absorbing dye (no fluorescence). Indicated.

Comparing FIG. 2 with FIG. 3, it can be seen that in the screen to which the fluorescent dye is added, the fluorescence below 500 nm is reduced and the fluorescence in the range of 500 to 600 nm is increased. This increase in the fluorescence in the range of 500 to 600 nm is due to the fact that the fluorescent dye absorbs the emission of the phosphor particles of 500 nm or less and fluoresces in the range of 500 to 600 nm. In addition, the spectrum of the front screen to which the yellow absorbing dye (not fluorescent) shown in FIG. 4 is added shows that the fluorescence of 500 nm or less is small due to the light absorption of the dye, but is in the range of 500 to 600 nm. Little change is seen in the fluorescence.

(Measurement of Optical Transmission Density of Dye in Photographic Material) Using a spectrophotometer, the amount of transmitted light was measured with an integrating sphere, and the transmission densities at wavelengths of 550 nm and 450 nm were determined. Regarding the optical transmission density of each wavelength of the dye in the photographic material, when the photographic material was processed after the fixing step without intentionally undergoing development processing in the above-described processing method, the dye in this experiment was hardly contained in the photographic material. Utilizing the fact that it is retained without being decolorized.

That is, 450 nm or 5 nm of the dye in the photographic material.
The optical transmission density at 50 nm was determined by the following equation. (Dye transmission density) = (Transmission density of sample subjected to processing after fixing) − (Transmission density of sample in which development processing was performed twice without exposure and dye was completely removed) Are shown in Table 2. 5 for the transmission density of 450 nm
The ratio of the transmission densities at 50 nm was expressed as the 550/450 concentration ratio of the dye.

(Measurement of Crossover Value) In this experiment, the front side FG1 and the back side intensifying screen BG1 containing the above-mentioned fluorescent dye were used. Each intensifying screen for the front side and the back side sandwiches each photographic material from both sides, and 80 kV with a three-phase pulse generator
Exposure was performed using the X-rays generated by applying the above voltage as a light source. The crossover value (%) was measured according to the definition described in JP-A-1-172828.

In a light-sensitive material for X-ray medical photography having a light-sensitive silver halide emulsion layer on both sides of a support, light transmitted through the support (an intensifying screen as an assembly absorbs X-rays and emits visible light) Fluorescence) reduces the sharpness of the image.

For this reason, the smaller the value of the crossover is, the more excellent the sharpness is. When the value is 12% or less, a medical image excellent in diagnosis can be obtained. In particular, it is preferable to reach 7% or less, because the diagnostic ability is further improved. Table 2 shows the obtained crossover values.

(Preparation of Concentrated Developing Solution) Concentrated developing solution A of the following formulation containing sodium erythorbate as a developing agent was prepared. -Diethylenetriaminepentaacetic acid 8.0 g-Sodium sulfite 20.0 g-Sodium carbonate monohydrate 52.0 g-Potassium carbonate 55.0 g-Sodium erythorbate 60.0 g-4-hydroxymethyl-4-methyl-1-phenyl- 13.2 g of 3-pyrazolidone 1.43 g of 3,3'-diphenyl-3,3'-dithiopropionic acid 50.0 g of diethylene glycol

[0228]

Embedded image

[0229]

Embedded image

Water was added to make up 1 liter. The solution pH was set to be the same as that of the developing mother liquor described below.

(Preparation of developer replenisher)
It was diluted twice and used as a developing replenisher.

(Preparation of developing mother liquor) A processing method using a developing solution prepared by adding a starter solution having the following composition to a diluted solution of 55 ml per liter of a developing solution and adjusting the pH to 9.0 with acetic acid or sodium hydroxide was applied to D1, pH10. The processing method using the developing solution adjusted to 5 was D2.

(Preparation of starter solution) Potassium bromide 11.1 g Acetic acid 10.8 g Water was added to 55 ml.

(Preparation of concentrated fixing solution) A concentrated fixing solution having the following formulation was prepared. Water 0.5 liter Ethylenediaminetetraacetic acid dihydrate 0.05 g Sodium thiosulfate 200 g Sodium bisulfite 98.0 g Sodium hydroxide 2.9 g Adjust the pH to 5.2 with NaOH, add water and add 1 Liters. pH was 5.4.

(Fixing Replenishment Method) The above-mentioned concentrated fixing solution was used as a fixing replenishing solution, and the replenishing amount of the concentrated solution and the amount of water flowing into the fixing tank from the second washing were set at 1: 1. Was used as the replenisher volume.

(Washing water replenisher)-Glutaraldehyde 0.3 g-Diethylene-triamine-penta-acetic-acid 0.5 g Diluted with distilled water, adjusted to pH 4.5 with NaOH, and finished solution 1 liter Was obtained.

(Processing process of photographic material) The drive system, tank and drying method of CEPROS P manufactured by Fuji Photo Film Co., Ltd. were changed, the washing layer was made two-stage washing, and washing water was replenished from the second washing tank. A two-stage countercurrent system was used. The opening ratios of the developing tank and the fixing tank were improved to 0.02 cm ^-1 . The capacity of each washing tank is 2.5 liters. In addition, a heat roller method was used for drying.

Using the above-mentioned developing mother liquor, fixing mother liquor and washing water replenisher, processing was carried out while replenishing the developing replenisher, fixing replenisher and washing water replenisher with 65 ml per m ² of the photographic material.

Process temperature Processing time Current image 35 ° C. 10 seconds Fixed 35 ° C. 10 seconds Rinse 1st 30 ° C. 8 seconds Rinse 2nd 25 ° C. 8 seconds Dry 55 ° C. 24 seconds Total 60 seconds

(Evaluation method of residual color) Processing method D described above
1 and D2, the following evaluation tests were performed. Each photographic material having a quarter size was developed without being exposed, and the degree of residual color of each dye was evaluated. A: Very good level with no residual color visually. ；: The residual color is extremely small, which is a practically acceptable level. Δ: A residual color is generated, and the color tone of the entire film is changed, which is a problem. C: The residual color is strongly generated, and there is a large period of residual color unevenness, which is a problem. Table 2 shows the evaluation results.

(Development processing method of photographic material) In order to obtain the above-mentioned crossover, the photographic material was processed by using the above-mentioned processing method D2.

[0242]

[Table 2]

(Results) The photographic materials 2 having a maximum absorption wavelength of 510 nm and the photographic materials 3 and 4 having a 490 nm wavelength have satisfactory values as crossovers, but at a level unacceptable for use in view of residual color in the processing method D1. is there.

The photographic materials 5 to 9 of the present invention have no problem in residual color, and the crossover value when using a Gd ₂ O ₂ S: Tb phosphor screen (FG1, BG1) containing a fluorescent dye. Is also preferably 12% or less.

In particular, the photographic materials 6 and 9 of the present invention have a crossover value of 6% or less, achieving a significant reduction in crossover. Are all 3 or more.

Example 2 Emulsion T1 was prepared by changing the grain formation method of emulsion T1 of Example 1.
The silver halide emulsions T2, T3, T4 and T5 having tabular grains having different aspect ratios and almost the same sensitivity as in the above were prepared. Table 3 shows the aspect ratio of each emulsion.

Further, silver halide emulsions T6 and T7 in which only the iodine amount was changed by adjusting the amount of the silver iodide fine grain emulsion added in the chemical sensitization step of the emulsion T1 were prepared.

Except for the grain formation method and the amount of silver iodide emulsion added,
The method for removing soluble salts, the method for dispersing, and the method for chemical sensitization were carried out in exactly the same manner as for Emulsion A. Table 3 shows the average iodine content of each emulsion.

(Preparation Method of Silver Chloride Tabular Grain Emulsion TC) In a reaction vessel, 1582 ml of an aqueous gelatin solution (10 g of gelatin-1 (deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g), an HNO ₃ IN solution 7.8
ml, pH 4.3), NaCl-1 solution (100 m
13 ml of NaCl (containing 10 g of NaCl), and keeping the temperature at 38 ° C., Ag-1 solution (A in 100 ml)
gNO ₃ 20 g) and X-1 solution (N in 100 ml)
aCl) at 62.4 ml / min.
5.6 ml were added simultaneously. After stirring for 3 minutes,
The Ag-2 solution (containing 2 g of AgNO _{3 in} 100 ml) and the X-2 solution (containing 1.4 g of KBr in 100 ml) were simultaneously mixed at 80.6 ml / min in 28.2 ml portions. Three
After stirring for 1 minute, 62.4 ml of the Ag-1 solution and the X-1 solution were added.
At the same time. After stirring for 2 minutes, 203 ml of an aqueous gelatin solution (gelatin-11
3g, 1.3g of NaCl, N to make pH 6.5
(including 1N aOH solution) to adjust the pCl to 1.75, then raise the temperature to 60 ° C., and then add 6 × 10 ^-4 mol of hydrogen peroxide to 1 g of gelatin, and add pCl to 1.7.
Aged for 3 minutes according to 0. Thereafter, 2.68 of the AgCl fine grain emulsion (E-1) (average grain diameter: 0.1 μm) was added.
AgCl was added for 20 minutes at an AgCl addition rate of × 10 ^-2 mol / min. After aging for 40 minutes after completion of the addition, a precipitant was added, the temperature was lowered to 35 ° C, and the precipitate was washed by settling. An aqueous gelatin solution was added and the pH was adjusted to 6.0 at 60 ° C.

A replica TEM image of the above particles was observed. The resulting emulsion had an AgBr of 0.4 based on silver.
Silver chloride tabular grains having a major plane of {100} containing 4 mol%. The shape characteristic value of the above particles is (the total projected area of {100} tabular grains having an aspect ratio of 2 to 25 / the sum of the projected areas of all AgX grains) × 100 =
a1 = 95% (average aspect ratio (average diameter / average thickness) of {100} tabular grains) = a2 = 7.0 (average diameter of {100} tabular grains having an aspect ratio of 2 to 30) = a3 = 1.0 μm (ratio of main surface edge length of {100} tabular grains having an aspect ratio of 2 to 30) = a4 = 0.90 (average thickness of {100} tabular grains having an aspect ratio of 2 to 30) = A5 = 0.09 μm (Coefficient of variation of thickness distribution of {100} tabular grains having an aspect ratio of 2 to 30 (standard deviation of thickness / average thickness) =
a6 = 0.12 ({100} tabular grains having an aspect ratio of 2 to 25, in which two dislocation lines extending from the corners of the grains can be observed with a transmission electron microscope / projected area / aspect ratio of 2 or more) Projected area of {100} tabular grains of 25 or less × 1
00) = a7 = 87 (average angle between two dislocation lines) = a8 = 56 ° Observation by a direct TEM image of the tabular grains revealed that even after the coating, the emulsion had a grain size of 57% of the projected area. In addition, the above dislocation lines could be observed.

First, photographic materials 10 to 16 were prepared by using photographic material 6 of the present invention as a basic formulation and changing emulsion T1 to emulsions T2 to T7 and TC, respectively. Except that the emulsion was changed, the procedure was the same as for photographic material 6.

Further, as comparative examples, photographic materials 17 and 18 were prepared by changing emulsion T1 of photographic materials 2 and 4 to emulsion TC. The photographic material 1 was used in the developing method D1 of Example 1.
The residual color of the dyes 0 to 16 was at a level without any problem.

(Measurement of Crossover and Sensitivity) Crossover was performed in the same manner as in Example 1. The relative sensitivity on the front side at that time was expressed as a relative value with the value of the photographic material 10 as 100%.

(Measurement of Spectral Sensitivity) The measurement was carried out in the same manner as in Example 1, and the value was described in Table 3 as 450/550 spectral sensitivity.

[0255]

[Table 3]

(Result) 550 nm giving the same developed silver concentration
The photographic materials 6, 10 to 14, and 16 of the present invention in which the logarithm of the ratio of the exposure amount at 450 nm to the exposure amount of the above were 0.8 or more gave small crossover values and gave favorable results. These photographic materials also obtained particularly high sensitivity. The photographic material 15 of the comparative example had a large crossover value, and the sharpness in practical shooting was not at a satisfactory level. In particular, photographic material 16 using a silver chloride emulsion exhibited high sensitivity, low crossover and favorable performance. On the other hand, in the photographic materials 17 and 18 as comparative examples, the emulsion was changed to TC, but the crossover did not change and the sensitivity was reduced.

[0257]

According to the present invention, both improvement of sharpness and reduction of residual color can be achieved even in low pH developer processing.

[Brief description of the drawings]

FIG. 1 is a graph showing an absorption spectrum of a dispersion of a dye in an example.

FIG. 2 is a graph showing a fluorescence emission spectrum of a front screen in an example.

FIG. 3 is a graph showing a fluorescence emission spectrum of a front screen in an example.

FIG. 4 is a graph showing a fluorescence emission spectrum of a front screen in an example.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 5/29 G03C 5/29 (72) Inventor Katsutoshi Yamane 210 Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F term (reference) 2H016 AA02 AA03 AB01 AB03 AC00 AE00 AE01 AG01 2H023 AA01 BA02 BA04 CA05 CE00 FA01 FD01

Claims (8)

[Claims] At least one side of a transparent support, at least one dye capable of being decolorized in a developing process for reducing crossover light, has an absorption maximum at a wavelength of 500 nm or more and 600 nm or less, and 55
Halogen fixed to at least one photosensitive layer or non-photosensitive layer in a state where the optical transmission density at 0 nm is three times or more the optical transmission density at a wavelength of 450 nm, and spectrally sensitized on both sides of the transparent support Having a photosensitive layer containing silver particles, in the photosensitive layer on at least one side of the transparent support, the exposure amount of the wavelength 450nm monochromatic light with respect to the exposure amount of the wavelength 550nm monochromatic light that gives a constant developed silver concentration Wherein the logarithm of the ratio is at least 0.8. _2. A phosphor which is substantially terbium-activated gadolinium oxysulfide (Gd ₂ O ₂ S: Tb), and further absorbs at least 500 nm or less of light emitted from the phosphor, A crossover of 0% or more and 12% or less when subjected to radiation exposure in combination with a radiation intensifying screen containing a fluorescent dye and / or a fluorescent pigment exhibiting an emission peak in a wavelength range of 500 nm to 600 nm. 2. The silver halide photographic light-sensitive material according to item 1. 3. The silver halide photographic light-sensitive material according to claim 1, wherein at least one kind of dye capable of being decolorized in a developing process for reducing crossover light is in the form of solid fine particles. 4. The silver halide photographic light-sensitive material according to claim 1, wherein said spectrally sensitized silver halide grains are tabular grains having an average aspect ratio of 4 to 30. 5. The silver halide according to claim 1, wherein the average amount of iodine contained in the spectrally sensitized silver halide grains is from 0 mol% to 0.4 mol%. Photosensitive material. 6. An average halogen composition of the spectrally sensitized silver halide grains is not less than 10 mol% and not more than 100 mol%.
The silver halide photographic light-sensitive material according to any one of claims 1 to 5, comprising at most mol%. 7. A method for processing a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to claim 1 is developed with a developer having a pH of 7 to less than 10. 8. The method for processing a silver halide photographic light-sensitive material according to claim 7, wherein the developer contains ascorbic acids and / or erythorbic acids as a developing agent.