JPH1010667A - Manufacture of photosensitive silver halide emulsion and silver halide photographic sensitive material and its processing method and photographing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material high in sensitivity and image quality and superior in rapid processing aptitude and resistance to processing fluctuation. SOLUTION: This photographic sensitive material has the photographic silver halide emulsion layer on a support and this emulsion layer is sensitized by adding a spectral sensitizing dye represented by the formula in a pH range of 3-7 and then a chemical sensitizer in a pH of higher by 0.5-5 than that in the case of the spectral sensitizing dye and subjected to chemical sensitization ripening. In the formula, each of R1 and R3 is an optionally substituted lower alkyl group; at least one of R2 and R4 is an alkyl group substituted by an hydrophilic group; X is ions necessary for neutralizing an intramolecular charge; (n) is 1 or 2 but when an intramolecular salt is formed, (n) is 1; and each of Z1 -Z4 is a substitutable group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a light-sensitive silver halide emulsion having high sensitivity, low dye contamination and excellent sharpness, a silver halide photographic light-sensitive material, a processing method thereof, and a photographing method. Among them, it relates to X-ray medical use.

[0002]

2. Description of the Related Art In recent years, with the increase in the processing of silver halide photographic light-sensitive materials, the demand for rapid processing has been increasing. For example, a similar tendency is seen in the field of medical X-ray films. Since the number of X-ray photographs has been increased due to the spread of health examinations and the increase in examination items for improving the accuracy of diagnosis, it has been strongly desired to reduce processing waste liquid. In addition, there is a need to notify the examinee of the diagnosis result earlier, and there is a strong demand for ultra-rapid processing after imaging.

In order to speed up the processing, it is necessary to shorten the processing time of each processing step such as development, fixing, washing and drying, but there is a problem that the load of each processing increases. For example, if the development time is simply shortened, the conventional photosensitive material has a problem that the image density is reduced, that is, the sensitivity is lowered and the gradation is deteriorated. On the other hand, if the fixing time is shortened, fixing of the silver halide becomes incomplete and causes deterioration of image quality. Further, shortening the time of each processing step causes a problem that the sensitizing dye is not sufficiently eluted in each of the processing of development, fixing, and washing with water, resulting in deterioration of image quality due to residual dye (residual color). Therefore, in order to solve such a problem, it is necessary to increase the developing speed and the fixing speed, to reduce the amount of the dye, and to accelerate the detachment and / or decoloration of the dye.

On the other hand, in order to reduce the processing waste liquid, it is necessary to reduce the fatigue of the processing liquid and / or to reduce the replenishing liquid. Accompany.

As a technique for improving these problems, EP
506,584, JP-A-5-88293 and 5-
No. 93975 discloses a technique using benzimidazolocarboxycyanines having good decoloring performance as spectral sensitizing dyes. JP-A-5-61148 discloses that oxacarbocyanines and benzimidazolocarboxycyanines are used in a specific ratio as a spectral sensitizer in a silver halide emulsion having an iodine content of 1 mol% or less. A technique for performing chemical sensitization with a selenium compound and / or a tellurium compound is disclosed.

However, these disclosed techniques alone, although improving the residual color property or the rapidity of development, are still insufficient to satisfy the recent demand levels for various performances. In particular, it has a disadvantage that the sensitivity and safelight resistance are not sufficient, and that the sensitivity is greatly reduced when the photosensitive material is stored at high temperature and high humidity.

On the other hand, various basic studies have been carried out on the adsorption of silver halide grains and spectral sensitizing dyes for a long time. When adsorbing a spectral sensitizing dye to silver halide grains, studies have been often made to uniformly and selectively adsorb spectral sensitizing dyes on the grain surface and between grains. As a method of adding a spectral sensitizing dye, it is also known that chemical sensitization is performed in the presence of a spectral sensitizing dye to control chemical sensitization and reduce intrinsic desensitization.

[0008] However, these techniques are also inadequate in terms of storage stability, pressure resistance, safelight resistance and illuminance failure.

Meanwhile, in the field of medical X-ray photographic materials, in order to improve patient service and operability, in addition to speeding up processing and reducing processing waste liquid, simplification over the entire processing operation is strongly required. Requested. However, the liquid processing agent that dilutes the concentrate of the processing agent and replenishes the processing tank has a problem that it is difficult to improve the efficiency of the operation because the weight and the volume are large. As an alternative to this, in recent years, a solid processing agent supplied with a solid component and dilution water to a processing layer of an automatic developing machine has been proposed. As a result, the transportation cost, the storage space and the working efficiency can be reduced, and the amount of packaging material used can be reduced, which is favorable for the environment. However, due to the solubility of the solid components, it is difficult to obtain sufficiently stable running performance, especially when the development processing is performed for an extremely short time.

[0010] The developer for the medical X-ray photographic light-sensitive material includes:
Conventionally, dihydroxybenzene compounds represented by hydroquinone have been frequently used as developing agents. However, in recent years, it has been clarified that hydroquinone is unfavorable from ecology and toxicological findings, and furthermore, it has been desired to take measures in consideration of the pollution load (high COD and BOD) of a developing waste solution in a laboratory.

[0011] As an alternative, reductones such as ascorbic acid have been re-examined as developing agents, and have recently attracted attention because they are compounds having no problem from the viewpoint of ecology and toxicology.

[0012]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a method for producing a photosensitive silver halide emulsion having low fog, high sensitivity, little dye contamination and excellent pressure resistance, and an emulsion prepared by the method. The object of the present invention is to provide a silver halide photographic light-sensitive material produced from the same.

A second object of the present invention is to provide a processing method which achieves rapid processing of the light-sensitive material, stabilization of running performance and reduction of processing waste liquid, and is environmentally excellent. is there. A third object of the present invention is to provide an imaging method with high sensitivity.

[0014]

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

(1) In a silver halide photographic material having a photographic component layer including at least one photosensitive silver halide emulsion layer on a support, the photosensitive silver halide emulsion layer has a pH of 3 to 7. Under the conditions of the range, the following general formula (1)
Is added, and a chemical sensitizer is added under a condition 0.5 to 5 higher than the pH at the time when the spectral sensitizing dye is added, and chemically sensitized and ripened. A silver halide photographic light-sensitive material comprising a light-sensitive silver halide emulsion.

[0016]

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In the formula, R ₁ and R ₃ each represent a substituted or unsubstituted lower alkyl group, and R ₂ and R ₄ each represent a lower alkyl group or an alkyl group substituted with a hydrophilic group. However, at least one of R ₂ and R ₄ represents an alkyl group substituted with a hydrophilic group. X represents an ion necessary to neutralize the charge in the molecule, and n represents 1 or 2. However, when an inner salt is formed, n is 1. Z _{1 to} Z ₄ represent a substitutable group.

(2) When the silver halide photographic material is processed by a processing method including development, fixing and drying steps,
A method for processing a silver halide photographic material, wherein the total processing time is 30 seconds or less.

(3) A method of continuously processing the silver halide photographic material in a processing step including development and fixing steps, wherein a solid processing agent is continuously processed in a processing solution in each processing step. A method for processing a silver halide photographic light-sensitive material, characterized in that it is supplied.

(4) After adding the spectral sensitizing dye represented by the above formula (1) under the condition that the pH of the photosensitive silver halide emulsion is in the range of 3 to 7, the spectral sensitizing dye is added. A method for producing a light-sensitive silver halide emulsion, characterized in that a chemical sensitizer is added thereto under a condition of 0.5 to 5 higher than the pH when the chemical sensitization is carried out.

(5) The silver halide photographic light-sensitive material is sandwiched between high-sensitivity intensifying screens having a phosphor filling ratio of 68 to 90% in a phosphor layer, and X-ray photography is performed. How to shoot photographic materials.

Hereinafter, the present invention will be described in detail.

In the general formula (1), R ₁ and R ₃ each represent a substituted or unsubstituted lower alkyl group, R ₂ and R ₄ each represent a lower alkyl group, and at least one of R ₂ and R ₄ is It is an alkyl group substituted for a hydrophilic group. X represents an ion necessary to neutralize the charge in the molecule, and n represents 1 or 2. However, when an inner salt is formed, n is 1 and Z _{1 to} Z ₄ represent a substitutable group.

In the spectral sensitizing dye represented by the general formula (1), R ₁ and R ₃ are a substituted or unsubstituted lower alkyl group, and the lower alkyl group has 1 to 6 carbon atoms.
And straight- and branched-chain groups such as a methyl group, an ethyl group, a propyl group and a 3-methylbutyl group. Examples of the substituted alkyl group include 2-
Hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, ethoxycarbonylethyl group, allyl group, phenethyl group, methanesulfonylethyl group and 3-
An oxobutyl group is exemplified. R ₁ and R ₃ are preferably a methyl group or an ethyl group, and at least one of R ₁ and R ₃ is preferably methyl.

Examples of the lower alkyl group represented by R ₂ and R ₄ include straight-chain and branched groups such as methyl, ethyl, butyl and isobutyl groups. Sulfo group, carboxy group, methanesulfonylaminocarbonyl group, methanesulfonylaminosulfonyl group, acetylaminosulfonyl group, sulfoamino group, trifluoroacetylaminosulfonyl group, acetylaminocarbonyl group, N-methylsulfamoyl group, etc. And specific examples thereof include a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 5-sulfopentyl group, a 2-N-ethyl-N-sulfaminoaminoethyl group, a carboxymethyl group, and a carboxyethyl group. Group, 3-sulfoaminopropyl group, 6-sulfo-
3-oxahexyl group, 10-sulfo-3,6-dioxadecyl group, 6-sulfo-3-thiahexyl group, o-sulfobenzyl group, P-carboxybenzyl group, methanesulfonylaminocarbonylmethyl group, acetylaminosulfonylmethyl group And the like. However, at least one of R ₂ and R ₄ represents an alkyl group substituted with a hydrophilic group.

The electron-withdrawing groups represented by R ₂ and R ₄ are preferably groups having a Hammett σp value of 0.01 or more, more preferably 0.05 to 0.95.

The Hammett σp value is a substituent constant defined by Hammett et al. Based on the relationship between the hydrolysis rate constant of benzoic acid ester and the dissociation constant of benzoic acid. Guidelines for Design and Working Machinery-”P96-103. Published by Nankodo or “Substitute Constance for Correlation Analysis in Chemistry and Biology”
ans for Correlation Analysis
sis in Chemistry and Bio
logy) "P69-161 Jhon Wiley &
It is described in detail in Sons and the like.

In the present invention, preferred groups having a Hammett σp value include, for example, a trifluoromethyl group, a cyano group,
Carboxy group, halogen atom group, carbamoyl group, ethynyl group, acetyl group, ethoxycarbonyl group, trifluoromethoxy group, sulfamoyl group, methanesulfonyl group, benzenesulfonyl group, trifluoromethylthio group, isothiocyanate group, 1-pyrroline group, Examples thereof include a 2-pyridyl group, and specific examples thereof include a trifluoroethyl group, a 2-cyanoethyl group, a carboxymethyl group, a carbamoylmethyl group, an N, N-tetramethylenecarbamoyl group, a 2- (1-pyrrolyl) ethyl group, Examples thereof include a 2- (2-pyridyl) ethyl group, a 2-morpholinosulfamoylethyl group, and a 2-methanesulfonylethyl group.

Examples of the substitutable group represented by Z _{1 to} Z ₄ include a halogen atom (for example, fluorine, chlorine, bromine, iodine atom, etc.) and an alkyl group (for example, lower alkyl group such as methyl, ethyl, propyl group, etc.) ), Alkoxy groups (eg, methoxy, ethoxy, propoxy groups, etc.), halogen-substituted alkoxy groups (eg, fluoromethoxy, trifluoromethyl, 2,2,2-trifluoroethyl groups, etc.),
An aryloxy group (eg, phenoxy, p-bromophenoxy group, etc.), an acyl group (eg, acetyl, benzoyl group, etc.), an acyloxy group (eg, acetyloxy, propionyloxy group, etc.), an alkylthio group (eg, methylthio, ethylthio group, etc.), A halogen atom-substituted alkylthio group (eg, trifluoromethylthio, difluoromethylthio group, etc.), an alkoxycarbonyl group (eg, methoxycarbonylmethyl, ethoxycarbonyl group, etc.), a carbamoyl group (eg, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl) , N, N-diethylcarbamoyl, N, N-3-oxa-pentamethylenecarbamoyl, N-phenylcarbamoyl group, etc.), sulfamoyl group (for example, N-methylsulfamoyl,
N, N-tetramethylenesulfamoyl, N, N-3-
Oxapentamethylene sulfamoyl, N-phenylsulfamoyl, N, N-diethylsulfamoyl group, etc., haloalkyl group (for example, monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl group, etc.), sulfonyl group ( For example, methanesulfonyl, ethanesulfonyl, trifluoromethanesulfonyl, fluorosulfonyl, benzenesulfonyl, p-toluenesulfonyl group, etc., acylamino group (eg, N-acetylamino, N-trifluoroacetylamino group, etc.), substituted or unsubstituted aryl group (E.g., phenyl, o-fluorophenyl, p-cyanophenyl, m-chlorophenyl, etc.). Examples of the heterocyclic group include substituted or unsubstituted ones, such as a 1-pyrrolyl group and a 2-furyl group. ,
Each group such as a 2-benzoxazolyl group is exemplified.

Depending on the substituents on R ₂ and R ₄ , a counter ion X may be required to neutralize the charge on the dye molecule.
For example, if the dye molecule has two anionic substituents (eg,
If substituted with a sulfone), X would be a cation. If the dye molecule is substituted with only one anionic substituent, there will be no counterion X and the dye molecule will be an anionic substituent. Such counterions X are well known in the art and include, for example, cations such as sodium, potassium and triethylammonium and anions such as chloride, bromide, iodide,
p-Toluenesulfolate, methanesulfate, methyl sulfate, ethyl sulfate, perchlorate, fluoroborate and the like.

Hereinafter, specific examples of the spectral sensitizing dye represented by the general formula (1) will be described, but the present invention is not limited thereto.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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As the spectral sensitizing dye represented by the general formula (1), in addition to the specific examples described above, for example, JP-A-7-114
Compounds listed in Tables 1 and 2 of JP-A-131 and Table 1 of JP-A-5-88293 can be used in the same manner.

In the present invention, the spectral sensitizing dye refers to a dye which is adsorbed on silver halide grains and contributes to sensitization. The spectral sensitizing dye used in the present invention is arbitrary as long as it has a spectral sensitizing function, and the spectral sensitizing dye represented by the above general formula (1) (hereinafter, referred to as the compound of the present invention) is used as a silver halide emulsion. When the particles are adsorbed on particles and the reflection spectrum is measured, it is necessary that the maximum absorption wavelength of the J aggregation band is 555 nm or less. In the application to X-ray medical light-sensitive materials utilizing a phosphor emitting green light, the compound of the present invention is adsorbed on silver halide emulsion grains, and when the reflection spectrum is measured, the green color from the phosphor is measured. It is preferable that the J-band is formed in the same wavelength region as the light. That is, it is preferable to select and combine the compounds of the present invention so that the J-band having the maximum absorption is preferably formed in the region of the maximum absorption wavelength of 520 to 555 nm. More preferably 530-553 nm, most preferably 540 nm.
５550 nm.

In the present invention, it is necessary to add the compound of the present invention under the condition that the pH of the photosensitive silver halide emulsion (hereinafter, also simply referred to as emulsion) is in the range of 3 to 7. Preferably, the pH can be set to an arbitrary pH in the range of 3.5 to 6.5, more preferably 4 to 6. Further, it is necessary to add a chemical sensitizer under a condition of pH 0.5 to 5 higher than the pH at the time of adding the compound of the present invention to perform chemical sensitization ripening. The applied pH is 3.5 to 1
2, preferably in the range of 3.5 to 10, more preferably in the range of 4.5 to 8. pH
The pH of the emulsion may be adjusted in advance to 3 to 7 or may be added as an acidic solution of the spectral sensitizing dye. Adjustment of the pH can be performed with a commonly used buffer.

The technique of using the compound of the present invention in combination with two kinds of spectral sensitizing dyes of oxacarbocyanines is useful for silver halide photographic materials requiring sensitivity to green light. In particular, it is remarkably effective in adapting to an X-ray recording material using a phosphor emitting green light in order to increase the recording sensitivity to X-rays, and is particularly effective in X-ray medical photosensitive materials. In order to further improve the sensitivity and the residual color, the ratio of the compound of the present invention is preferably at least 40 mol% of all the dyes in the silver halide light-sensitive material (hereinafter simply referred to as light-sensitive material).

Specific examples of the above-mentioned oxacarbocyanines spectral sensitizing dyes are shown below, but the compounds usable in the present invention are not limited to these.

[0047]

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[0048]

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In the present invention, other spectral sensitizing dyes may be used in combination. Examples of the spectral sensitizing dye used include a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holobora cyanine dye, a hemicyanine dye, a styryl dye, and a hemioxonol dye. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. These dyes can be applied to any of the nuclei commonly used. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus and the like, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei, Indolenine nucleus, benzindolenin nucleus, indole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

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

These spectral sensitizing dyes are described, for example, in German Patent 929,080, US Pat. No. 2,231,658,
2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,655,394, 3,656,959, and 3 , 672,897 and 3,649,217, British Patent 1,242,588 and JP-B-44-14030.
No. etc. In addition to these spectral sensitizing dyes, dyes that do not have spectral sensitization or substances that do not substantially absorb visible light and that exhibit supersensitizing action are used in combination with a photosensitive silver halide emulsion layer (hereinafter, referred to as a light-sensitive silver halide emulsion layer). , Simply referred to as an emulsion layer).

The addition amount of the compound of the present invention alone or the compound of the present invention and the other spectral sensitizing dyes described above is as follows.
Type of dye and structure, composition, ripening condition of silver halide,
The monolayer coverage of the surface of each photosensitive silver halide grain in the emulsion is 30 to 90, although it depends on the purpose and use.
%, Preferably 40-80%
Is preferred. In the present invention, the monolayer coverage is 5%.
The saturated adsorption amount when an adsorption isotherm is created at 0 ° C. is relatively determined as an amount corresponding to a monolayer coverage of 100%.

The appropriate amount per mol of silver halide varies depending on the total surface area of the silver halide grains in the emulsion.
It is preferably less than 00 mg, more preferably 450 mg or less.

In the present invention, the addition of the spectral sensitizing dye as an acidic solution or a dispersion of solid fine particles is more preferable than the case where the spectral sensitizing dye is added as a solution in an organic solvent, since the effect is increased. Preferably, at least one of the spectral sensitizing dyes is added in the form of a solid fine particle dispersion substantially insoluble in water dispersed in an aqueous system substantially free of an organic solvent and / or a surfactant. . here,
The aqueous system substantially free of an organic solvent and / or a surfactant is water containing impurities at a level not to adversely affect the silver halide photographic emulsion, more preferably ion-exchanged water and distilled water. .

The compound of the present invention is added at the time of the chemical ripening step, particularly preferably at the start of the chemical ripening step, and when the compound is added from the step of forming the nucleus of the emulsion to the end of the desalting step, the spectral sensitization efficiency is improved. High-sensitivity silver halide emulsion can be obtained, but at any time after the completion of the desalting step, immediately after the chemical ripening step and immediately before the coating step, the above-mentioned step (from the time of the nucleation step to the end of the desalting step) May be additionally added. At this time, the compounds of the present invention may be other than the same species.

The silver halide solvent used for chemical sensitization may be added as a mixture with a chemical sensitizer. The amount of the silver halide solvent to be added is preferably 60 mg or more, more preferably 90 mg or more per mol of silver. In the present invention, the conditions of the step of chemical sensitization, for example, pAg, temperature, time and the like can be performed under the conditions generally used in the art. Further, the pH change during the chemical ripening step in the present invention can be carried out with a commonly used acid or potassium buffer.

Chemical sensitizers capable of reacting with silver ions for chemical sensitization and methods of sensitizing the same include a sulfur sensitization method using a compound containing sulfur or active gelatin, a selenium sensitization method using a selenium compound, tellurium Tellurium sensitization using a compound, reduction sensitization using a reducing substance, gold or the like, noble metal sensitization using a noble metal, or the like can be used alone or in combination. Among them, selenium sensitization, tellurium sensitization And a reduction sensitization method are preferably used, and particularly, a sulfur sensitization method, a gold sensitization method and a selenium sensitization method are preferably used.

For the chemical sensitization method used for chemical sensitization, the sensitization method described in JP-A-7-114131 can be referred to.

The selenium sensitizers used for chemical sensitization include a wide variety of selenium compounds. For example, in this regard, U.S. Pat. Nos. 1,574,944 and 1,602,592
No. 1,623,499, JP-A-60-15004
No. 6, JP-A-4-25832, JP-A-4-109240, and JP-A-4-147250. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylseleno). Urea, N, N,
N'-trimethyl-N'-heptafluoroselenourea,
N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (for example, selenoacetone, seleno Acetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphate Class (eg, tri-p
-Triselenophosphate, etc.) and selenides (diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides and selenium ketones. However, in the present invention, it is preferable to add the selenium sensitizer as a dispersion in the form of solid fine particles, as compared with the case where the selenium sensitizer is added as a solution of an organic solvent, since the effect is increased.

Examples of the gold sensitizer include chloroauric acid, gold thiosulfate, and gold thiocyanate, as well as gold complexes of thioureas, rhodanines, and other various compounds. Sulfate and allylthiourea can be mentioned.

The amounts of the sulfur sensitizer and the gold sensitizer used are not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions and the like, but are usually 1 per mol of silver halide. It is preferably from × 10 ^-4 to 1 × 10 ^-9 mol. Further, it is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

In the present invention, silver halide grains such as silver chloride, silver iodochloride, silver iodobromochloride and silver bromochloride can be used. Of these, silver chloride and silver iodochloride are more preferred. The silver halide grains contained in the silver halide emulsion preferably contain 50 mol% or more of silver chloride, more preferably 70 mol% or more, and more preferably 90 mol% or more.
More preferably, the content is at least mol%. In the case of silver iodochloride, the content of silver iodide is preferably 0.01 to 1.0 mol% as an average iodide content of the whole silver halide grains.
0.01-0.5 mol% is more preferable.

The shape of the silver halide grains used in the present invention may be any shape. For example, cube, octahedron,
It may have a shape such as a tetrahedron, a sphere, a tabular shape, and a potato shape, and particularly preferred are tabular grains.

Hereinafter, tabular grains will be described as typical examples of silver halide grains preferably used in the present invention.

In the present invention, the silver iodide content and the average silver iodide content of each silver halide grain are determined by the EPMA method (E
Electron Probe Micro Analysis
zer method). In this method, a sample in which emulsion grains are well dispersed so as not to be in contact with each other is prepared and irradiated with an electron beam to perform X-ray analysis by electron beam excitation. Elemental analysis of a very minute portion can be performed. By determining the characteristic X-ray intensity of silver and iodine emitted from each grain by this method, the silver halide composition of each grain can be determined. If the iodine content is determined for at least 50 particles by the EPMA method, the average iodine content is determined from the average thereof.

The tabular silver halide grains contained in the silver halide emulsion preferably have a more uniform iodine content between grains. When the distribution of iodine content between particles was measured by the EPMA method, the relative standard deviation was 35% or less,
Further, it is preferably at most 20%.

In the present invention, the tabular silver halide grains preferably contain silver iodide, but the silver iodide is preferably contained at least inside. If inside,
More preferably, it exists at least at the center. In this case, the internal composition preferably contains 0.1 to 5 mol% of silver iodide. The distribution of the halogen composition inside the silver halide grains can be determined by pretreating the grains into ultrathin sections and then observing and analyzing them with a transmission electron microscope while cooling. Specifically, silver halide grains are taken out of the emulsion, embedded in a resin, and cut with a diamond knife to produce a 60-nm-thick section. This section can be obtained by observation and point analysis with a transmission electron microscope equipped with an energy dispersive X-ray analyzer while cooling the section with liquid nitrogen, and by quantitative calculation (Inoue, Nagasawa: Photographic Society of Japan, 1987) Conference Abstracts p. 62).

It is also preferred that silver iodide be present on the outermost surface. In this case, the iodine content on the outermost surface is 1 mol% or more and 1
It is preferably at most 0 mol%. Here, the silver iodide content of the outermost surface of the tabular silver halide grains is defined by an XPS method (X-ray Photoelectron Spec).
troscopy (X-ray photoelectron spectroscopy) means the silver iodide content of a portion up to a depth of 50 °, which can be determined as follows.

That is, the sample was cooled to −110 ° C. or less in an ultra-high vacuum of 1 × 10 ⁻⁸ torr or less, and MgKα was used as a probe X-ray with an X-ray source voltage of 15 kv and an X-ray source current of 40 kV.
Irradiation at mA, Ag3d5 / 2, Br3d, I3d3 /
Measure for two electrons. The integrated intensity of the measured peak is determined by a sensitivity factor.
And the halide composition on the outermost surface is determined from these intensity ratios.

The purpose of cooling the sample is to eliminate measurement errors caused by destruction of the sample (decomposition of silver halide and diffusion of halide (particularly iodine)) due to X-ray irradiation at room temperature, and to increase measurement accuracy. By cooling to −110 ° C., sample destruction can be suppressed to a level that does not hinder measurement.

It is also preferred that silver bromide be present on the outermost surface. In this case, the silver bromide content on the outermost surface is preferably from 1 mol% to 10 mol%.

The average aspect ratio of the tabular silver halide grains is preferably 8 or less, more preferably less than 7,
Most preferably it is less than 5.

In the present invention, 50% or more of the total projected area of the silver halide grains contained in the emulsion is preferably composed of tabular silver halide grains having a (100) plane as a main plane, and preferably 70%. More preferably, 90% or more is composed of tabular silver halide grains having a (100) plane as a main plane. The fact that the main plane is the (100) plane can be confirmed by an X-ray diffraction method or the like.

In the present invention, the shape of the main plane of the tabular silver halide grains is a right-angled parallelogram, a shape of a right-angled parallelogram with missing corners and a rounded shape. The adjacent side ratio of the right-angled parallelogram is less than 10, preferably less than 5,
More preferably, it is less than 2.

In the case where the corner is missing or rounded, the length of the side is defined by the intersection of the straight line of the side of the right-angled parallelogram and the line extending the straight line of the adjacent side. Expressed in length.

The average grain size of the tabular silver halide grains is 0.1.
It is preferably from 15 to 5.0 μm, and from 0.4 to 3.0 μm.
More preferably, it is 0 μm, most preferably 0.1 μm.
4 to 2.0 μm. The average thickness of the tabular silver halide grains is preferably from 0.01 to 1.0 μm, more preferably from 0.02 to 0.40 μm, even more preferably from 0.02 to 0.30 μm. Particle size and thickness can be optimized to optimize sensitivity and other photographic properties. Sensitivity and other factors that make up the photosensitive material that affect photographic properties (thickness of hydrophilic colloid layer, hardness,
The optimal particle size and the optimal thickness vary depending on the conditions of chemical ripening, the sensitivity of the photosensitive material, the amount of silver, etc.).

Tabular silver halide grains are monodisperse grains having a narrow particle size distribution. Specifically, when the width of the distribution is defined by (standard deviation of particle size / average particle size) × 100 = width (%) of particle size distribution, it is 20% or less, preferably 18%. Below, more preferably 15
% Or less.

The tabular silver halide grains preferably have a narrow thickness distribution. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) × 100 = width (%) of thickness distribution, it is preferably 25% or less, more preferably 20%. The content is particularly preferably 15% or less.

The tabular silver halide grains may have dislocations. Dislocations are described in F. Hamilton, P
hot. Sci. Eng., 57 (1967); S
hiozawa, J .; Soc. Photo. Sci. Ja
Pan, 35, 213 (1972), which can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by an electron beam. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for an electron beam to pass through. Therefore, a high-pressure type (200 kV or more for a particle having a thickness of 0.25 μm)
Can be observed more clearly using an electron microscope.

When a dye capable of decoloring and / or flowing out during development processing is contained in at least any one of the layers containing the emulsion and the constituent layers other than the emulsion layer, high sensitivity and high sharpness can be obtained. In addition, a light-sensitive material having less dye stain can be obtained. The dye used in the photosensitive material may be appropriately selected from dyes that can improve sharpness by absorbing a desired wavelength and removing the influence of the wavelength, depending on the photosensitive material. I can do it. It is preferable that the dye is decolorized or flows out during the development processing of the light-sensitive material, and that the coloring is not visible when the image is completed.

Various photographic additives can be used in the light-sensitive material of the present invention. Known additives include, for example, Research Disclosure (RD) No. 1
No. 7643 (December 1978); 18716
(November 1979) and the same No. 308119 (19
(December 1989). The types of compounds and the locations described in these three RDs are listed below.

[0082]

[Table 1]

The emulsion may contain a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine and 3-pyrazolidone in an emulsion layer or any other layer.

As the support used in the light-sensitive material of the present invention, for example, RDNo. 17643, page 28 and RD No. 308119 on page 1009. A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer. The undercoat layer preferably contains an antistatic improver such as tin oxide sol.

When a silver halide emulsion layer and a crossover cut layer are provided on both sides of the support to be used, a light-sensitive material having high sensitivity, high sharpness and excellent processability can be obtained. The amount of gelatin in the silver halide emulsion layer, surface protective layer and other layers is 0.5 to 3.5 g in total on one side of the support.
/ Range of m ² are preferred, in particular in the range of 1.5～3.0G / m ² is preferred.

Hereinafter, the processing method of the present invention will be described in more detail.

In the present invention, the total processing time is 30 seconds or less (Dry to Dry), preferably 15 to 30 seconds, more preferably 20 to 30 seconds. The total processing time means the time from when the leading end of the photosensitive material starts to be immersed in the developing solution to when the leading end comes out of the drying zone through a processing step.

The replenishment in the present invention replenishes the treatment agent fatigue and oxidative fatigue. As a replenishment method, JP-A-55-55
No. 126243, replenishment by width and feed speed, area replenishment described in JP-A-60-104946,
No. 49156, the area replenishment controlled by the number of continuously processed sheets may be used.
0 ml / m ² .

In the present invention, the term “fixing solution” refers to a solution in a fixing tank. Preferred fixing solutions can include fixing materials commonly used in the art. The iodine content is preferably 0.3 g / liter or less, more preferably 0.1 g / liter or less. The pH is 3.8 or more, preferably 4.2 to 5.5. The preferred replenishment amount is 500
１００100 ml / m ² .

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

The fixing solution may be one that forms an acidic hardening. In this case, aluminum ions are preferably used as the hardener. For example, it is preferable to add in the form of aluminum sulfate, aluminum chloride, potassium alum and the like.

Other fixing solutions include a sulfite, if desired.
Preservatives such as bisulfite, pH buffers such as acetic acid and boric acid, mineral acids (sulfuric acid, nitric acid), organic acids (citric acid, oxalic acid, malic acid, etc.), various acids such as hydrochloric acid, and metal hydroxides ( PH adjusters such as potassium hydroxide and sodium hydroxide) and chelating agents having water softening ability.

Examples of the fixing accelerator include, for example,
No. 35754, No. 58-122535, No. 58-12
Thiourea derivatives described in U.S. Pat.
Thioether described in US Pat. No. 6,459.

The emulsion layer has a swelling ratio of 150 to 150 during the development process.
It is preferably 250%, and the film thickness after expansion is preferably 70 μm or less. When the water swelling ratio exceeds 250%, poor drying occurs, and for example, conveyance failure also occurs in automatic developing machine processing, particularly in rapid processing. On the other hand, if the water swelling ratio is less than 150%, development unevenness and residual color tend to be deteriorated during development. Here, the water swelling ratio is obtained by calculating the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, dividing the difference by the film thickness before processing and multiplying by 100. .

The silver halide photographic light-sensitive material of the present invention does not substantially contain a dihydroxybenzene-based developing agent, and the main developing agent is a compound represented by the general formula (2). Developed. The term “substantially” as used herein means that a dihydroxybenzene compound is not contained in an amount having a developing ability.

The developing solution preferably contains a 1-phenyl-3-pyrazolidone-based auxiliary developing agent and / or a P-aminophenol-based auxiliary developing agent as an auxiliary developing agent.

The compound represented by formula (2) will be described in detail. In the general formula (2), R ₅ and R ₆ each represent a hydroxy group or an amino group (as a substituent, an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, and n
-Including those having a butyl group, a hydroxyethyl group or the like as a substituent. ), Acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (Methoxycarbonylamino group, etc.), mercapto group, and alkylthio group (methylthio group, ethylthio group, etc.). Preferred examples of R ₅ and R ₆ are a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q represent a hydroxy group, a carboxy group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, a mercapto group, an alkyl group and an aryl group. P and Q are attached, it represents an atomic group in which two vinyl carbon atoms and Y for R ₅ and R ₆ is substituted to form a 5- to 8-membered ring together with the carbon atoms to which they are substituted. Specific examples of the ring structure, -O -, - C (R 8) (R 9) -, - C
_{(R 10) =, - C} (= O) -, - N (R 11) -, - N =
Are configured in combination. Here, R _{8 to} R ₁₁ are a hydrogen atom, a substitutable alkyl group having 1 to 10 carbon atoms (such as a hydroxy group, a carboxy group or a sulfo group as a substituent), and a substitutable aryl group having 6 to 15 carbon atoms (substituent group). Represents an alkyl group, a halogen atom, a hydroxy group, a carboxy group and a sulfo group), a hydroxy group, a carboxy group and the like. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 8-membered ring. Examples of the 5- to 8-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cycloxenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacycloquinone ring, and a uracil ring. .

Y represents ＝ O or ＮN—R ₇ . R ₇ represents a hydrogen atom, a hydroxyl group, an alkyl group (eg, a methyl group, an ethyl group, etc.), an acyl group (acetyl group), a hydroxyalkyl group (a hydroxymethyl group, a hydroxyethyl group, etc.), a sulfoalkyl group (a sulfomethyl group, And a carboxyalkyl group (such as a carboxymethyl group and a carboxyethyl group).

The compound represented by the above general formula (2) is preferably used in an amount of 0.005 to 0.5 mol per liter of a developing solution, more preferably 0.02 to 0. 4mo
l. Specific examples of the compound represented by the general formula (2) are shown below, but the present invention is not limited thereto.

[0101]

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[0102]

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[0103]

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[0104]

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The silver halide photographic material of the present invention can be processed using a solid processing agent. The solid processing agent referred to in the present invention is a powder processing agent, a solid processing agent such as tablets, pills and granules, etc., which is subjected to a moisture-proof treatment as required.

In the present invention, the powder refers to an aggregate of fine crystals, and the granules refer to a powder obtained by subjecting a powder to a granulation step and have a particle size of 50 to 5000 μm.
In addition, the tablet in the present invention refers to a tablet obtained by compression-molding a powder or granules into a certain shape. The silver halide photographic material of the present invention is supplied and processed while continuously processing such a solid processing agent.

In order to solidify the processing agent, a concentrated solution or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded processing agent is sprayed with the water-soluble binder. Or any other means such as forming a coating layer. A preferred tablet production method is a method of granulating a powdery solid processing agent and then performing a tableting step to form the tablet.

Compared to a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet, the solubility and storage properties are improved, and as a result, the photographic performance becomes stable. As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used. For tablet formation, the average particle size of the obtained granules is 100 to 800 μm, because when mixing the granules and compressing and compressing, the components become non-uniform, so-called segregation hardly occurs. Is preferably used, and more preferably 200 to 750 μm. Further, the particle size distribution is such that 60% or more of the granulated particles are ± 10%.
Those having a deviation of 0 to 150 μm are preferable. Next, when the obtained granules are compressed under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, and a pre-ketting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity, handling, or dust when used on the user side, a cylindrical type, so-called tablet, is preferable. .

Preferably, at the time of granulation, the above effect is further remarkable by separately granulating each component such as an alkali agent, a reducing agent, a preservative and the like.

In the present invention, the solid processing agent is used for a photographic processing agent such as a developer, a fixing agent, and a rinsing agent. The developer which has a large effect of the present invention, particularly, the effect of stabilizing photographic performance is large.

In the present invention, as a supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Utility Model Application Laid-Open Nos. 63-137783 and 63-9752.
No. 2, Japanese Utility Model Laid-Open No. 1-85732, etc., but any method may be used as long as the function of supplying tablets to the processing tank is provided at a minimum. When the solid processing agent is in the form of granules or powders, see JP-A-62-81964, 6
3-84151, JP-A-1-292375, and Japanese Utility Model Laid-Open Nos. 63-105159 and 63-105159.
A method using a screw or a screw described in -195345 or the like is known.

The place where the solid processing agent is introduced may be in the processing tank, but is preferably in a place where the processing liquid is in communication with the processing section for processing the photosensitive material and the processing liquid flows between the processing section and the processing section. In addition, it is preferable that the processing solution circulates at a constant rate between the processing section and the dissolved component and moves to the processing section. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

The silver halide photographic light-sensitive material of the present invention is subjected to X-ray photography by sandwiching it with a high-sensitivity intensifying screen (radiation intensifying screen).

The filling rate of the phosphor in the phosphor layer of the high-sensitivity intensifying screen used in the present invention is 68% or more, preferably 70% or more, more preferably 72% or more.

The phosphor layer has a thickness of 150 to 250 μm. If the thickness of the phosphor layer is less than 150 μm, sharpness tends to be sharply deteriorated. It is preferable that the high-sensitivity intensifying screen is filled with a phosphor in a gradient particle size structure.

In particular, it is preferable to coat large-sized phosphor particles on the surface protective layer side and small-sized phosphor particles on the support side. And those having a large particle diameter are preferably in the range of 10 to 30 μm. In the high-sensitivity intensifying screen used in the present invention, the X-ray absorption of each intensifying screen may be 30% or more per 100 μm of the thickness of the phosphor layer by increasing the filling rate of the phosphor particles. preferable. Note that the X-ray absorption was determined as follows.

That is, an X-ray generated from a tungsten target operated at 80 kVp from an X-ray generator whose intrinsic filtration is 2.2 mm of aluminum and supplied with three-phase power is converted into an aluminum plate having a thickness of 3 mm and a purity of 99% or more. 200c from the tungsten anode of the target tube
to the radiation intensifying screen fixed at position m,
Next, 50c from the phosphor layer of the radiographic intensifying screen.
The position after m was measured using an ionizing dosimeter to determine the amount of X-ray absorption. As a reference, the X-ray dose at the measurement position was used without passing through the intensifying screen.

Preferred binders for use in the high-sensitivity intensifying screen of the present invention include thermoplastic elastomers. Specifically, polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene,
Examples include at least one thermoplastic elastomer selected from the group consisting of ethylene vinyl acetate, polyvinyl chloride, natural rubber, fluororubber, polyisoprene, chlorinated polyethylene, styrene-butadiene rubber, silicon rubber, and the like.

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

[0120]

(Equation 1)

Preferred phosphors for use in the high-sensitivity intensifying screen of the present invention include the following.

For example, a tungstate-based phosphor (Ca
WO 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: Tb, La ₂ O ₂ S: Tb, (Y, Gd) ₂ O
₂ S: Tb, Tm, etc.], terbium activated rare earth Tonarisan based phosphor _{(YPO 4: Tb, GdPO 4} : Tb, LaP
O ₄ : Tb, etc.), terbium-activated rare earth oxyhalide-based phosphors (LaOBr: Tb, LaOBr: Tb.
Tm, LaOCl: Tb, LaOCl: Tb. TmGd
OBr: Tb, GdOCr: Tb, etc.), thulium-activated rare earth oxyhalide-based phosphor (LaOBr: Tm,
LaOCl: Tm, etc.), barium sulfate-based phosphor [BaS
O ₄ : Pb, BaSO ₄ : Eu ²⁺ , (Ba.Sr) S
O ₄ : Eu ²⁺ etc.], divalent eurobium-activated alkaline earth metal phosphate phosphor [Ba ₃ (PO ₄ ) ₂ : Eu ²⁺ ,
(Ba, Sr) ₃ , (PO ₄ ) ₂ : Eu ²⁺ etc.], divalent eurobium-activated alkaline earth metal fluorinated halide-based phosphor [BaFCl: Eu ²⁺ , BaFBr: Eu ²⁺ , Ba
FCl: Eu ²⁺ . Tb, BaFBr: Eu ²⁺ . Tb, B
aF ₂ . BaCl ₂ . XBaSO ₄ . KCl: Eu ²⁺ ,
(Ba.Mg) F2 _. BaCl ₂ . KCl: Eu ²⁺ etc.],
Iodide phosphor (CSI: Na, CSI: Tl, Na
I. KI: Tl, etc.), sulfide-based phosphor [ZnS: Ag,
(Zn.Cd) S: Ag, (Zn.Cd) S: Cu,
(Zn. Cd) S: Cu. Al etc.], and a hafnium phosphate-based phosphor (HfP ₂ O ₇ : Cu etc.). However, the phosphor used in the present invention is not limited to these, and any phosphor that emits light in the visible or near ultraviolet region upon irradiation with radiation can be used.

[0123]

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

Example 1 <Preparation of Em-1> Em-1 was prepared as follows.

A1 Low methionine gelatin 214.37 g Sodium chloride 1.995 g Potassium iodide 149.6 mg Make up to 6090 ml with water B1 Sodium chloride 10.48 g Potassium iodide 149.4 g Make up to 90 ml with water C1 Silver nitrate 30.58 g with water Finish to 90 ml D1 Sodium chloride 165.0 g Finish to 5640 ml with water E1 479.0 g silver nitrate Finish to 5640 ml with water While keeping solution A1 at 40 ° C. in a reaction vessel, vigorously stir, and add the total amount of solution B1 and solution C1 there. 180ml per minute
At the same flow rate over 30 seconds. next,
After keeping this mixed solution at 40 ° C. for 10 minutes, the solution D1 and the solution E1 are added at a flow rate of 24 ml / min over 40 minutes by the simultaneous mixing method, and then the remaining amounts of the solution D1 and the solution E1 are further initialized. The addition was performed over 130 minutes by the simultaneous addition method while linearly increasing the flow rate so that the flow rate became 24 ml and the final flow rate became 48 ml. During this time, pCl was kept at 2.35 throughout. Then adjust to 1.30 with sodium chloride,
The pCl was adjusted to 2.0 using an ultrafiltration membrane, and the pCl was adjusted to 1.65 by adding sodium chloride.

The resulting silver halide emulsion had an iodine of 0.0
6% by mole, observed by an electron microscope, the average particle diameter (diameter in circle) was 0.86 μm, and the average thickness was 0.19 μm.
m, the average parallel aspect ratio was 4.5.

<Aging of Em-1>
-1 was aged.

That is, the above-mentioned emulsion Em-1 was divided into four parts at a temperature of 55 ° C., and as shown in Table 2, p
After the H (A) adjustment, the following compound was added and stirred for 15 minutes. The additives and their amounts (per mole of AgX) are shown below.

Compound Y-1 (adenine) 12 mg spectral sensitizing dye * 4-hydroxy-6-methyl-1,3,3a, 7 200 mg-tetrazaindene (TAI) shown in Table 2 *: It was added as a solid particulate dispersion.

Thereafter, the pH (B) was adjusted as shown in Table 2,
The following composition was added and stirred for 15 minutes.

Ammonium thiocyanate 145 mg Chloroauric acid 18.5 mg Sodium thiosulfate (pentahydrate) 15.0 mg Triphenylphosphine selenide * 3.0 mg *: Added as a solid particulate dispersion.

Then, as shown in Table 2, the pH (C) was adjusted to 30
The mixture was aged for 2 minutes, further adjusted to pH (D), and added with fine silver bromide particles, and aged for a total of 2 hours.

Silver bromide fine particles 0.2 mol% At the end of ripening, 1-phenyl-5-mercaptotetrazole (PMT) and TAI were added as stabilizers, and Em1
-1 to 1-4 were produced.

PMT 10 mg TAI 100 mg

[0135]

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<Preparation of Emulsion Em-2> —Preparation of Seed Emulsion 1— Seed Emulsion 1 was prepared as follows.

A2 Ossein gelatin 24.2 g Water 9657 ml Polypropyleneoxy-polyethyleneoxy 6.78 ml-Disuccinate sodium salt (10% ethanol aqueous solution) Potassium bromide 10.8 g 10% nitric acid 114 ml B2 2.5N silver nitrate aqueous solution 2825 ml C2 Potassium bromide 841 g Water 2825 ml D2 1.75 N Potassium bromide aqueous solution The following silver potential control amount: at 42 ° C, JP-B-58-58288 and 58-582
Solution B was added to Solution A2 using a mixing stirrer shown in No. 89
464.3 ml of each of Solution No. 2 and Solution C2 were added by a double jet method over 1.5 minutes to form nuclei.

After the addition of the solution B2 and the solution C2 was stopped, the temperature of the solution A2 was raised to 60 ° C. over 60 minutes, the pH was adjusted to 5.0 with 3% KOH, and then the solution was again cooled. B2 and solution C2 were each mixed with 55.4 by a simultaneous mixing method.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B2 and C2 was measured using the solution D2.
It was controlled to be 8 mV and +16 mV.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and immediately, desalting and washing were performed. In this seed emulsion 1, 90% or more of the total projected area of the silver halide grains consisted of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains was 0.064 μm. It was confirmed by an electron microscope that the particle size (in terms of circular diameter) was 0.595 μm. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%. Seed emulsion 1 obtained subsequently
And three kinds of solutions shown below were used to prepare a tabular pure silver bromide emulsion E
m-2 was prepared.

A3 Ossein gelatin 34.03 g Polypropylene oxy-polyethylene oxy 2.25 ml-Disuccinate sodium salt (10% ethanol aqueous solution) Seed emulsion 1 1.218 mol equivalent Equivalent to 3150 ml with water B3 1747 g potassium bromide with water Finish to 3669 ml C3 2493 g Finish to 4193 ml with water While keeping the solution A3 at 60 ° C. in a reaction vessel, the solution A3 was vigorously stirred, and the total amount of the solution B3 and the solution C3 was added thereto over 100 minutes by the simultaneous mixing method. During this time, the pH was adjusted to 5.8 and p
Ag was kept at 8.8 throughout. Here, solution B3 and solution C3
The addition rate was varied as a function of time to match the critical growth rate. That is, they were added at an appropriate addition rate so as to prevent generation of small particles other than the growing seed particles and to prevent polydispersion by Ostwald ripening.

After the addition was completed, the emulsion was cooled to 40 ° C.
As an aggregating polymer agent, 1800 ml of a 13.8% (by weight) aqueous solution of a modified gelatin modified with a phenylcarbamoyl group (substitution rate: 90%) was added and stirred for 3 minutes. Thereafter, a 56% (by weight) aqueous solution of acetic acid was added to adjust the pH of the emulsion to 4.
After adjusting to 6 and stirring for 3 minutes, the mixture was allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then 40
9.0 L of distilled water at ℃ was added, the supernatant liquid was drained after stirring and standing, further 11.25 L of distilled water was added, and the supernatant liquid was drained after stirring and standing. Subsequently, an aqueous gelatin solution and a 10% (by weight) aqueous sodium carbonate solution were added to adjust the pH to 5.
It was adjusted to 80 and stirred at 50 ° C. for 30 minutes to redisperse. After the redispersion, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C.

When the obtained silver halide emulsion was observed with an electron microscope, the average particle size (diameter in terms of circle) was 0.77 μm.
Tabular silver halide grains having an average thickness of 0.17 μm, an average aspect ratio of about 4.5, and a particle size distribution of 18.1% were obtained.

<Maturation of Em-2>
-2 was aged.

That is, Em-2 obtained was divided into four parts, and sensitized and ripened in the same manner as in Em-1, using the compounds shown below to obtain Em2-1 to 2-4. The additives and their amounts (per mole of AgX) are shown below.

Compound Y-2 1.5 mg spectral sensitizing dye * TAI shown in Table 2 200 mg ammonium thiocyanate 95 mg chloroauric acid 12.5 mg sodium thiosulfate (pentahydrate) 10.0 mg triphenylphosphine selenide * 2. 0 mg Silver iodide fine particles 0.2 mol% Stabilizer (PMT) 5 mg Stabilizer (TAI) 200 mg *: Added as solid fine particle dispersion.

[0146]

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The solid fine particle dispersion of the spectral sensitizing dye was prepared by a method according to the method described in JP-A-5-297496. That is, a predetermined amount of the spectral sensitizing dye is
With a high-speed stirrer (dissolver)
Obtained by stirring at 3,500 rpm for 30-120 minutes. The obtained Em1-1 to 1-4 and Em2-1 to 2-4 are shown in Table 2 below.

[0148]

[Table 2]

The obtained Em1-1 to 1-4 and Em2-
The following additives were added to 1-2 to 1-4 to prepare an emulsion layer coating solution. At the same time, the following coating solution for the protective layer was prepared. Using both coating solutions, the coating amount was 1.6 g / m ^{2 of} silver per side,
Using two slide hopper type coaters, the two sides were simultaneously coated on the support at a speed of 80 m / min so that the amount of gelatin applied was 2.5 g / m ^2, and dried for 2 minutes and 20 seconds. 1-8 were obtained. As a support, glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%
% And a copolymer aqueous dispersion obtained by diluting a copolymer comprising three kinds of monomers of 40% by weight of butyl methacrylate to 10% by weight as a subbing liquid.
A polyethylene terephthalate film base obtained by coloring an X-ray film having a blue color to a density of 0.15 was used.

The additives used in the emulsion are as follows.
The amount of addition is shown in an amount per mole of silver halide.

First Layer (Dye Layer) Solid Fine Particle Dispersion Dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium Dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2,4- Dichloro-6-hydroxy-5 mg / m ² 1,3,5-triazine sodium salt Colloidal silica (average particle size 0.014 μm) 10 mg / m ² Second layer (emulsion layer) Various additives were added.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-5 mg / m ² diethylamino-1,3,5-triazine t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone ( 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / M ² 1,3-dihydroxybenzene-4-sulfone 500 mg / m ² ammonium 2-mercaptobenzimidazole-5-5 mg / m ² sodium sulfonate Compound (H) 0.5 mg / m ² nC ₄ H _{9 OCH 2 CH (OH) CH 2} N ( _{H 2 COOH) 2 350mg / m} 2 Compound (M) 5 mg / m ² Compound (N) 5 mg / m ² Colloidal silica 0.5 g / m ² Latex (L) 0.2 g / m ² Dextrin (average molecular weight 1000) 0 0.2 g / m ² 1- (4-carboxyphenyl) tetrazole 15 mg / m ² However, the gelatin was adjusted to be 1.0 g / m ² .

Third layer (protective layer) Solid fine particle dispersion dye 50 mg / m ² Gelatin 0.8 g / m ² TAI 15 mg / m ² Matting agent composed of polymethyl methacrylate 50 mg / m ² (area average particle size 7.0 μm ) Formaldehyde 20 mg / m ² 2,4-Dichloro-6-hydroxy-1,3,5 10 mg / m ² -Triazine sodium salt bis-vinylsulfonylmethyl ether 36 mg / m ² Latex (L) 0.2 g / m ² Polyacrylamide (average molecular weight 10,000) 0.1 g / m ² Sodium polyacrylate 30 mg / m ² Polysiloxane (S1) 20 mg / m ² Compound (I) 12 mg / m ² Compound (J) 2 mg / m ² Compound (S- 1) 7 mg / m ² compound (K) 15 mg / m ² compound (O)
50 mg / m ² compound (S-2) 5 mg / m ² C ₉ F ₁₉ -O- (CH ₂ CH ₂ O) ₁₁ -H 3 mg / m ² C ₈ F ₁₇ SO ₂ N- (C ₃ H ₇ ) ( _{CH 2 CH 2 O) 15 -H} 2mg / m 2 C 8 F 17 SO 2 N- (C 3 H 7) (CH 2 CH 2 O) 4 - (CH 2) 4 SO 3 Na 1mg / m 2

[0154]

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[0155]

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[0156]

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Next, each sample was stored for 7 days under the following two conditions.

Condition A: 23 ° C., 55% RH Condition B: 40 ° C., 80% RH The photographic characteristics were evaluated using 1 to 8. First, the sample was sandwiched between two high-sensitivity intensifying screens (KO-250, manufactured by Konica Corporation), and exposed to X-rays at a tube voltage of 80 kVp and a tube current of 100 mA for 0.05 seconds through an aluminum wedge. . Then, it was processed with a developing solution and a fixing solution having the following formulation using an automatic developing machine (manufactured by Konica Corporation, SRX-502).

A developing tablet was prepared according to the following procedure. These are also used for replenishment.

Operation (A) As a comparative example, 3,000 g of dihydroxybenzene (hydroquinone) as a developing agent is pulverized in a commercially available bandam mill until the average particle size becomes 10 μm. To this fine powder, 3000 g of sodium sulfite, 2000 g of potassium sulfite, and 1000 g of Dimezone S are added, 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. After that, the granulated product is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove the moisture of the granulated product almost completely. In this manner, 100 g of polyethylene glycol 6000 was added to the adjusted granules at 25 ° C and 40 ° C.
After mixing uniformly for 10 minutes using a mixer in a room humidified to less than% RH, the resulting mixture is mixed with Kikusui Seisakusho Co., Ltd.
A tableting machine modified from Tough Press Collect 1527HU was used to perform compression tableting at a filling amount of 3.84 g per tablet to produce 2500 tablets A for development.

Procedure (B) 100 g of DTPA, 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 7 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohypoxanthine, 200 g of KOH, and 10 g of N-acetyl-D, L-penicillamine Pulverization and granulation are performed in the same manner as in the operation (A).
The amount of water added was 30.0 ml, and after granulation,
After drying for a minute, the water content of the granules is almost completely removed. The mixture thus obtained was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., with the filling amount per tablet being 1.73 g, and 2500 tablets for development were obtained. Agent B was prepared.

Next, a fixing tablet was prepared by the following operation.
These are also used for replenishment.

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is pulverized in the same manner as in the operation (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in the operation (A), granulation is performed with the addition amount of water being 500 ml. After granulation, the granulated product is
For 30 minutes to remove the moisture of the granules almost completely. 4 g of sodium N-lauroylalanine is added to the granules thus adjusted, and mixed for 3 minutes in a room conditioned at 25 ° C. and 40% RH or less using a mixer.
Next, the obtained mixture was subjected to compression tableting using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., with the filling amount per tablet being set to 6.202 g.
500 tablets A for fixing were prepared.

Operation (D): 1000 g of boric acid, 150 aluminum sulfate / hydrate
0 g, sodium hydrogen acetate (3,000 g of glacial acetic acid and sodium acetate mixed and dried), tartaric acid 200
g is ground and granulated in the same manner as in the operation (A). The amount of water to be added is 100 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. 4 g of sodium N-lauroylalanine was added to the thus-prepared mixture, and the mixture was mixed for 3 minutes. Then, the obtained mixture was converted into a tablet per tablet using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Compression tableting was performed at a filling amount of 4.562 g to prepare 1250 fixing tablets B.

(Developer) Starter Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make up to 1 liter.

At the start of processing of the developer (start of running), the developer 1 obtained by diluting the obtained developing tablets with dilution water was used.
The processing was started by filling the developing tank with a liquid obtained by adding 330 ml of the above starter to 6.5 liters as a starting liquid. The pH of the developer to which the starter was added was 1
0.45. The previously prepared sample No. Exposure to 1 to 8 so that the optical density after development processing is 1.0,
I ran. Automatic developing machine SRX for running
At −502, a member for charging a solid processing agent was attached, and a member modified so that processing could be performed in 15 seconds was used. During running, A and B were obtained per 0.62 m ² of the photosensitive material in the developer.
The test was carried out by adding two of each agent and 76 ml of water. When each of the A agent and the B agent was dissolved in 38 ml of water, the pH was 10.7.
It was 0.

To the fixing solution, ^{two of the} above-mentioned A agent, one of the B agent and 74 ml of water were added per 0.62 m ² of the light-sensitive material.
The rate of water addition for each treatment agent starts at almost the same time as the addition of the treatment agent and is approximately 10 in proportion to the dissolution rate of the treatment agent.
Minutes at a constant speed.

[0168] A developing replenisher and a fixing replenisher were prepared as follows.

(Development replenisher composition D-1) Potassium carbonate 40 g Hydroquinone 30 g Dimezone S 10 g Diethylene triamine pentaacetic acid / 5Na 1 g (DTPA) Potassium bromide 1 g 5-methylbenzotriazole 0.1 g 1-phenyl-5-mercapto Tetrazole 0.07 g 2-mercaptohypoxanthine 0.05 g sodium sulfite 30.00 g potassium sulfite 25 g KOH 2 g diethylene glycol 50 g N-acetyl-D, L-penicillamine 0.1 g These are dissolved in 300 ml of water and finally 400 m in pure water.
l. This concentrated solution was diluted to 1 liter with water to obtain a developing replenisher. The pH of this replenisher was 10.70.

(Composition of Fixing Replenisher) Sodium thiosulfate 42.0 g Potassium thiosulfate 98.0 g Sodium sulfite 15.0 g Boric acid 10.0 g Sodium hydrogen acetate 30.0 g Glacial acetic acid 17.3 g Sodium acetate 12.7 g Tartaric acid 2. 0g These are dissolved in 400ml of water and finally 500m with pure water
l. This concentrated solution was diluted to 1 liter with water to obtain a replenisher. The pH of this replenisher was 4.50.

(Evaluation) The processing stability was determined by uniformly exposing the prepared sample with tungsten light so that the transmitted light darkening concentration was 1.0, and then changing the processing level to an equilibrium state (quarter size). 2,000 sheets were processed, and sensitometry was performed at the initial level and the level after running to compare.

The photographic performance of each sample was measured.

-Sensitivity-Sample No. The results were shown as relative values when the result of storage condition A of No. 1 was taken as a reference 100. The smaller the value of the difference between the storage conditions A and B is, the smaller the change is, the better the storage condition is.

-Residual Color- The evaluation of the residual color was as follows.
m was measured with a spectrophotometer, and the sample no.
The results were shown as relative values when the result of storage condition A of No. 1 was taken as a reference 100.

-Safelight Resistance- The safelight resistance was evaluated by irradiating each sample through a red filter having the transmittance shown in FIG. 1 with white light bulb light from 1.2 m above the sample for 30 minutes. The development was performed in the same manner, and the increase in fog was measured and determined. Sample No. The relative value when the result of fog under storage condition A of 1 was taken as a reference 100 was taken as safelight resistance. The smaller the value, the better the safelight resistance.

Table 3 shows the obtained results.

[0177]

[Table 3]

As is clear from Table 3, the sample N of the present invention
o. Nos. 2 to 4 and 6 to 8 have low fog and high sensitivity, and also have remarkably excellent safelight resistance and residual color. In addition, it can be seen that the composition is excellent in environmental preservability, such as a small variation in processing of sensitivity even in storage under high temperature and high humidity.

When the sample of the present invention is processed using a solid processing agent, it can be processed with almost no loss of sensitivity even in a rapid processing such as a total processing time of 15 seconds, and it can be seen that there is no problem at all.

It was also found that the same effect as described above was obtained when the sample of the present invention was processed using another developing agent such as sodium erythorbate instead of hydroquinone as the developing agent used in the developing replenisher. .

Example 2 (Regarding Claim 8) <Preparation of Em-3> Preparation of Seed Emulsion 2 Seed Emulsion 2 was prepared as follows.

A3 ossein gelatin 100 g potassium bromide 2.05 g 11.5 l with water B3 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2N sulfuric acid 38.5 ml water 2.6 l C3 ossein gelatin 75 g of potassium bromide 950 g of potassium iodide 27 g of water 3.0 l of D3 silver nitrate 95 g of water 2.7 l of E3 silver nitrate 1410 g of 3.21 of water Control of A3 solution, B3 solution and D3 solution kept at 60 ° C in a reaction vessel The solution was added over 30 minutes by the double jet method, and then the solution C3 and the solution E3 were added over 105 minutes by the control double jet method. 50 stirring
It was performed at 0 rpm. The flow rate was such that no new nuclei were generated with the growth of the particles and so-called Ostwald ripening was performed, so that the particle size distribution was not widened. At the time of adding the silver ion solution and the halide ion solution, the pAg was adjusted to 8.3 ± 0.05 using a potassium bromide solution, and the pH was adjusted to 2.0 ± 0.1 using sulfuric acid. After the addition is completed, the pH is adjusted to 6.0 to remove excess salts.
A desalting treatment was performed according to the method described in JP-A-16086. When this seed emulsion 2 was observed with an electron microscope, it was a cubic monodisperse emulsion having an average grain size of 0.27 μm and a grain size distribution of 17% with a slightly rounded corner.

A monodisperse core / shell emulsion was prepared using the above seed emulsion 2 and the following seven kinds of solutions.

A4 ossein gelatin 10 g ammonia water (28%) 28 ml glacial acetic acid 3 ml seed emulsion 2 0.119 mol equivalent Equivalent to 600 ml with water B4 ossein gelatin 0.8 g potassium bromide 5 g potassium iodide 3 g to 110 ml with water Finish C4 Ossein gelatin 2g Potassium bromide 90g Finish to 240ml with water D4 Silver nitrate 9.9g Ammonia water (28%) 7.0ml Finish to 110ml with water E4 Silver nitrate 130g Ammonia water (28%) 100ml Finish to 240ml with water F4 94 g of potassium bromide Finished to 165 ml with water G4 9.9 g of silver nitrate 7.0 ml ammonia water (28%) Finished to 110 ml with water The A4 solution was kept at 40 ° C. and stirred at 800 rpm with a stirrer. The pH of solution A4 was adjusted to 9.90 using acetic acid,
Seed emulsion 2 was collected and dispersed and suspended, and then G4 solution was added at a constant speed over 7 minutes to adjust the pAg to 7.3. Furthermore, B4
Solution D4 and Solution D4 were added simultaneously over 20 minutes. At this time, the pAg was kept constant at 7.3. PH = 8.83, pAg using potassium bromide solution and acetic acid over 10 minutes
= 9.0, C4 solution and E4 solution were simultaneously added to 30
It was added over a minute.

At this time, the flow ratio between the addition speed and the end of the addition was 1:10, and the flow rate was increased with time.
Further, the pH was lowered from 8.83 to 8.00 in proportion to the flow rate ratio. Further, when each of the C4 solution and the E4 solution was added by ２ of the total amount, the F4 solution was additionally injected and added at a constant speed over 8 minutes. At this time, the pAg is from 9.0 to 1
It rose to 1.0. Further, acetic acid was added to adjust the pH to 6.0.

After the addition, to remove excess salts, precipitation and desalting were carried out in the same manner as in seed emulsion 1 described above, and pAg
Emulsion Em-3 having an average iodine content of about 2 mol% at pH 5.85 at 8.5 and 40 ° C. was obtained. Emulsion Em obtained
-3 was observed with an electron microscope.
This was a rounded tetrahedral monodisperse core / shell emulsion having a size of 14 μm and a particle size distribution of 14%.

The obtained emulsion Em-3 was replaced with Em2 of Example 1.
The emulsion was sensitized in the same manner as in Example 2 to obtain an emulsion layer coating solution. 14 was produced. The layer was thinned so that the amount of silver applied per side was 1.5 g / m ² and the amount of gelatin applied was 2.0 g / m ² , thereby obtaining a coated sample. Further, using Em1-2 and Em2-2 obtained in Example 1, it was prepared as shown in Table 4, and sample No. 2 was prepared. 9-13
I got

[0188]

[Table 4]

The obtained sample was sandwiched between the following two high-sensitivity intensifying screens (S-1), and a tube voltage of 60 was applied through an aluminum wedge.
X-rays of kVp and a tube current of 200 mA were irradiated for 0.05 seconds for exposure. In addition, it evaluated similarly using the high sensitivity intensifying screen (S-2) produced as follows instead of the said high sensitivity intensifying screen (S-1).

(Production of high-sensitivity intensifying screen (S-1)) Phosphor Gd ₂ O ₂ S: Tb (average particle size 1.8 μm) 200 g Binder Polyurethane-based thermoplastic elastomer 20 g Demolac TPKL-5-2525 < Solid content 40%> (manufactured by Sumitomo Bayer Urethane Co., Ltd.) Nitrocellulose (digestibility: 11.5%) A methyl ethyl ketone solvent is added to 2 g, and dispersed with a propeller mixer to form a phosphor layer having a viscosity of 25 PS (25 ° C.). A coating solution was prepared (binder / phosphor ratio = 1/22).
Separately, 90 g of a soft acrylic resin solid content and 50 g of nitrocellulose are added to methyl ethyl ketone as a coating liquid for forming an undercoat layer, dispersed and mixed, and the viscosity is 3 to 6 PS (25 ° C.).
Was prepared. A 250 μm-thick polyethylene terephthalate kneaded with titanium dioxide is horizontally placed on a glass plate, and the above-mentioned coating solution for forming an undercoat layer is uniformly coated on the support using a doctor blade.
The coating film is dried by gradually increasing the temperature to 5 to 100 ° C.,
An undercoat layer having a thickness of 15 μm was formed on the support.

The above-mentioned coating solution for forming a phosphor layer was uniformly coated thereon with a doctor blade to a thickness of 240 μm, dried, and then compressed. Compression was performed using a calender roll at a pressure of 300 kgW / cm ² and a temperature of 80 ° C. After this 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. The characteristics of the obtained high-sensitivity intensifying screen are as follows.
0 μm, phosphor filling rate 68%, sharpness (CTF) 48%
Met.

(Production of high-sensitivity intensifying screen (S-2): for comparison) The above-mentioned (S-1) was applied except that the thickness of the coating solution for forming the phosphor layer was uniformly applied at 150 μm, and no compression was performed at all. ), A high-sensitivity intensifying screen (S-2) comprising a support, an undercoat layer, a phosphor layer and a transparent protective film was produced. The characteristics of the obtained high-sensitivity intensifying screen were that the thickness of the phosphor layer was 105 μm and the filling rate of the phosphor was 65%.

(Evaluation) The photographic performance of each sample was measured. Sample No. Based on 14 results (10
0).

-Sensitivity-Sample No. 1 photographed using a high-sensitivity intensifying screen (S-2) 1
The sensitivity of No. 4 was set as a reference (100) and compared with the above (S-1).

-Pressure fog-For evaluation of pressure fog, a needle head 0.3
After applying a load of 5 g with a needle hardness meter, the same developing treatment as described above was performed, and the pressure fogging density was measured with a microdensitometer. Table 5 shows the obtained results.

[0196]

[Table 5]

In general, when the emulsion layer is made thinner, the processability is improved, but the sensitivity and pressure resistance tend to be reduced. However, as is clear from Table 5, the sample No. in which the average iodine content was kept low. 9 to 12 show that the pressure resistance can be improved while maintaining high sensitivity even when the film is made thin. Exposure treatment with the high-sensitivity intensifying screen (S-1) of the present invention having a phosphor filling rate of 68% resulted in higher sensitivity.

Example 3 (Regarding Claims 3 to 6) In place of hydroquinone as the above developing agent, a compound of the general formula (2)
A developer (D-2) was prepared in the same manner except that Exemplified Compound 2-1 of the compound represented by Formula (1) was used. 9 to 11, 13 and the sample Nos. 1 was evaluated as follows.

(Evaluation)-Low illuminance failure characteristics-Each sample was sandwiched between two high-sensitivity intensifying screens so that the same amount of explosion was obtained as that of normal exposure, and the tube voltage was set to 60 through an aluminum wedge.
X-rays having a tube current of 50 mA and a kvp of 50 mA were applied for 0.2 seconds for exposure.

The smaller the difference between the low illuminance exposure sensitivity and the normal exposure sensitivity, the smaller the change and the better the sensitivity. In addition, sample No. Based on the result of treating No. 13 with developer D-1 (containing hydroquinone) as a reference 100, measured values of other samples were relatively determined.

-Developing unevenness-After uniformly exposing each sample of 35 cm x 43 cm so that the concentration becomes 1.0, the above-mentioned developing treatment is performed, and the processed film is visually evaluated according to a four-level evaluation level. Was.

A: No unevenness was observed at all. O: Some unevenness was observed. Δ: Unevenness was considerably observed. X: Unevenness was observed over the entire surface. The obtained results are shown in Table 6 below.

[0203]

[Table 6]

As is clear from the results shown in Table 6, the silver halide photographic light-sensitive material of the present invention was subjected to solid processing, a developer substantially not containing a dihydroxybenzene-based developing agent was used, and the entire processing was carried out. The sample processed by the rapid processing of 15 seconds, that is, the sample No. 9 to 11 with a developer (D-
It can be seen that the sample treated in 2) has high sensitivity, is less affected by low illuminance failure, and has no development unevenness. In addition, sample No. In No. 13, slight differences between low-illumination exposure sensitivity and normal exposure sensitivity and uneven development were observed. This is presumed to be due to the large content of the average iodine content. Liquid (D
Those treated in -2) can be said to be generally good.

[0205]

The silver halide photographic light-sensitive material of the present invention comprises:
It has a remarkably excellent effect that it has low fog, high sensitivity, little dye stain, good storage stability over time, and excellent pressure resistance and rapid processing suitability. Further, with the reduction of the processing waste liquid, the efficiency of the entire processing operation is promoted.

[Brief description of the drawings]

FIG. 1 is a diagram showing the transmittance of a red filter used in an example.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location G03C 5/17 G03C 5/17 5/26 5/26 520 520 5/30 5/30 G21K 4 / 00 G21K 4/00 A

Claims (8)

[Claims] 1. A silver halide photographic material having a photographic component layer comprising at least one photosensitive silver halide emulsion layer on a support, wherein the photosensitive silver halide emulsion layer has a pH of 3 to 7. The spectral sensitizing dye represented by the following general formula (1) is added under the condition of (1), and the chemical sensitizer is added under a condition 0.5 to 5 higher than the pH when the spectral sensitizing dye is added. A silver halide photographic light-sensitive material comprising a light-sensitive silver halide emulsion which has been subjected to chemical sensitization ripening. Embedded image (Wherein, R ₁ and R ₃ each represent a substituted or unsubstituted lower alkyl group, and R ₂ and R ₄ each represent a lower alkyl group or an alkyl group substituted with a hydrophilic group, provided that R ₂ and R ₄ X represents an alkyl group substituted with a hydrophilic group.
Represents an ion necessary for neutralizing the charge in the molecule, and n represents 1 or 2. However, when an inner salt is formed, n is 1. Z _{1 to} Z ₄ represent a substitutable group. ) 2. The silver halide grain contained in the photosensitive silver halide emulsion contains silver halide grains having an average iodine content of 1.0 mol% or less. Silver halide photographic material. 3. Developing said silver halide photographic material,
A processing method for a silver halide photographic material, wherein a total processing time is 30 seconds or less when the processing is performed by a processing method including a fixing and drying step. 4. The developer according to claim 3, wherein the developing solution in the developing step does not substantially contain a dihydroxybenzene-based developing agent but contains a developing agent represented by the following general formula (2). For processing silver halide photographic light-sensitive materials. Embedded image (Wherein, R ₅ and R ₆ represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group, and an alkylthio group, respectively. P, Q
Represents a hydroxy group, carboxy group, alkoxy group, hydroxyalkyl group, carboxyalkyl group, sulfo group, sulfoalkyl group, amino group, aminoalkyl group, mercapto group, alkyl group and aryl group, and P and Q are Represents a group of atoms forming a 5- to 8-membered ring together with two vinyl carbon atoms substituted by R ₅ and R ₆ and a carbon atom substituted by Y. Y represents ＝ O or ＮN—R ₇ .
R ₇ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group. ) 5. A method for developing said silver halide photographic material,
A method for continuously processing in a processing step including each step of fixing, wherein a solid processing agent is supplied to a processing liquid in each processing step while continuously processing the processing solution, wherein the processing solution is supplied. . 6. The developer according to claim 5, wherein the developing solution in the developing step does not substantially contain a dihydroxybenzene-based developing agent, but contains a developing agent represented by the general formula (2). For processing silver halide photographic light-sensitive materials. 7. The photosensitive silver halide emulsion has a pH of 3-7.
After the addition of the spectral sensitizing dye represented by the general formula (1) under the conditions of
A method for producing a light-sensitive silver halide emulsion, characterized in that a chemical sensitizer is added under conditions 0.5 to 5 higher than H to carry out chemical sensitization ripening. 8. A silver halide, characterized in that said silver halide photographic light-sensitive material is sandwiched between high sensitivity intensifying screens having a phosphor filling ratio of 68 to 90% in a phosphor layer and X-ray photography is performed. How to shoot photographic materials.