JPH09319038A - Silver halide photographic sensitive material, method for forming x-ray image by using the same and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material prevented from occurrence of oil sludge and superior in antistaticness and silver color tone and capable of obtaining satisfactory photographic performances even in the case of low replenished rapid processing and to provide the X-ray image forming method and its processing method. SOLUTION: This photosensitive material has on a support hydrophilic colloidal layers including a silver halide emulsion layer and contains a leuco compound for giving a blue dye after processing in at least one of the hydrophilic colloidal layers and a conductive substance on the side of the support the same as the emulsion. This photosensitive material is imagewise exposed by sandwiching it with fluorescent sensitizing papers having an absorbance of >=45% of 80kVp energized X-rays and a fluorescent material filling rate of >=68% and a fluorescent layer thickness of 135-200μm. This photosensitive material is processed with an automatic developing machine provided with solid processing agents into a processing bath.

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 light-sensitive material and an X-ray image forming method and processing method using the same. The present invention relates to a silver halide photographic light-sensitive material which is excellent in color tone of a silver image and has a neutral black color and hardly contaminates an intensifying screen, and an X-ray image forming method and a processing method using the same.

[0002]

2. Description of the Related Art In recent years, the consumption of silver halide photographic light-sensitive materials (hereinafter also referred to as "light-sensitive materials") has been steadily increasing. There is a demand for speeding up, that is, an increase in the amount of processing within a unit time.

For example, in an X-ray photosensitive material for medical use,
In addition to the rapid increase in the number of diagnoses and the increase in the number of inspection items, the number of X-ray photographs taken is increasing, and it is necessary to notify the examinee of the diagnosis result as soon as possible, and further rapid processing is desired. Especially for angiography and intraoperative photography, it is necessary to see the photograph immediately after the photography.

However, such rapid processing has various problems. For example, in order to convey a film at a high speed in an automatic processor, it is easy to be charged due to friction with a conveying roller or peeling between films.
Therefore, the occurrence of fog or static blackening, which is called static mark, is likely to occur due to the discharge of static electricity.

Although a number of techniques for preventing electrification of light-sensitive materials have been disclosed in the past, few of them have sufficient antistatic effect and do not cause fluctuation deterioration in photographic performance. For example,
It has been found that the antistatic agent used for the light-sensitive material flows out and accumulates in the developing solution, and it adheres as oil sludge to the surface of the film to be subjected to the running process, resulting in poor fixing.

On the other hand, recently, due to strict environmental regulations, there is an urgent need to reduce the amount of processing waste liquid. Therefore, it is desired to further reduce the amount of replenishment to the automatic processor. However, it has been found that when the processing is carried out under such a low replenishment rate, the water-soluble components eluted from the light-sensitive material are accumulated in the processing solution, resulting in processing fluctuation and deterioration of photographic performance.

Further, in order to reduce the amount of processing waste liquid, it is necessary to improve the developability. Therefore, it is desirable to use silver halide grains having a high covering power and a high concentration to obtain a high concentration with a small amount of silver. It is known that tabular grains are suitable in terms of sharpness and color sensitization efficiency.

However, when the grain size or grain thickness of the silver halide grains is reduced, the light scattering of the blue light component due to silver formed by the development process is increased, and the light becomes strongly yellowish, so the silver image becomes yellowish. The result will be tinged with. This phenomenon occurs particularly when silver halide emulsions such as fine grain emulsions (for example, average grain size of 0.4 μm or less) and thin tabular grains (for example, grain thickness of 0.4 μm or less) are used. It is known that when the content is reduced or when the content of silver chloride is increased, it tends to become yellowish.

Conventionally, as a technique for improving the color tone of image silver, many studies have been reported from the side of light-sensitive materials and development processing solutions, and for example, a specific mercapto compound is well known as a representative color tone agent. . More recently, for example, a technique has been proposed in which a specific dye is dissolved in a water-insoluble high-boiling point organic solvent, as described in JP-A-5-165147, and dispersed in a fine size in a water solvent to be contained in a light-sensitive material. However, the sensitivity was changed depending on the storage conditions before exposure. Particularly, in the case of the X-ray photosensitive material for medical use, there is a problem that the intensifying screen brought into contact with the photosensitive material during exposure is stained. Further, this technique also has a drawback that the fog density is increased because the unexposed area contains the same amount of dye as the exposed area.

In order to solve this drawback, Japanese Patent Laid-Open No. 3-1
No. 57645 proposes a technique in which a dye image corresponding to silver development is formed by a diffusion resistant compound that releases a diffusible dye by the action of silver ions, together with the formation of a silver image. And the effect of reducing fog were insufficient. Further, JP-A-3-153234 proposes a technique using a leuco dye which gives a blue image corresponding to a silver image. Although the development of stains and stains of the developer is suppressed by the technique, the blue dye formed from the leuco dye described has a long-wavelength color tone and is tinged with a green color, so that the effect of improving the blackness of image silver is obtained. Was insufficient. In addition, the leuco dye remaining in the unexposed portion of the processed light-sensitive material tends to develop color over time, which causes a problem of increased fog.

[0011]

DISCLOSURE OF THE INVENTION The object of the present invention is to prevent generation of oil sludge, excellent antistatic performance and silver tone,
Another object of the present invention is to provide a silver halide photographic light-sensitive material, an image forming method and a processing method therefor capable of obtaining a sufficient photographic performance with a low replenishment speedy processing.

[0012]

The above object has been attained by the following constitutions.

(1) A hydrophilic colloid layer containing a silver halide emulsion layer is provided on a support, and at least one of the hydrophilic colloid layers contains a leuco compound which gives a blue dye after treatment, and A silver halide photographic light-sensitive material containing a conductive substance on the side having an emulsion layer on a support.

(2) The silver halide photographic light-sensitive material described in (1), wherein the leuco compound is represented by the following general formula (I).

[0015]

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In the formula, R ₁ and R ₂ each represent an alkyl group or an aryl group. R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, and n represents an integer of 1 to 3. X, Z
₁ and Z _2, 5-6 together with the carbon atom adjacent to Z _1, Z ₂
Represents an atomic group necessary for forming a member aromatic carbon ring or aromatic heterocycle. R ₄ represents a hydrogen atom, an acyl group, a sulfonyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. CP represents the following group.

[0017]

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In the formula, R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom, a halogen atom or a substituent capable of substituting on the benzene ring. R ₅ and R ₆ and R ₇ and R ₈ may be bonded to each other to form a 5- to 7-membered ring. R ₉ and R ₁₂ have the same meaning as R ₄ . R ₁₀ and R ₁₁ each represent an alkyl group, an aryl group or a heterocyclic group. R ₁₃ , R ₁₄ and R ₁₅ have the same meanings as R ₁₀ , R ₁₁ and R ₁₂ , respectively. R ₁₆ represents an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ has the same meaning as R ₄ , R ₁₈ has the same meaning as R ₃ , and m represents an integer of 1 to 3. R ₁₉ and R ₂₀ each represent an alkyl group or an aryl group. R ₂₁ and R ₂₄ have the same meaning as R ₄ , and R ₂₂ and R ₂₃ have the same meaning as R ₁₉ and R ₂₀ , respectively. Y represents an atomic group necessary for forming a 5- or 6-membered monocyclic or condensed nitrogen-containing heterocyclic ring together with two nitrogen atoms. * Indicates a bonding point between CP and other partial structures in the general formula (I).

(3) The silver halide according to (1) or (2), which contains the leuco compound represented by the general formula (I) in an amount of 1 × 10 ^{-6 to} 5 × 10 ^-1 mol per mol of silver. Photographic material.

(4) The silver halide photographic light-sensitive material as described in (1), (2) or (3), wherein the conductive substance is a metal oxide.

(5) The silver halide photographic light-sensitive material according to (4), wherein the metal oxide is a colloidal tin oxide sol and is contained in the undercoat layer.

(6) The silver halide grains contained in the silver halide emulsion layer are tabular having a main plane composed of two parallel (100) faces, and the silver chloride content is 10 mol% or more ( The silver halide photographic light-sensitive material described in any one of 1) to (5).

(7) The total amount of the hydrophilic binder on the support is 1.0 to 3.0 g / m ² per side (1) to
The silver halide photographic light-sensitive material described in any one of (6).

(8) The amount of silver applied per side is 1.0 to 2.
The silver halide photographic light-sensitive material according to any one of (1) to (7), which has an amount of 0 g / m ² .

(9) The silver halide photographic light-sensitive material described in any one of (1) to (8), which has emulsion layers on both sides of the support, has an X-ray energy of 45 with respect to X-rays of 80 kVp. The absorption rate of the phosphor is 68% or more and the filling rate of the phosphor is 68.
%, And an X-ray image forming method in which imagewise exposure is performed by irradiating with X-rays sandwiched between fluorescent intensifying screens having a phosphor thickness of 135 to 200 μm.

(10) A silver halide in which the silver halide photographic light-sensitive material described in any one of (1) to (8) is processed by an automatic processor having a mechanism for supplying a solid processing agent to a processing tank. Processing method of photographic light-sensitive material.

(11) The method for processing a silver halide photographic light-sensitive material according to (10), wherein the amount of the replenisher replenished in at least one of the developing step and the fixing step is represented by the following formula.

1 ≦ amount of replenishing liquid / amount taken out by the photosensitive material ≦ 5 (12) Processing time required for all processing steps (Dry to
The processing method of the silver halide photographic light-sensitive material according to (10) or (11), wherein the Dry) is within 20 seconds.

The present invention will be described in detail below.

The silver halide emulsion layer of the present invention contains the compound represented by the general formula (I).

In the general formula (I), the alkyl group represented by R ₁ and R ₂ is preferably a group such as methyl, ethyl, propyl or butyl. These may be further substituted, and as a preferable substituent, a hydroxyl group,
Examples include sulfonamide groups. The aryl group represented by R ₁ and R ₂ is preferably a phenyl group.
Examples of the monovalent substituent represented by R ₃ include alkyl groups (methyl, ethyl, i-propyl, hydroxyethyl,
Methoxymethyl, trifluoromethyl, t-butyl, etc.), cycloalkyl group (cyclopentyl, cyclohexyl, etc.), aralkyl group (benzyl, 2-phenethyl, etc.), aryl group (phenyl, naphthyl, p-tolyl,
p-chlorophenyl, etc.), alkoxy group (methoxy, ethoxy, i-propoxy, butoxy, etc.), aryloxy group (phenoxy, etc.), cyano group, acylamino group (acetylamino, propionylamino, etc.), alkylthio group (methylthio, ethylthio, Butylthio, etc.), arylthio group (phenylthio, p-tolylthio, etc.), sulfonylamino group (methanesulfonylamino, benzenesulfonylamino, etc.), ureido group (3-methylureido,
3,3-dimethylureido, 1,3-dimethylureide, etc.), sulfamoylamino group (dimethylsulfamoylamino, etc.), carbamoyl group (methylcarbamoyl,
Ethylcarbamoyl, dimethylcarbamoyl, etc.), sulfamoyl group (ethylsulfamoyl, dimethylsulfamoyl, etc.), alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (phenoxycarbonyl, etc.), sulfonyl group (methanesulfonyl) , Butanesulfonyl, phenylsulfonyl, etc.), an acyl group (acetyl, propanoyl, butyroyl, etc.), an amino group (methylamino, ethylamino,
Dimethylamino, etc.), hydroxyl group, nitro group, imide group (phthalimide, etc.), and heterocyclic group (pyridyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, etc.).

Examples of the alkali metal represented by Z include sodium and potassium. Examples of the quaternary ammonium group include ammonium groups having 8 or more carbon atoms, such as trimethylbenzylammonium, tetrabutylammonium, and tetradecylammonium.

Examples of the 5- or 6-membered aromatic carbocycle formed by carbon atoms adjacent to X, Z ₁ and Z ₂ and Z ₁ and Z ₂ include a benzene ring and a naphthalene ring, and preferably a benzene ring. And similarly, as the 5- or 6-membered aromatic heterocycle, each ring of pyridine, pyrimidine, pyridazine, pyrazine, triazine, tetrazine, pyrrole, furan, thiophene, thiazole, oxazole, imidazole, thiadiazole, oxadiazole, etc. Can be mentioned,
Preferably it is a pyridine ring.

Examples of the substituent capable of substituting on the benzene ring represented by R _{5 to} R ₈ include the above-mentioned monovalent substituents. Preferably it is an alkyl group.

Examples of the 5- to 7-membered ring formed by R ₅ and R ₆ and R ₇ and R ₈ bonded to each other include an aromatic carbocycle and an aromatic heterocycle, and a benzene ring is preferable.

Examples of the alkyl group represented by R ₁₀ and R ₁₁ include methyl, ethyl, propyl and butyl groups. Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a 5- to 6-membered aromatic heterocycle (pyridine, pyrazine, pyrimidine ring) having at least one of oxygen, sulfur and nitrogen atoms in the ring. 6-membered ring azines and their benzerogues; pyrrole, thiophene, furan and their benzerogues; imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, thiadiazole, oxadiazole and other 5-membered ring azoles and their residues Is mentioned. R
Preferably as ₁₀ and R ₁₁ phenyl, pyrazolyl,
And groups such as pyridyl.

Examples of the alkyl group represented by R ₁₆ include methyl, i-propyl, pentyl and t-butyl groups, and examples of the aryl group include phenyl and naphthyl groups. Examples of the sulfonyl group include benzenesulfonyl and the like, examples of the aryloxycarbonyl group include phenoxycarbonyl and the like, examples of the alkoxycarbonyl group include ethoxycarbonyl and the like, and examples of the carbamoyl group include diethylaminocarbonyl and the like.

Examples of the nitrogen-containing heterocycle represented by Y include imidazole, triazole and tetrazole rings and their benzo-fused rings.

Examples of the alkyl group represented by R ₁₉ and R ₂₀ include methyl, pentyl and t-butyl groups, and examples of the aryl group include phenyl and naphthyl groups.

Typical specific examples of the compound represented by formula (I) are listed below, but the invention is not limited thereto.

[0041]

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[0042]

[Chemical 6]

[0043]

[Chemical 7]

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

[Chemical 12]

[0049]

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It is preferable that the compound represented by the general formula (I) contains 1 × 10 ^{−6 to} 5 × 10 ⁻¹ mol per mol of silver for achieving the effect of the present invention. The effect of improving the tonality is small, and if it exceeds this, the whole image is felt dark, which is not preferable. More preferably, it contains 5 × 10 ^{−5 to} 5 × 10 ⁻² mol per mol of silver, and particularly preferably 5 × 10 ⁻⁴ to 1 × 10 ⁻² mol per mol of silver.

As the method for adding the compound represented by the general formula (I), any method may be used depending on the properties of each compound.
For example, a method of adding as a solid fine particle dispersion, a method of dissolving in a high boiling point solvent and then performing the above dispersion, and then adding a water-miscible organic solvent (methanol, ethanol, acetone, etc.)
And adding to the solution.

The preferred method is to add it as a solid fine particle dispersion or to dissolve it in a water-miscible organic solvent (methanol, ethanol, acetone, etc.) and add it. When added as a solid fine particle dispersion, a known dispersion method such as an acid precipitation method, a ball mill, a jet mill or an impeller dispersion method can be applied, and the average particle size of the dye fine particles to be solid-dispersed may take an arbitrary value. However, it is preferably 0.01 to 20 μm, more preferably 0.1 to 20 μm.
03 to 2 μm.

The compound represented by the general formula (I) can be contained in any layer of the photographic constitutional layers, but from the viewpoint of intensifying screen contamination, it is used as an emulsion layer or emulsion for radiography. It is preferably contained in a layer between the layer and the support, and particularly preferably in the transverse light blocking layer.

In the present invention, the amount of the hydrophilic binder in the silver halide emulsion layer is preferably 1.0 to 3.0 g / m ² per one side of the support, and more preferably, when the emulsion layer is on both sides of the support. It is 1.5 to 2.5 g / m ² .
Further, when the emulsion layer is provided on only one side of the support, 2.0 to 2.0
6.0 g / m ² is preferred, and more preferably 2.5 to
4.0 g / m ² .

In the present invention, it has been found that the conductive substance is contained on the side having the emulsion layer on the support so that the fixing defect does not occur even when the rapid processing is performed with a low replenishment.

The conductive substance preferably used in the present invention is a metal oxide, but a conductive polymer is also preferably used. As an antistatic method using a conductive polymer, (a) a water-soluble conductive polymer (such as styrenesulfonic acid sodium salt-maleic acid disodium salt copolymer) described in JP-A-4-80744, (b) hydrophobic An antistatic layer composed of a reactive polymer (butyl acrylate-monosodium maleate salt copolymer and the like) and a reaction product of (c) a curing agent (a compound having a plurality of ethyleneimino groups and glycidyl groups) is particularly effective.

The metal oxide is preferably used in the form of colloid, for example, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ ,
Examples thereof include colloids such as In ₂ O ₃ , SiO ₂ , MgO, BaO, and MoO, which are not particularly limited, but among these, Z
nO, TiO ₂ and SnO ₂ are preferable, and SnO ₂ (tin oxide) colloid is particularly preferable.

Since particles having a diameter of 10 ^-5 to 10 ^-7 cm are stable in dispersion state, this size is referred to as a colloidal dimension. A state in which colloidal particles are dispersed is referred to as colloidal in the present invention.

The method for producing the colloidal tin oxide sol of the present invention includes a method of dispersing tin oxide ultrafine particles in a suitable solvent, a method of producing a tin compound soluble in a solvent from a decomposition reaction in a solvent, and the like. Any method can be adopted.

In the production method using the tin oxide ultrafine particles, the temperature condition is particularly important, and the method involving the high temperature heat treatment is not preferable because of the growth of primary particles and the appearance of crystallinity, and it is unavoidable. When heat treatment is performed without heat treatment, the temperature is 300 ° C. or lower, preferably 200 ° C. or lower, and further 150 ° C. or lower. However, heating in the range of 150-250 ° C is preferred for dispersion in the binder.

In addition, a tin oxide prepared by a wet method is sprayed into an electric furnace, a high temperature thermal decomposition method of an organic tin compound, or the like, followed by a manufacturing process for isolating only tin oxide, and then tin oxide is added to a solvent. The redispersion method is very unsuitable for use as an antistatic agent for photography, because redispersion is very difficult and agglomerated particles are generated.

When the compatibility of the solvent of the tin oxide sol dispersion liquid with the protective colloid binder at the time of production is poor, the solvent is preferably compatible with the production solvent in order to substitute the solvent suitable for dispersing in the binder. Alternatively, a compound capable of stably dispersing the tin oxide sol is appropriately added, and the temperature is 300 ° C. or lower, preferably 20
The tin oxide ultrafine particles are dried and separated together with the compound added by heating to 0 ° C or lower, further 150 ° C or lower, and redispersed in water or water mixed with another solvent.

As the tin compound used in the method for producing from the decomposition reaction of the tin compound soluble in the solvent in the solvent, K
Compounds containing an oxo anion such as ₂ SnO ₃ .3H ₂ O; water-soluble halides such as SnCl ₄ ; R ′ ₂ SnR
(CH ₃ ) ₃ S having a structure of ₂ , R ₃ SnX, R ₂ SnX ₂
nCl. (Pyridine), (C ₄ H ₉ ) ₂ Sn (OCC
₂ H ₅ ) _{2 and} other organometallic compounds; Sn (SO ₄ ) ₂ .2H ₂ O
And oxo salts thereof.

After dissolving the tin compound soluble in these solvents in the solvent, a tin oxide sol is produced by a physical method such as heating or pressurizing, or a chemical method such as oxidation, reduction or hydrolysis. Alternatively, a tin oxide sol is produced via an intermediate. For example, in Japanese Examined Patent Publication No. 35-6616, SnCl ₄ is dissolved in 100 times the volume of distilled water to precipitate stannic hydroxide, and then aqueous ammonia is added to weakly alkaline the precipitate to dissolve it.
A method for producing a colloidal tin oxide sol by heating until there is no ammonia odor is described.

As the solvent, in addition to water, alcohol solvents such as methanol, ethanol and isopropanol; ether solvents such as tetrahydrofuran, dioxane and diethyl ether; aliphatic organic solvents such as hexane and heptane; aromatics such as benzene and pyridine Various solvents such as an organic solvent can be used depending on the tin compound, but water and alcohols are preferable.

According to this method, it is possible to add a compound containing an element other than a tin compound which is soluble in a solvent during the production. For example, a fluorine-containing compound or a metal capable of having a trivalent or pentavalent coordination number. A compound can be introduced.

As the fluorine-containing compound soluble in the solvent, either an ionic fluoride or a covalent fluoride may be used.
₂ TiF ₆ , HF, KHF ₂ Sb, F ₃ MoF _{6 and} other metal fluorides, NH ₄ MnF ₃ , NH ₄ BiF _{4 and} other compounds that generate fluoro complex anions, BrF ₃ , SF ₄ , SF _{6 and} other such compounds Inorganic molecular fluoride, CF ₃ I, CF ₃ OOH, P (CF ₃ ) ₃
And the like, and when the solvent is water, a combination of a fluorine-containing compound and a non-volatile acid, such as a combination of CaF ₂ and sulfuric acid, can also be used.

Examples of the metal compound which is soluble in a solvent and can have a trivalent or pentavalent coordination number include Al, Ga, In and Tl.
Group III elements or Group V elements such as P, As, Sb, Bi, Nb, V, Ti, which can have trivalent or pentavalent coordination numbers,
It is a group of compounds containing transition metals such as Cr, Mo, Fe, Co and Ni.

The silver halide grains according to the present invention (hereinafter, also referred to as the tabular silver halide grains of the present invention) are preferably tabular having two parallel (100) planes as main planes and have an aspect ratio of Is 2.0 or more, preferably 15.0
Less than. The principal plane here is a set of parallel planes having the largest area among the crystal surfaces forming substantially rectangular parallelepiped emulsion grains, and the aspect ratio is the principal plane of the grain with respect to the thickness between the principal planes. Is the ratio of the average edge lengths that form.

The average edge length of the main plane is, for example, taken by enlarging the particles with an electron microscope 10,000 to 50,000 times, and measuring the edge length of the particles on the print or the area at the time of projection. Required by Similarly, the particle thickness can be obtained by actually measuring an electron micrograph.

The fact that the main plane is the (100) plane can be determined by an electron diffraction method or an X-ray diffraction method. In observation with an electron micrograph, particles having a (100) principal plane can be examined because the principal plane is an orthogonal square (square or rectangular) plane.

It is preferable that 50% or more of the total projected area of the silver halide grains contained in the silver halide emulsion layer are tabular silver halide grains of the present invention, and more preferably 8
0% or more.

In the present invention, silver iodochloride, silver chloroiodobromide and the like having a silver chloride content of 10 mol% or more can be used, but a silver chloride content of 30 to 70 mol% and a silver iodide content are preferable. Rate 1.0 mol% or less (more preferably 0.5 mol%
Below).

In the emulsion having tabular silver halide grains of the present invention, (a) a step of introducing a silver salt and a halide into a dispersion medium to form nuclei of tabular grains, and (b) subsequent to nucleation, It is prepared by a step of performing Ostwald ripening under the condition of maintaining the (100) main surface of tabular grains, and (c) a step of growing grains so as to obtain a desired grain size and silver chloride content.

The double jet method (simultaneous mixing method) is preferably used as a method of reacting a silver salt and a halide during nucleation.

The simultaneous mixing method is also used at the time of grain growth. As one type of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is, a so-called controlled double jet method is used. It can also be used.
According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, a part or all of the steps during grain formation may be a grain formation step by supplying fine silver halide grains.

Since the grain size of fine grains controls the supply rate of halide ions, the preferable grain size varies depending on the size and the halogen composition of the silver halide grains of the host, but the average equivalent spherical diameter is 0.3 μm or less. Used. More preferably, it is 0.1 μm or less. In order for the fine particles to be laminated on the host particles by recrystallization, the size of the fine particles is desirably smaller than the equivalent sphere diameter of the host particles, and more preferably 1/10 or less of the equivalent sphere diameter.

For the silver halide emulsion, after completion of the growth of silver halide grains, a Nudel water washing method, a flocculation sedimentation method or the like is used in order to remove soluble salts to obtain an Ag ion concentration suitable for chemical sensitization. As a preferable washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B No. 35-16086, or a polymer flocculant described in JP-A-2-7037, Example G -3, G-8 and the like can be mentioned as a desalting method. In addition, Research Disclosure (Res
search Disclosure (hereinafter abbreviated as RD) 1
02 (October 1972) 10208 and 131 (1)
Desalting may be carried out using the ultrafiltration method described in Mar. 1975, 13122.

In the silver halide emulsion, various hydrophilic colloids for wrapping silver halide are used as a binder. For this purpose, gelatin as well as synthetic polymers such as polyvinyl alcohol and polyacrylamide, and photographic binders such as colloidal albumin, polysaccharides and cellulose derivatives may be used.

The silver halide emulsion can be chemically ripened. Chemical aging process conditions such as pH, pA
There are no particular restrictions on g, temperature, time, etc., and the conditions generally used in the art can be used. For chemical sensitization, a sulfur sensitizing method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitizing method using a selenium compound, a tellurium sensitizing method using a tellurium compound,
A reduction sensitization method using a reducing substance, a gold or other noble metal sensitization method using a noble metal, and the like can be used alone or in combination. Among them, the selenium sensitization method and the tellurium sensitization method are preferably used.

Examples of selenium sensitizers used in selenium sensitization include US Pat. Nos. 1,574,944 and 1,60.
No. 2,592, No. 1,623,499;
150046, JP-A-4-25832, 4-10
No. 9240 and No. 4-147250.

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (allyl isoselenocyanate, etc.), selenoureas (N, N-dimethylselenourea, N, N, N'-triethyl). Selenourea, N,
N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-nitrophenylcarbonylseleno Urea, etc., selenoketones (selenoacetone, selenoacetophenone, etc.), selenoamides (selenoacetamide,
N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates (tri-p-triselenophosphate, etc.), selenides (Triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.) and the like. Particularly preferred selenium sensitizers are selenoureas, selenamides, selenoketones, selenides.

The photographic emulsion used in the present invention may be spectrally sensitized with cyanine dyes and the like. The sensitizing dyes may be used alone, or a combination thereof may be used,
Combinations of sensitizing dyes are often used especially for the purpose of supersensitization.

Various techniques applicable to the light-sensitive material of the present invention are described in, for example, RD17643 (December 1978).
18716 (November 1979) and 308
119 (December 1989).

When the light-sensitive material of the present invention is applied to medical X-ray radiography, a fluorescent intensifying screen containing a phosphor that emits near-ultraviolet light to visible light as a main component upon exposure to penetrating radiation is used. To be This is exposed by contacting both sides of a light-sensitive material obtained by coating an emulsion on both sides. The penetrating radiation referred to here is a high-energy electromagnetic wave and means X-rays and γ-rays.

Examples of preferable phosphors used in the fluorescent intensifying screen include those shown below.

Tungstate phosphor (CaWO ₄ ,
MgWO ₄ , CaWO _4, Pb, etc.), terbium-activated rare earth oxysulfide-based phosphor (Y ₂ O ₂ S: Tb, Gd ₂ O ₂ S: T)
b, La ₂ O ₂ S: Tb, (Y.Gd) ₂ O ₂ S: Tb,
(Y. Gd) O ₂ S: Tb. Tm, etc.), terbium-activated rare earth phosphate-based phosphor (YPO ₄ : Tb, GdPO ₄ : T
b, LaPO ₄ : Tb, etc.), terbium-activated rare earth oxyhalide phosphor (LaOBr: Tb, LaOB)
r: Tb. Tm, LaOCl: Tb, LaOCl: T
b. Tm, LaOCl: Tb. Tm. LaOBr: Tb
GdOBr: TbGdOCl: Tb), thulium-activated rare earth oxyhalide-based phosphor (LaOBr: T
m, LaOCl: Tm, etc.), barium sulfate-based phosphor (B
aSO ₄ : Pb, BaSO ₄ : Eu ²⁺ , (Ba.Sr)
SO ₄ : Eu ^2+, etc.), a divalent eurobium-activated alkaline earth metal phosphate-based phosphor ((Ba ₂ PO ₄ ) ₂ : Eu ²⁺ ,
(Ba ₂ PO ₄ ) ₂ : Eu ^2+, etc.) Divalent eurobium-activated alkaline earth metal fluorohalide-based phosphor (BaF)
Cl: Eu ²⁺ , BaFBr: Eu ²⁺ , BaFCl: Eu
²⁺ . Tb, BaFBr: Eu ²⁺ . Tb, BaF ₂ · Ba
Cl · KCl: Eu ²⁺ , (Ba · Mg) F ₂ · BaCl
・ KCl: Eu ^2+, etc., iodide type phosphor (CsI: N)
a, CsI: Tl, NaI, KI: Tl, etc.), a sulfide-based phosphor (ZnS: Ag (Zn.Cd) S: Ag, (Z
n. Cd) S: Cu, (Zn. Cd) S: Cu. Al
Etc.), Hafnium phosphate phosphor (HfP ₂ O ₇ : Cu
etc).

However, the phosphor used in the present invention is not limited to these, and any phosphor can be used as long as it emits light in the visible or near-ultraviolet region upon irradiation with radiation.

The fluorescent intensifying screen used in the present invention is preferably filled with a phosphor in a gradient particle size structure. In particular, it is preferable to apply phosphor particles having a large particle size on the surface protective layer side and phosphor particles having a small particle size on the support side, and those having a small particle size are 0.5 to 2.0 μm. 10 to 30 μm for particles
Is preferred.

The fluorescent intensifying screen is produced by a step of forming a phosphor sheet composed of a binder and a phosphor, placing the phosphor sheet on a support, and heating the binder sheet at a temperature not lower than the softening temperature or melting point of the binder. It is preferable to manufacture the phosphor sheet in a step of adhering the phosphor sheet to a support while compressing.

For the phosphor sheet which becomes the phosphor layer of the fluorescent intensifying screen, the coating solution in which the phosphor is uniformly dispersed in the binder solution is applied onto a temporary support for forming the phosphor sheet and dried. After that, it can be manufactured by peeling from the temporary support. That is, first, a binder and phosphor particles are added to an appropriate organic solvent, and the mixture is stirred and mixed to prepare a coating liquid in which the phosphor is uniformly dispersed in the binder.

The binder has a softening temperature or melting point of 30.
A thermoplastic elastomer of 150 ° C is used alone or together with other binders. Since the thermoplastic elastomer has elasticity at room temperature and becomes fluid when heated, it is possible to prevent the phosphor from being damaged by the pressure during compression. Examples of thermoplastic elastomers include polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, ethylene-vinyl acetate, polyvinyl chloride, natural rubber, fluororubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber and silicone rubber. At least 1 selected from the group consisting of
A class of thermoplastic elastomers may be mentioned.

The mixing ratio of the thermoplastic resin in the binder is
It may be 10 to 100% by weight, but it is preferable that the binder is composed of as many thermoplastic elastomers as possible, particularly 100% by weight of the thermoplastic elastomer.

Examples of the solvent for preparing the coating liquid include lower alcohols such as methanol, ethanol, propanol and butanol, chlorine atom-containing hydrocarbons such as methylene chloride and ethylene chloride, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, Mention may be made of esters of lower fatty acids and lower alcohols such as methyl acetate, ethyl acetate, butyl acetate, ethers such as dioxane, ethylene glycol monoethyl ester, ethylene glycol monomethyl ester and mixtures thereof.

The mixing ratio of the binder and the phosphor in the coating solution varies depending on the characteristics of the target fluorescent intensifying screen, the type of the phosphor, etc., but generally the mixing ratio of the binder and the phosphor is 1: 1. To 1: 100 (weight ratio), particularly preferably 1: 8 to 1:40 (weight ratio).

In the coating liquid, a dispersant for improving the dispersibility of the phosphor in the coating liquid or a binding force between the binder and the phosphor in the formed phosphor layer is improved. Various additives such as a plasticizer may be mixed.

Examples of dispersants include phthalic acid, stearic acid, caproic acid, lipophilic surfactants and the like.

Examples of the plasticizer include triphenyl phosphate, tricresyl phosphate, diphenyl phosphate, and other phosphate esters, diethyl phthalate, dimethoxyethyl phthalate, and other phthalate esters, ethyl phthalyl glycolate, and butyl phthalbutyl glycolate. And the like, polyesters of triethylene glycol and adipic acid, polyesters of polyethylene glycol and aliphatic dibasic acids such as polyesters of diethylene glycol and succinic acid, and the like.

The coating solution containing the phosphor and the binder prepared as described above is uniformly applied to the surface of the temporary support for sheet formation to form a coating film.

As the coating means, for example, a doctor blade, a roll coater, a knife coater or the like can be used.

As the temporary support, for example, those made of various materials such as glass, wool, cotton, paper and metal can be used, and a sheet or a sheet which is flexible in handling as an information recording material can be used. What can be processed into a roll is preferable. From this point, for example, cellulose acetate film, polyester film, polyethylene terephthalate film, polyamide film, polyimide film, triacetate film, plastic film such as polycarbonate film, aluminum foil, metal sheet such as aluminum alloy foil, general paper and photographic base paper, Printing paper such as coated paper or art paper, baryta paper, resin coated paper, Belgian patent 78
Particularly preferred are processed papers such as papers sized with polysaccharides as described in No. 4,615, pigment papers containing pigments such as titanium dioxide, and papers sized with polyvinyl alcohol.

After coating and drying the coating solution for forming a phosphor layer on the temporary support, it is peeled off from the temporary support to obtain a phosphor sheet which becomes the phosphor layer of the fluorescent intensifying screen. Therefore, it is preferable that the surface of the temporary support is coated with a release agent in advance so that the formed phosphor sheet can be easily separated from the temporary support.

The following will be described. A sheet for setting the phosphor formed as described above is prepared. This support can be arbitrarily selected from the materials listed for the temporary support.

In order to strengthen the bond between the support and the phosphor layer, the fluorescent intensifying screen may be coated with a polymeric substance such as gelatin on the surface of the support to provide an undercoat layer for imparting adhesiveness, sensitivity,
In order to improve the image quality (sharpness, graininess), a light reflecting layer made of a light reflecting substance such as titanium dioxide or a light absorbing layer made of a light absorbing substance such as carbon black may be provided.

The fluorescent intensifying screen used in the present invention can also be provided with these various layers, and the structure thereof can be arbitrarily selected according to the desired purpose and application of the fluorescent intensifying screen.

The phosphor sheet obtained in the above is placed on a support, and the phosphor sheet and the phosphor sheet are adhered to the support while being compressed at a softening temperature or a temperature equal to or higher than the melting point of the binder.

In this way, by utilizing the method of pressing the phosphor sheet onto the support for the phosphor sheet without fixing it beforehand, the sheet can be spread thinly and not only the damage of the phosphor is prevented but also the sheet is prevented. It is possible to obtain a high phosphor filling rate even at the same pressure as compared with the case of fixing and pressurizing.

Examples of the compressing device used for the compressing treatment include calender rolls, hot presses and the like generally known. For example, the compression treatment using a calender roll is performed by placing the phosphor sheet obtained on a support and passing the phosphor sheet at a constant speed between rollers heated to a temperature higher than the softening temperature or melting point of the binder. The pressure during compression is preferably 50 kg / cm ² or more.

Usually, in the fluorescent intensifying screen, a transparent protective film for physically and chemically protecting the phosphor layer is provided on the surface of the phosphor layer on the side opposite to the side in contact with the support. . Such a transparent protective film is also preferable in the fluorescent intensifying screen of the present invention. The thickness of the protective film is generally 0.1 to 20.
in the range of μm.

The transparent protective layer includes, for example, cellulose derivatives such as cellulose acetate and nitrocellulose, polymethyl methacrylate, polyethylene terephthalate,
It may be formed by a method in which a solution prepared by dissolving a synthetic polymer substance such as polyvinyl butyral, polyvinyl formal, polycarbonate, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer in a suitable solvent is applied to the surface of the phosphor layer. it can. Alternatively, a plastic sheet made of polyethylene terephthalate, polyethylene naphthalate, polyethylene, polyvinylidene chloride, polyamide, etc., and a protective film forming sheet such as a transparent glass plate are separately prepared, and an appropriate adhesive is applied to the surface of the phosphor layer. It can be formed by a method such as bonding using.

In the present invention, the protective layer used in the fluorescent intensifying screen is preferably a film formed of a coating film containing a fluorine-based resin soluble in an organic solvent. The fluorine-based resin refers to a polymer of an olefin containing fluorine (fluoroolefin) or a copolymer containing an olefin containing fluorine as a copolymer component. The film formed of the coating film of the fluororesin may be crosslinked.

The protective film made of a fluorine-based resin is made of other materials or X
When a line film or the like comes into contact, stains such as a plasticizer coming out of the film or the like are less likely to permeate the inside of the protective film, so that there is an advantage that the stains can be easily removed by wiping or the like.

When an organic solvent-soluble fluorine resin is used as the protective film forming material, this resin is prepared by dissolving it in an appropriate solvent. That is, the protective film is formed by uniformly applying a protective film-forming material coating solution containing an organic solvent-soluble fluorine-based resin on the surface of the phosphor layer using a doctor blade or the like, and then drying. The formation of this protective film may be performed simultaneously with the formation of the phosphor by simultaneous multilayer coating.

The fluorine-based resin is a polymer of a fluorine-containing olefin (fluoroolefin) or a copolymer containing a fluorine-containing olefin as a copolymer component, such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyfluorine. Ethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, fluoroolein-vinyl ether copolymer and the like.

Fluorine-based resins are generally insoluble in organic solvents, but a copolymer containing a fluoroolefin as a copolymer component becomes soluble in an organic solvent due to a constitutional unit other than the fluoroolefin to be copolymerized. The protective layer can be easily formed by coating a solution prepared by dissolving in a suitable solvent on the phosphor layer and drying. Examples of such a copolymer include a fluoroolefin-vinyl ether copolymer. Further, since polytetrafluoroethylene and its modified products are also soluble in a suitable fluorine-based organic solvent such as a perfluoro solvent, they are protected by coating similarly to the copolymer containing the above fluoroolefin as a copolymer component. A film can be formed.

The protective film may contain a resin other than the fluorine-based resin, and may contain a crosslinking agent, a film hardener, an anti-yellowing agent and the like. However, in order to sufficiently achieve the above object, the content of the fluorine-based resin in the protective film must be 30% by weight.
Or more, more preferably 50% by weight.
As described above, most preferably 70% by weight or more.

Examples of the resin other than the fluorine-based resin contained in the protective film include polyurethane resin, polyacrylic resin, cellulose derivative, polymethylmethacrylate, polyester and epoxy resin.

The protective film of the fluorescent intensifying screen used in the present invention may be formed from a coating film containing either one or both of the polysiloxane skeleton-containing oligomer and the perfluoroalkyl group-containing oligomer.

The polysiloxane skeleton-containing oligomer has, for example, a dimethylpolysiloxane skeleton,
It preferably has at least one functional group, for example, a hydroxyl group, and has a molecular weight of 500 to 100,000.
Is preferably within the range. Especially when the molecular weight is 1000
It is desirable that it is in the range of 100,000, more preferably in the range of 3,000 to 10,000.

The oligomer containing a perfluoroalkyl group such as a tetrafluoroethylene group preferably has at least one functional group such as a hydroxyl group in the molecule and has a molecular weight of 500 to 100,000.
Is preferably within the range. Especially the molecular weight is from 1000
The range of 100,000, and more preferably 100 to 100,000 is desirable.

If an oligomer containing a functional group is used, a cross-linking reaction occurs between the oligomer and the protective layer film forming resin during the formation of the protective film, and the oligomer is incorporated into the molecular structure of the film forming resin. It is advantageous that the oligomer is not removed from the protective film even by operations such as repeated use of the fluorescent intensifying screen for a long period of time or cleaning of the surface of the protective film, and the effect of adding the oligomer is effective for a long period of time.

The oligomer is preferably contained in the protective film in an amount of 0.01 to 10% by weight, particularly 0.1 to 2%.
% By weight is preferred.

The protective layer may contain perfluoroolefin resin powder or silicone resin powder. As the perfluoroolefin resin powder and the silicone resin powder, those having an average particle size of 0.1 to 10 μm are preferable, and an average particle size of 0.3 to 5 μm is particularly preferable.

These perfluoroolefin resin powders or silicone resin powders are preferably contained in the protective film in a proportion of 0.5 to 30% by weight based on the weight of the protective film,
2 to 20% by weight is more preferable, and most preferably 5 to 1
It is 5% by weight.

The protective film of the fluorescent intensifying screen is preferably a transparent synthetic resin layer having a thickness of 5 μm or less formed by coating on the phosphor layer. By using such a thin protective layer, the distance from the phosphor of the fluorescent screen to the silver halide emulsion can be shortened, which contributes to the improvement of the sharpness of the obtained X-ray image.

The filling rate of the phosphor in the present invention can be obtained from the following formula from the porosity of the phosphor layer formed on the support.

[0128]

[Equation 1]

Where V: total volume of the phosphor layer Vair; air volume in the phosphor A; total weight of the phosphor px; density of the phosphor py; density of the binder pair; air density a; density of the phosphor Weight b; Weight of binder Furthermore, since the pair is 0 in the formula (1), the formula (1) can be approximately represented by the following formula (2).

[0130]

[Equation 2]

However, V, Vair, A, px, py,
a and b are synonymous with Formula (1).

The porosity of the phosphor layer was calculated by the equation (2). Further, the filling rate of the phosphor can be obtained by the following equation (3).

[0133]

(Equation 3)

However, V, A, px, py, a and b have the same meanings as in formula (1).

In the present invention, the X-ray energy of an X-ray generator having an intrinsic filtration of 2.2 mm of aluminum equivalent to that of X-rays having an X-ray energy of 80 kVp is 45% or more, more preferably 50% or more. It is preferable to use a sensitive paper. The X-ray absorption of the fluorescent intensifying screen can be measured by the following method.

X-rays generated from a tungsten target tube operated at 80 kVp with a three-phase power supply were made to have a thickness of 3
mm through the aluminum plate and reach the fluorescent screen of the sample fixed at a position 200 cm from the tungsten anode of the target tube. Then, the amount of X-rays transmitted through the fluorescent screen is measured by the fluorescent screen. 50cm from the phosphor layer
Measurement is performed at a later position 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 can be used.

The thickness of the phosphor of the fluorescent intensifying screen used in the present invention is 135 to 200 μm, and the filling rate of the phosphor at this time is 68.
% Or more is preferable.

The light-sensitive material of the present invention has, for example, the above-mentioned RD1.
7643, XX-XXI, pp. 29-30, 308119.
The treatment with the treatment liquid as described in paragraphs XX to XXI, pages 1011 to 1012 can be performed.

Developers for black and white photographic processing include dihydroxybenzenes (hydroquinone etc.), 3-pyrazolidones (1-phenyl-3-pyrazolidone etc.), aminophenols (N-methyl-aminophenol etc.) and the like. They can be used alone or in combination. In the developer, a preservative, an alkaline agent, a pH buffer, an antifoggant, a hardener, a development accelerator, a surfactant, an antifoaming agent, a color tone, a water softener, a dissolution aid, and a viscosity-imparting agent. Agents and the like can be used as needed.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution, and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. A regulator, a water softener, etc. may be included.

Advantageous for processing the light-sensitive material of the present invention,
An automatic processor having a mechanism for supplying a solid processing agent to a processing tank will be described.

As the means for supplying the treating agent, when the solid treating agent is a tablet, there are disclosed in Japanese Utility Model Publication Nos. 63-137783 and 63-63.
Reference can be made to the description in No. 97522, No. 1-85732, and in the case of granules or powders, No. 62-81.
No. 964, No. 63-84151, JP-A No. 1-2923.
No. 75, etc.
Nos. 59 and 63-195345 can be referred to, but not limited to.

The location where the solid processing agent is charged is in the processing tank, but preferably it communicates with the processing section for processing the light-sensitive material,
It is preferable that the treatment liquid is flowing between the treatment unit and the treatment unit, and a certain amount of the treatment liquid is circulated between the treatment unit and the dissolved components to move to the treatment unit. Further, it is preferable that the solid processing agent is introduced into a processing liquid whose temperature is controlled.

In the developer used in the processing method of the present invention, dihydroxybenzenes, aminophenols and pyrazolidones described in Japanese Patent Application No. 4-286232 as developing agents are disclosed in JP-A-5-165161. The described reductones can also be used. As the pyrazolidones, those substituted at the 4-position are preferable since they have little water-soluble property or change with time of the solid processing agent itself. Further, it is preferable that a reductone typified by ascorbic acid or erythorbic acid is allowed to be present in the developer because the processability is improved.

For the developer, Japanese Patent Application No. 4-286 is used as a preservative.
In addition to the sulfites described in No. 232, organic reducing agents can be used. In addition, the chelating agent described in Japanese Patent Application No. 4-586323, page 20, and the bisulfite salt of the hardening agent described in page 21 thereof. Adducts can be used. Also, Japanese Patent Application No. 4-92
It is also preferable to add the silver sludge inhibitor described in Nos. 947 and 5-96118, the cyclodextrin compound described in JP-A No. 1-124853, and the amine compound described in U.S. Pat. No. 4,269,929.

It is necessary to use a buffer for the developer,
Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, 3 sodium phosphate, 3 potassium phosphate, 2 potassium phosphate, sodium borate, potassium borate, 4 sodium borate (boric acid), 4 potassium borate, sodium o-hydroxybenzoate ( Sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like. You can

As the development accelerator, Japanese Patent Publication No. 37-160
88, 37-5987, 38-7826, 44-12380, 45-9019 and U.S. Pat. No. 3,813,247; thioether compounds; JP-A-52-49829. And ibid 50-15554
P-phenylenediamine compounds described in JP-A No. 6-58200;
0-137726, JP-B-44-30074, JP-A-56-156826, JP-A-52-43429 and the like; quaternary ammonium salts; US Pat. No. 2,610,1.
22 and 4,119,462, p-aminophenols; US Pat. Nos. 2,482,546 and 2,
No. 494,903, No. 2,596,926, No. 3,1
28,182, 3,582,346, 4,23
Nos. 0,796 and 3,253,919,
Amine compounds described in No. 11431 and the like; JP-B-37-
No. 16088, No. 41-11431, No. 42-238
83, 42-25201, U.S. Pat. No. 3,128,
No. 183, No. 3,532,501 and the like; other 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. are added as necessary. be able to.

Antifoggants include alkali metal halides such as potassium iodide and benzotriazole,
6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole,
Organic antifoggants such as 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be used.

Further, in the developer composition, methyl cellosolve, methanol, acetone, dimethylformamide, cyclodextrin compound, JP-B-47-33378,
The compounds described in JP-A-44-9509 can be used as an organic solvent for increasing the solubility of the developing agent, and other stain preventing agents, sludge preventing agents and layering effect promoters can also be used.

The fixing agent includes a fixing agent, a chelating agent, and a pH.
Well-known compounds such as buffering agents, hardening agents, preservatives can be adopted, for example, JP-A-4-242246, page 4, and the same 5
No. 113363, pages 2 to 4 can be used. In addition, a chelating agent described in Japanese Patent Application No. 4-586323, page 20, a bisulfite adduct of a hardening agent described in page 21, and a known fixing accelerator can be used.

Prior to the treatment, it is also preferable to add a starter, and the starter is preferably solidified and added. As the starter, in addition to organic acids such as polycarboxylic acid compounds, halides of alkaline earth metals such as potassium bromide, organic inhibitors, and development accelerators are used.

The light-sensitive material of the present invention is preferably processed for a total processing time (Dry to Dry) of 5 to 45 seconds using an automatic processor, but the effect is also obtained when it is processed for 10 to 20 seconds. Can be demonstrated without regret.

Here, the time from when the front end of the photosensitive material to be processed is immersed in the developing tank solution of the automatic developing machine until it comes into contact with the fixing tank solution in the next step is "developing time". "Fixing time" is the time from contact with the washing tank liquid (stabilizing liquid), "Washing time" is the immersion time in the washing tank liquid, and "Time is the time in the drying zone of the automatic processor". "Drying time", developing time is 3 to 15 seconds (further 3 to 10 seconds), developing temperature is 25 to 50 ° C (further 30 to 40 ° C), fixing time is 2 to 12 seconds (further 2 to 10 seconds).
Sec), fixing temperature 20-50 ° C (further 30-40 ° C),
Water washing (stabilization) time 2 to 15 seconds (further 2 to 8 seconds), water washing (stabilization) temperature 0 to 50 ° C (further 15 to 40 ° C),
Drying time 3-12 seconds (further 3-8 seconds), drying temperature 35
-100 degreeC (further 40-80 degreeC) is preferable.

The light-sensitive material is subjected to development, fixing and washing (or stabilization), water is squeezed with a squeeze roller, and then dried.

In processing the light-sensitive material of the present invention with an automatic developing machine, it is preferable from the viewpoint of drying efficiency to employ an automatic developing machine having a conveying roller (heat roller) whose outer periphery is heated by a heat source in the drying step. Further, the transport roller preferably has a heat source inside the roller.

The light-sensitive material of the present invention can be processed by reducing the replenishment amounts of the developing solution and the fixing solution to 4 to 216 ml per 1 m ² of the light-sensitive material.

The amount of replenisher is the amount of replenisher replenished in the developing tank and the fixing tank when one sheet of photosensitive material is passed through.

The carry-out amount by the light-sensitive material means the amount obtained by subtracting the weight of the light-sensitive material before processing from the weight of the light-sensitive material containing the developing solution after the development processing step is completed.
The same applies to the fixing step, and in the present invention, it is preferable that all values satisfy 1 ≦ replenisher amount / take-out amount of the photosensitive material ≦ 5.

[0159]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of hexagonal tabular seed emulsion Em-1) A hexagonal tabular seed emulsion Em-1 of pure silver bromide was prepared by the following method.

A1 liquid ossein gelatin 60.2 g distilled water 20.0 liter 10% aqueous solution of surfactant (SU-1) in methanol 5.6 ml potassium bromide 26.8 g 10% sulfuric acid 144 ml B1 liquid silver nitrate 1487.5 g distilled C1 liquid made into 3500 ml with water 1050 g Potassium bromide 1050 g D1 liquid made into 3500 ml with distilled water 1.75 N potassium bromide aqueous solution Silver potential control amount SU-1: HO (CH ₂ CH ₂ O) n [CH (CH ₃ ) C
H ₂ O] ₁₇ (CH ₂ CH ₂ O) mH [n + m = 5-7] At 35 ° C., using a mixing stirrer shown in JP-B-58-58288, the B1 solution and the C1 solution were each added to the A1 solution.
4.1 ml was added by the simultaneous mixing method over a period of 2 minutes to form nuclei.

After stopping the addition of solution B1 and solution C1, 6
It takes 0 minutes to raise the temperature of the A1 solution to 60 ° C.,
Again, the B1 solution and the C1 solution were each mixed for 68.5 by the simultaneous mixing method.
It was added at a flow rate of ml / min for 50 minutes. During this period, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to be +6 mV using the D1 solution. After the addition is completed, pH is adjusted with 3% potassium hydroxide.
To 6 and immediately desalting and washing with water to obtain seed emulsion EM-1
And

In the seed emulsion Em-1 thus prepared, 90% or more of the total projected area of silver halide grains was composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average hexagonal tabular grain was used. Thickness 0.07μm, average diameter (circle diameter conversion) 0.5
μm and a coefficient of variation of 25% were found by electron microscope observation.

(Preparation of tabular pure silver bromide emulsion EM-1) A tabular pure silver bromide emulsion was prepared using the following four kinds of solutions.

A2 solution ossein gelatin 29.4 g 10% aqueous methanol solution of surfactant (SU-1) 1.25 ml seed emulsion EM-B 2.65 mol equivalent B2 solution 3.50 N silver nitrate aqueous solution made up to 3000 ml with distilled water 1760 ml C2 liquid Potassium bromide 737 g D2 liquid to make 1760 ml with distilled water 1.75 N potassium bromide aqueous solution At the following silver potential control amount of 60 ° C., a mixing stirrer shown in JP-B-58-58288 was used to prepare A2 liquid. The total amount of the B2 solution and the C2 solution was mixed by a simultaneous mixing method (double jet method) so that the flow rate at the end of addition was 3 times the flow rate at the start of addition.
It took a minute to add and grow. During this time, the silver potential was controlled to be +40 mV using D2 solution.

After completion of the addition, in order to remove excess salts,
Precipitation and desalting were performed using an aqueous solution of Demol (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate.

About 3,000 emulsions EM-1 thus obtained were observed and measured with an electron microscope to analyze the shape. As a result, they were hexagonal tabular grains having an average circle-equivalent diameter of 0.59 μm and an average thickness of 0.17 μm. The coefficient of variation was 24%.

(Preparation of Silver Chlorobromide (100) Tabular Emulsion EM-2 with Silver Chloride Content of 30 Mol%) A3 Liquid Ossein Gelatin 37.5 g Potassium Iodide 0.625 g Potassium Bromide 23.6 g Sodium Chloride 5.0 g distilled water to 7500 ml B3 liquid silver nitrate 1500 g distilled water to 2500 ml C3 liquid potassium iodide 4 g potassium bromide 200 g sodium chloride 42 g distilled water 684 ml D3 liquid potassium bromide 535 g sodium chloride 113 g distilled water 1816 ml At 40 ° C., 684 ml of the B3 liquid and the total amount of the C3 liquid were added to the A3 liquid in the mixing stirrer disclosed in JP-B-58-58288 over 1 minute. The EAg was adjusted to 220 mV, and after aging for 20 minutes in Ostwald, the remaining total amount of the B3 solution and the total amount of the D3 solution were added over 40 minutes. Meanwhile, EAg was controlled at 220 mV.

After completion of the addition, precipitation and desalting were carried out to remove excess salts, and then a gelatin solution was added and dispersed to prepare an emulsion EM-2.

About 3,000 emulsions EM-2 were observed and measured by an electron microscope, and the shape was analyzed. As a result, a flat plate having a (100) plane having an average circle-equivalent diameter of 0.8 μm and an average thickness of 0.1 μm as a main plane. The particles were in the form of particles and had a coefficient of variation of 20%.

(Preparation of silver chlorobromide (100) tabular emulsion EM-3 having a silver chloride content of 70 mol%) A4 liquid ossein gelatin 37.5 g potassium iodide 0.625 g potassium bromide 16.8 g sodium chloride 8.3 g B4 solution made into distilled water to 7500 ml Silver nitrate 1500 g Made up in distilled water to 2500 ml C4 solution Potassium iodide 4 g Potassium bromide 143 g Sodium chloride 70 g D4 solution made up to 684 ml Potassium bromide 382 g Sodium chloride 188 g Distilled water Emulsion EM-3 was obtained by the same method as EM-2 using the above A4 liquid to D16 liquid.

Approximately 3000 emulsions EM-3 were observed and measured by an electron microscope, and the shape was analyzed. As a result, the (100) plane having an average circle-equivalent diameter of 0.8 μm and an average thickness of 0.1 μm was used as a main plane. It was a tabular grain and had a coefficient of variation of 20%.

(Preparation of Pure Silver Chloride (100) Tabular Emulsion EM-4) A5 Liquid Ossein Gelatin 37.5 g Potassium Iodide 0.625 g Sodium Chloride 16.5 g B5 Liquid Silver Nitrate 1500 g Distilled Water C5 liquid potassium iodide 4 g sodium chloride 140 g distilled water 684 ml D5 liquid sodium chloride 375 g distilled water 1816 ml EM-2 except that the above A5 liquid to D5 liquid was adjusted to 150 mV Emulsion EM-4 was obtained by the same method as described above.

Approximately 3000 emulsions EM-4 were observed and measured by an electron microscope, and the shape was analyzed. As a result, the (100) plane having an average circle-equivalent diameter of 0.8 μm and an average thickness of 0.1 μm was taken as the main plane. It was a tabular grain and had a coefficient of variation of 20%.

(Preparation of silver iodide fine particles) A6 solution ossein gelatin 100 g Potassium iodide 8.5 g Made to 2000 ml with distilled water B6 solution Silver nitrate 360 g Made to 605 ml with distilled water C6 solution Potassium iodide 352 g Distilled water to 605 ml Solution A6 is added to the reaction vessel, and the temperature is maintained at 40 ° C with stirring,
Solution B6 and solution C6 were added at a constant rate over 30 minutes by the simultaneous mixing method. The pAg during the addition was kept at 13.5 by a conventional pAg control means.

The produced silver iodide has an average grain size of 0.06 μm.
It was a mixture of β-AgI and γ-AgI. This emulsion is called a silver iodide fine grain emulsion.

(Preparation of Solid Fine Particle Dispersion of Spectral Sensitizing Dye) The following sensitizing dye (SD-1) and sensitizing dye (SD-
2) was added to water previously adjusted to 27 ° C. at a ratio of 100: 1, and the mixture was stirred with a high-speed stirrer (dissolver) at 3500 rpm for 30 to 120 minutes to disperse the solid fine particles of the spectral sensitizing dye. I got something. At this time, SD-1
Was adjusted to be 2%.

SD-1: Anhydro-5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl)
Oxacarbocyanine hydroxide SD-2: Anhydro-5,5'-di (butoxycarbonyl) -1,1'-diethyl-3,3'-di (4-sulfobutyl) benzimidazolocarbocyanine hydroxide Sodium salt (selenium sensitized) emulsions EM-1 to EM-4 were subjected to spectral sensitization and chemical sensitization by the following method to obtain chemically sensitized emulsion EM-A.
~ EM-D was obtained.

After heating the emulsion to 60 ° C., the sensitizing dye (S
After the solid fine particle dispersion was added so that D-1) was 460 mg per mole of silver, ammonium thiocyanate was added at 7.0 × 10 ⁻⁴ mole per mole of silver, and potassium chloroaurate and thiosulfate were added. Optimum chemical ripening was performed by adding sodium and triphenylphosphine selenide in an amount of 3.0 × 10 ⁻⁶ mol per mol of silver, and then the above silver iodide fine grain emulsion was added in an amount of 3 × 10 ⁻³ mol / Ag 1 mol. And the stabilizer (ST-1) was stabilized with 3 × 10 ^-2 mol.

ST-1: 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene (Synthesis Example 1 of colloidal tin oxide sol dispersion liquid) 65 g of stannic chloride hydrate was dissolved in 2 liters of a water / ethanol mixed solution to obtain a uniform solution. Then, this was boiled to obtain a coprecipitate. The precipitate is removed by decantation and washed with distilled water many times. An aqueous solution of silver nitrate is added dropwise to the washing solution, and after confirming that there is no chloride ion reaction, the washed precipitate is dispersed in distilled water to bring the total amount to 2 liters. Furthermore,
40 ml of 30% ammonia water was added and heated in a water bath to obtain a tin oxide sol solution.

When it is used as a coating solution, it is concentrated to about 8% concentration while blowing ammonia into the sol solution.

A value obtained by forming a thin film on silica glass using a sol solution and measuring by a four-terminal method was taken as the volume resistivity of particles contained in the sol solution. The volume resistivity of this sol is 3.
It was 4 × 10 ⁴ Ωcm.

(Synthesis Example 2 of colloidal tin oxide sol dispersion liquid) 65 g of stannic chloride hydrate and antimony trichloride 1.
0 g was dissolved in 2 liters of a water / ethanol mixed solution to obtain a uniform solution. Then, this was boiled to obtain a coprecipitate. The precipitate is removed by decantation and washed with distilled water many times. An aqueous solution of silver nitrate is added dropwise to the washing solution, and after confirming that there is no chloride ion reaction, the washed precipitate is dispersed in distilled water to bring the total amount to 2 liters. Further, 40 ml of 30% ammonia water was added and heated in a water bath to obtain a tin oxide sol solution.

This sol solution was sprayed in an electric furnace heated to 400 ° C. to obtain a conductive powder. After molding this powder with a tablet molding machine, the volume resistivity measured by the 4-terminal method is 1.5 ×
It was 10 Ωcm.

The conductor powder was dispersed in ammonia water having a pH of 10 to have a concentration of 8 wt%.

(Preparation of Substrate 1 with Subbing for Comparison) On both sides of a polyethylene terephthalate film base for X-rays (thickness 175 μm) colored blue with a concentration of 0.17,
After subjecting to 0.5 kV · A · min / m ² corona discharge treatment, the undercoating latex liquid shown in the following (L-2) was applied so that the film thickness after drying would be 0.2 μm (L-1). Are sequentially applied so that the film thickness after drying is 0.053 μm, and 1
It was dried at 23 ° C. for 2 minutes. This is referred to as support 1.

[0187]

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<< L-2 >> Butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyethyl acrylate (10/35/27/28 weight ratio) copolymer latex (solid content 30%) (tin oxide of the present invention Preparation of sol-undercoated support 2) The same undercoat as the support 1 is provided on one side of the same base, and the tin oxide sol prepared in (Preparation Example 1) is provided on the lower layer on the other side. The coating liquid prepared by mixing the liquid (L-2) and the liquid (L-4) below at a volume ratio of 35:15:50 has a dried film thickness of 0.12 μm and a sol component loading of 250 mg / m ² . As described above, the coating solution prepared by mixing the above (L-1) and the following (L-3) solution at a volume ratio of 70:30 was simultaneously applied to the upper layer so that the film thickness after drying was 0.053 μm. It was dried at ℃ for 1 minute. Before application, 0.5 kV ・ A ・ min
/ M ² of corona discharge treatment. This support is support 2
And

<< L-3 >> Dimethyl terephthalate 34.0
2 parts, dimethyl isophthalate 25.52 parts, 5-sulfoisophthalic acid dimethyl sodium salt 12.97 parts, ethylene glycol 47.85 parts, 1,4-cyclohexanedimethanol 18.95 parts, calcium acetate monohydrate 0.
065 parts and 0.022 part of manganese acetate tetrahydrate were subjected to transesterification under a nitrogen stream at 170 to 220 ° C. while distilling off methanol, and then trimethyl phosphate of 0.1.
04 parts, 0.04 parts of antimony trioxide and 15.08 parts of 1,4-cyclohexanedicarboxylic acid as a polycondensation catalyst were added, and the mixture was reacted at 220 to 235 ° C., and a theoretical amount of water was distilled off for esterification. It was

Thereafter, the pressure inside the reaction system is further reduced over about 1 hour and the temperature is raised, and finally at about 280 ° C. and 1 mmHg or less, about 1
Polycondensation was performed for a time to obtain a polyester polymer (here, “parts” indicate “parts by weight”.
5).

Aqueous Solution 73 of Polyester Polymer Obtained
30 g of styrene and 30 g of butyl methacrylate
g, glycidyl methacrylate 20 g, acrylamide 20 g and ammonium persulfate 1.0 g.
The mixture was reacted at 5 ° C. for 5 hours, cooled to room temperature, and the solid content was adjusted to 10% by weight to obtain a coating solution.

<< L-4 >> Butyl acrylate / styrene / glycidyl methacrylate (40/20/40 weight ratio) copolymer latex solution (synthesis of composite latex) Stirrer, thermometer, dropping funnel in 1000 ml four-necked flask. A nitrogen inlet tube and a reflux condenser were attached, and while degassing by introducing nitrogen gas, 360 ml of distilled water and 126 g of 30% colloidal silica dispersion were added and heated to an internal temperature of 80 ° C. 1.0 g of dodecylbenzenesulfonic acid (surfactant) is added,
As a polymerization initiator, 0.023 g of ammonium persulfate and then 12.6 g of vinyl pivalate were added and reacted for 4 hours. Then cool and pH with aqueous sodium hydroxide
Was adjusted to 6 to obtain a composite latex Lx-1.

(Preparation of Photosensitive Material Samples) A transverse light-shielding layer, an emulsion layer coating solution and a protective layer coating solution having the following compositions were successively applied on both surfaces of each of Supports 1 and 2 shown in Table 1 in a predetermined coating amount (photosensitive). simultaneous multilayer coating so that the material 1m shown by weight with per ^2), and dried.

First layer (transverse light shielding layer) Gelatin 0.2 g Solid fine particle dispersion dye (AH) 20 mg Sodium dodecylbenzenesulfonate (surfactant) 5 mg Surfactant (SU-1) 5 mg Hardener (H -1) 5 mg colloidal silica (average particle diameter 0.014 μm) 10 mg Second layer (emulsion layer) The following various additives were added to the above emulsions EM-A to D.

Gelatin (including those in emulsions EM-A to D) 1.2 mg Compound (A) 0.5 mg Compound (B) 5 mg t-butyl-catechol 5 mg Polyvinylpyrrolidone (molecular weight 10,000) 20 mg Styrene-anhydrous Maleic acid copolymer 80 mg Sodium polystyrene sulfonate 80 mg Trimethylol propane 350 mg Diethylene glycol 50 mg Nitrophenyl triphenylphosphonium chloride 1 mg Resorcin-4-ammonium sulfonate 50 mg Compound (C) 5 mg Compound (D) 0.5 mg C ₄ H ₉ OCH _{2 CH (OH) CH 2 N} (CH 2 COOH) 2 20mg stabilizer (ST-2) 5mg stabilizer (ST-3) 5mg colloidal silica 0.5g latex (L-5) 0.5g composite latex (L -1) 1.0 g Dextrin (molecular weight ≈ 100,000) 0.5 g Third layer (lower layer of protective layer) Gelatin 0.3 g Dioctyl phthalate (high boiling point solvent) 0.2 g Fourth layer (containing nonionic surfactant) Protective layer upper layer) Gelatin 0.3 g Matting agent (PMMA having an area average particle size of 7.0 μm) 27 mg Formaldehyde (hardening agent) 20 mg Hardening agent (H-1) 10 mg Latex (L-5) 0.2 g Complex latex ( Lx-1) 0.2 g Polysiloxane (SI) 50 mg Surfactant (SU-1) 30 mg Surfactant (SU-2) 2 mg Surfactant (SU-3) 7 mg Surfactant (SU-4) 5 mg Compound (E) 15 mg C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₅ H 50 mg C ₉ F ₁₉ O (CH ₂ CH ₂ O) ₁₁ H 3 mg C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₁₅ H 2 mg Surfactant (SU-5) 1 mg C ₇ F ₁₅ CH ₂ O (CH ₂ CH ₂ O) ₁₃ H 10 mg 4th layer (containing nonionic surfactant) No protective layer Upper layer) Gelatin 0.3 g Matting agent (PMMA having an area average particle size of 7.0 μm) 27 mg Formaldehyde (hardening agent) 20 mg Hardening agent (H-1) 10 mg Latex (L-5) 0.2 g Composite latex (Lx-1) 0.2 g Polysiloxane (SI) 50 mg Surfactant (SU-2) 30 mg Surfactant (SU-3) 7 mg Surfactant (SU-4) 5 mg H-1: 2,4-dichloro -6-Hydroxy-s-triazine sodium compound (B): 2,6-bis (hydroxyamino) -4
-Diethylamino-1,3,5-triazine compound (C): 2-mercaptobenzimidazole-5
-Sodium sulfonate ST-2: 1- (3-sulfophenyl) -5-mercaptotetrazole sodium salt ST-3: 1- (3-carboxyphenyl) -5-mercaptotetrazole SU-2: ethylene oxide of p-nonylphenol 1
2 mol adduct SU-3: i-pentyl decyl sulfosuccinate sodium salt SU-4: di (2,2,3,3,4,4, sulfosuccinate)
5,5,6,6,7,7-dodecylfluoroheptyl)
Sodium salt _{SU-5: C 8 F 17} SO 2 N (C 3 H 7)
(CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ SO ₃ Na

[0196]

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[0197]

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As the upper layer of the protective layer, as shown in Table 1, any one was selected and applied. The amount of each material was for one side, and the amount of silver applied was adjusted to 1.5 g / m ² as one side. Thus, X-ray photosensitive material samples 1 to 23 were prepared.

[0199]

[Table 1]

[0200]

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(Production of Fluorescent Intensifying Screen 1) Phosphor Gd ₂ O ₂ S: Tb (average particle size 1.8 μm) 200 g Conjugated polyurethane thermoplastic elastomer 20 g (Demolac TPKL-5-2625 (solid content 40%) ): Sumitomo Bayer Urethane Co., Ltd.) Nitrocellulose (nitrification degree 11.5%) 2 g Methyl ethyl ketone solvent was added to the above and dispersed by a propeller type mixer to prepare a coating solution for forming a phosphor layer having a viscosity of 25 ps (25 ° C.). (Binder / phosphor ratio = 1/22 weight ratio).

Separately, as an undercoat layer forming coating solution, 90 g of a soft acrylic resin solid content and 50 g of nitrocellulose were dispersed and mixed by adding methyl ethyl ketone to obtain a viscosity of 3 to 6
A ps (25 ° C.) dispersion was prepared.

Thickness 250 μm in which titanium dioxide is kneaded
The polyethylene terephthalate base (support) was placed horizontally on a glass plate, and the undercoat layer-forming coating solution was uniformly applied on the support using a doctor blade.
To 100 ° C gradually to dry the coated film,
An undercoat layer having a dry film thickness of 15 μm was formed.

Onto this undercoat layer, the above-mentioned phosphor layer forming coating solution was uniformly applied and dried to a film thickness of 240 μm using a doctor blade, and then compressed. The compression was performed using a calender roll at 800 kg / cm ² and 80 ° C. After compression, a transparent protective film having a thickness of 3 μm was formed by the method described in Example [1] of JP-A-6-75097.

As described above, a fluorescent intensifying screen 1 comprising the support / undercoat layer / phosphor layer / transparent protective film was produced.

(Production of Fluorescent Intensifying Screen 2) In the production of the fluorescent intensifying screen 1, the film thickness of the coating liquid for forming the phosphor layer was 150 μm.
A fluorescent intensifying screen 2 composed of a support / undercoat layer / phosphor layer / transparent protective film was produced in the same manner as in the fluorescent intensifying screen 1 except that the coating was carried out in step 1 above and no compression was performed.

(Measurement of Characteristics of Fluorescent Intensifying Screen) <Sensitivity> For the MRE single-sided photographic light-sensitive material manufactured by Eastman Kodak Company, the fluorescent intensifying screen to be measured was placed on the front side of the X-ray source, and then the light-sensitive material. Place the fluorescent intensifying screen in contact,
Change the X-ray exposure by the distance method and logE = 0.15
Step exposure with a width of.

The exposed light-sensitive material was developed by the method described in the method for measuring characteristics of photographic light-sensitive material described below to obtain a measurement sample.

With respect to the measurement sample, the concentration was measured with visible light to obtain a characteristic curve. Sensitivity is expressed as the reciprocal of the X-ray exposure amount that gives a density of Dmin + 1.0.
It was expressed by the relative sensitivity as (reference value). The results are shown in Table 3.

<X-ray absorption> 80 KV with three-phase power supply
Intrinsic filtration operated at p transmits X-rays generated from a tungsten target tube corresponding to 2.2 mm of aluminum through an aluminum plate with a thickness of 3 mm and fixes the sample tube at a position 200 cm from the tungsten anode of the target tube. After reaching the intensifying screen, the X-ray dose transmitted through the intensifying screen was measured using an ionization dosimeter at a position 50 cm behind the phosphor layer of the fluorescent intensifying screen, and the X-ray absorption amount was obtained. It was In addition, the X-ray dose at the above measurement position measured without passing through the fluorescent intensifying screen was used as a reference.

Table 2 shows the measured values of the X-ray absorption amount of each of the obtained fluorescent intensifying screens.

[0212]

[Table 2]

(Preparation of Development Replenishing Tablet) A development supplementing tablet was prepared according to the following procedures (A) and (B).

Operation (A) 12500 g of a developing agent, sodium erythorbate, is ground in a commercially available bandam mill until the average particle size becomes 10 μm. 2000 g of sodium sulfite, 2700 g of phenidone, 1250 g of DTPA (pentasodium diethylenetriaminepentaacetate), 12.5 g of 5-methylbenzotriazole, 4 g of 1-phenyl-5-mercaptotetrazole, 60 g of N-acetyl-D, L-penicillamine And mixed in a mill for 30 minutes, and granulated by adding 30 ml of water at room temperature for about 10 minutes in a commercially available stirring granulator.
And dried for 2 hours to almost completely remove the water content of the granulated product.

To the granules thus prepared, 1670 g of polyethylene glycol # 6000 and 1 unit of Mannitol were added.
After 670 g of the mixture was uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less, the obtained mixture was tough press-collected by Kikusui Seisakusho 1527HU.
Using a modified tableting machine to reduce the filling amount per tablet to 8.77.
g and compression tableting to prepare 2500 tablets A for development replenishment.

Operation (B) 4000 g of potassium carbonate, 2100 g of mannitol, and 2100 g of polyethylene glycol # 6000 are ground and granulated in the same manner as in the operation (A). The amount of water added is 30.0
ml, and after granulation, dried at 50 ° C. for 30 minutes to remove almost completely the moisture of the granulated material. The obtained mixture was charged in the same tableting machine as in the operation (A) to a filling amount of 3.2 per tablet.
The tablet was compressed to 8 g and compression tableting was performed to prepare 2500 tablets B for replenishment for development.

(Preparation of Fixing Replenishing Tablet) Next, a fixing replenishing tablet was prepared by the following procedure.

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 5
After the granulation, the granulated product is dried at 60 ° C. for 30 minutes to remove the moisture of the granulated product almost completely. 4 g of sodium N-lauroylalanine is added to the granules thus prepared, and mixed for 3 minutes in a room adjusted to 25 ° C. and 40% RH or less using a mixer. The obtained mixture was charged with a tableting machine described above to a filling amount of 6.202 per tablet.
g and compression tableting to prepare 2500 fixing supplementary tablets C.

Operation (D) Boric acid 1000 g, aluminum sulfate · 18-hydrate 1500
g, sodium hydrogen acetate (equimolar mixture of glacial acetic acid and sodium acetate and dried) 3000 g, tartaric acid 200 g
Is pulverized and granulated in the same manner as in the operation (A). The amount of water added is 1
The volume of the granules is adjusted to 00 ml, and after granulation, the granules are dried at 50 ° C. for 30 minutes to almost completely remove water. 4 g of sodium N-lauroylalanine was added to the thus-prepared product, and after mixing for 3 minutes, the obtained mixture was compressed to a filling amount of 4.5562 g per tablet using the above-mentioned tableting machine. Tableting was performed to prepare 1250 fixing replenishing tablets D.

Developer starter Glacial acetic acid 2.98 g Potassium bromide 4.0 g Water was added to make 1 liter.

At the start of processing of the developing solution (starting of running), a solution prepared by diluting 434 pieces of each of agent A and agent B of developing replenishing tablet with diluting water to 16.5 liters of developing solution and adding 330 ml of a starter was added. Processing was started by filling the developing tank as a start solution. The pH of the developer to which the starter was added was 10.45.

As the fixing start solution, 11.0 liters of the fixing solution prepared by diluting the fixing replenishing tablet with the agent C corresponding to 298 g and the agent D with 149 g was diluted to fill the fixing tank.

The light-sensitive material prepared above was exposed to light so that the optical density after development was 1.0, and running was carried out.

During the running, the developing solution contained in the photosensitive material 0.
The above-mentioned ^two agents A and B and 62 ml of water were added per 62 m ² . When A and B were dissolved in 20 ml of water, the pH was 10.70. 0.6 for the fixing solution
^Two C agents, one D agent and 74 water per 2 m ^2.
ml was added. The rate of addition of water to each treating agent was started almost simultaneously with the addition of the treating agent, and was added at a constant speed for 10 minutes approximately in proportion to the dissolution rate of the treating agent.

<Evaluation of Sensitometry> The obtained light-sensitive material sample was sandwiched between fluorescent intensifying screens 1, irradiated with X-rays through a penetrometer B type (manufactured by Konica Medical), and then an automatic processor SRX-manufactured by Konica. A solid processing agent charging member was attached to 701, and the above solid processing agent was used to perform processing at a developing temperature of 35 ° C. for a total processing time of 30 seconds. At this time, the replenishment amount of the processing liquid was the amount shown in Tables 3 and 4 for both the developing solution and the fixing solution.

The sensitivity was shown as a relative value with the reciprocal of the X-ray exposure amount required to obtain the density of Sample 1 being +1.0 as the minimum density.

<Evaluation of ultra-rapid processability> Similar to the evaluation of sensitometry, each sample was sandwiched between fluorescent intensifying screens 1 and irradiated with X-rays, and then SRX-701 with a solid processing agent charging member was attached. Then, the processing was carried out at a developing temperature of 35 ° C. with a processing solution prepared by modifying the processing time as follows to prepare it using the above solid processing agent. Replenishment of the processing solution was performed while replenishing the developing solution and the fixing solution in the amounts shown in Table 4.

Development time: 4 seconds Fixing time: 3.1 seconds Water washing time: 2 seconds Water washing-drying (squeeze): 1.6 seconds Drying time: 4.3 seconds Total processing time: 15 seconds <Evaluation of silver tone > The obtained sample was cut into 10 cm × 30 cm, sandwiched between the fluorescent intensifying screens 1, irradiated with X-rays, subjected to the same treatment as the evaluation of sensitometry, and visually evaluated in the following 5 grades. .

5: There is no yellowish tint and it is in a cold black tone. 4: A slight yellowish tint is seen, but it is at a level that is hardly noticeable. 3: Yellowish tint is seen, but it is at a level where there is no practical problem. 2: Strong yellow color, which is a problem for practical use 1: Extremely strong yellow color, not suitable for practical use <Evaluation of fixing failure due to oil sludge> Exposure to a density of 0.9 using a large-angle size running film After that, 1000 sheets were continuously processed. After the running process, the film was left for 6 hours and then 10 unexposed films were processed. The ten processed films were observed and evaluated according to the following five grades.

5: No defective fixing was observed at all 4: After film processing, a small amount of defective fixing occurred in the range of 1 cm at the edge. 3: Partial defective pitch-like fixing of the roller was observed. Occurred at about 1/10 2: Streak-shaped improper fixing occurred on the entire surface along the roller pitch 1: Poor fixing occurred on the entire surface at 20 or more points within 5 cm ² <Evaluation of static mark occurrence rate> 4 cm x The unexposed sample cut into 30 cm is conditioned at 25 ° C. and 20% RH for 2 hours, and a neoprene rubber roller and a stainless roller are used.
After rubbing independently of each other, the above-mentioned development processing was carried out, and the following criteria were evaluated.

A: No static mark was generated at all B: A slightly small static mark was generated C: A small number of static marks were generated on the entire surface although the number was small D: Static in about 1/3 of the total sample area Marks are generated E: Static marks are generated in ½ or more of the total sample area. The results are shown in Tables 3 and 4.

[0232]

[Table 3]

[0233]

[Table 4]

[0234]

Industrial Applicability According to the present invention, a silver halide photographic light-sensitive material and an X-ray image formation which do not generate oil sludge, are excellent in antistatic performance and silver tone, and can obtain sufficient photographic performance by quick processing with low replenishment. It was possible to provide a method, and a processing method thereof.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location G03C 5/26 G03C 5/26 520 520 5/31 5/31 5/395 5/395 G21K 4/00 G21K 4 / 00 A

Claims (12)

[Claims] 1. A hydrophilic colloid layer containing a silver halide emulsion layer is provided on a support, and at least one of the hydrophilic colloid layers contains a leuco compound which gives a blue dye after treatment, and the support. A silver halide photographic light-sensitive material comprising a conductive substance on the side having an emulsion layer on the body. 2. The silver halide photographic material according to claim 1, wherein the leuco compound is represented by the following general formula (I). Embedded image [Wherein, R ₁ and R ₂ each represent an alkyl group or an aryl group. R ₃ represents a hydrogen atom, a halogen atom or a monovalent substituent, and n represents an integer of 1 to 3. X, Z ₁ and Z
₂ represents an atomic group necessary for forming a 5- to 6-membered aromatic carbocyclic ring or aromatic heterocyclic ring together with carbon atoms adjacent to Z ₁ and Z ₂ . R ₄ represents a hydrogen atom, an acyl group, a sulfonyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. CP represents the following group. Embedded image In the formula, R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom, a halogen atom or a substituent capable of substituting on a benzene ring. or,
R ₅ and R ₆ and R ₇ and R ₈ may be bonded to each other to form a 5- to 7-membered ring. R ₉ and R ₁₂ have the same meaning as R ₄ . R
₁₀ and R ₁₁ each represent an alkyl group, an aryl group or a heterocyclic group. R ₁₃ , R ₁₄ and R ₁₅ are respectively R ₁₀ , R ₁₁
And it is synonymous with R _12. R ₁₆ represents an alkyl group, an aryl group, a sulfonyl group, a trifluoromethyl group, a carboxyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. R ₁₇ is R
Has the same meaning as ₄ , R ₁₈ has the same meaning as R ₃ , and m represents an integer of 1 to 3. R ₁₉ and R ₂₀ each represent an alkyl group or an aryl group. R ₂₁ and R ₂₄ have the same meanings as R _4, R ₂₂
And R ₂₃ have the same meanings as R ₁₉ and R ₂₀ respectively. Y represents an atomic group necessary for forming a 5- or 6-membered monocyclic or condensed nitrogen-containing heterocyclic ring together with two nitrogen atoms. * Indicates a bonding point between CP and other partial structures in the general formula (I). ] 3. The halogenated product according to claim 1, wherein the leuco compound represented by the general formula (I) is contained in an amount of 1 × 10 ^{−6 to} 5 × 10 ⁻¹ mol per mol of silver. Silver photographic light-sensitive material. 4. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein the conductive substance is a metal oxide. 5. The silver halide photographic light-sensitive material according to claim 4, wherein the metal oxide is a colloidal tin oxide sol and is contained in the undercoat layer. 6. The silver halide grains contained in the silver halide emulsion layer are tabular having a main plane composed of two parallel (100) faces, and the silver chloride content is 10 mol% or more. A silver halide photographic light-sensitive material according to any one of claims 1 to 5. 7. The silver halide according to claim 1, wherein the total amount of the hydrophilic binder on the support is 1.0 to 3.0 g / m ² per side. Photographic material. 8. A silver coating weight per side of 1.0 to 2.0 g.
8. The silver halide photographic light-sensitive material according to any one of claims 1 to 7, which is / m ² . 9. A support having emulsion layers on both sides of the support.
The silver halide photographic light-sensitive material according to any one of 1 to 8 is 45% with respect to X-rays having an X-ray energy of 80 kVp.
The above absorption amount is shown, and the filling rate of the phosphor is 68% or more,
An X-ray image forming method characterized in that imagewise exposure is performed by irradiating X-rays with a fluorescent substance sandwiched between fluorescent intensifying screens having a thickness of 135 to 200 μm or less. 10. A halogen characterized by processing the silver halide photographic light-sensitive material according to claim 1 by an automatic processor having a mechanism for supplying a solid processing agent to a processing tank. Processing method of silver halide photographic light-sensitive material. 11. At least one of a developing step and a fixing step.
11. The method of processing a silver halide photographic light-sensitive material according to claim 10, wherein the amount of replenisher replenished in the step is represented by the following formula. 1 ≦ replenisher / amount taken out by the photosensitive material ≦ 5 12. A processing time (Dry) required for all processing steps.
12. The method for processing a silver halide photographic light-sensitive material according to claim 10, wherein the to dry is within 20 seconds.