JPH04369643A - Development processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the generation of silver stains by incorporating core/shell type fine silver halide particles of a specific size into the surface protective layer of emulsion layers and processing the photographic sensitive material with a developer contg. a silver sludge preventive agent. CONSTITUTION:The core/shell type fine silver halide particles having <0.27mum average particle size are incorporated into the surface protective layer existing in the position further from the silver halide emulsion layers when viewed from a base. Such silver halide photographic sensitive material is processed with the developer contg. the silver sludge preventive agent. The compd. expressed by formula I is used as the silver sludge preventive agent. In the formula I, X denotes a hydrogen atom or sulfonic acid group; M1 denotes a hydrogen atom or alkaline metal atom; M2 denotes a hydrogen atom, alkaline metal atom or ammonium group. The silver stains sticking to developing tanks, developing racks and rollers, i.e., silver sludge, are decreased in this way even when the developer contg. the salt of high-concn. sulfurous acid or silver halide solvent is used.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a method for developing silver halide photographic light-sensitive materials (hereinafter referred to as "sensitized materials"), and in particular uses a developing solution containing a highly concentrated sulfite salt or silver halide solvent. This invention relates to a method for reducing silver sludge, that is, silver stains that sometimes adhere to developing tanks, developing racks, and rollers, facilitating equipment maintenance, and hardly changing the photographic performance of photosensitive materials.

0002

BACKGROUND OF THE INVENTION In recent years, there has been an increasing demand for rapid processing in the development processing of silver halide photosensitive materials. In order to perform rapid processing, it is necessary to increase the activity of the developer, but this is largely due to the properties of the silver halide photosensitive material. When using an automatic developing machine (hereinafter referred to as an automatic developing machine), there are usually steps such as developing, fixing, washing, and drying.
The drying process is particularly important. In order to finish drying quickly, it is most effective to reduce the amount of silver in the photosensitive material. Since tabular silver halide grains have high covering power, it is possible to reduce the amount of silver without impairing performance such as photographic properties and image quality. This is advantageous not only in the drying process but also in rapid processing of development, fixing, and water washing processes. It has long been known that when silver halide photographic materials are rapidly processed, silver gradually adheres to and accumulates on the developing tank, vat, wall of the developing tank of automatic processing machines, developing tank, and developing roller depending on the amount of processing. ing. This is also called silver stain or silver sludge, and it adheres to the photosensitive material being processed and stains the image, requiring periodic cleaning and maintenance of the equipment.

[0003] For cleaning to remove silver stains, each time the developer is removed from the developer tank, the tank is filled with a very strong oxidizer solution such as cerium sulfate. It must be left stirring for more than 30 minutes. Furthermore, if traces of this oxidizing agent remain in the developing tank after this, the developing solution will be oxidized and deteriorated, so it must be thoroughly washed with water. This cleaning work is one of the biggest daily maintenance burdens, especially for automatic processors, and improvements are desperately needed from the standpoint of work safety and the pollution burden of cleaning agents. It is. On the other hand, as a method of reducing this silver sludge, as described in Japanese Patent Publication No. 62-4702, a compound is added that reduces the amount of silver ions eluted into the developer and/or suppresses the reduction of silver ions to silver. There are known ways to do this. Also, 2-mercapto-1 is used as a sludge inhibitor for such purposes.
, 3,4-thiadiazoles (UK Patent No. 940169)
2-mercapto-1,3,4-oxadiazoles or 1-phenyl-5-mercaptotetrazole (US Pat. No. 3,173,789), DL-
6,8-dithiooctanoic acid (U.S. Pat. No. 3,318,701)
Specification), o-mercaptobenzoic acid (British Patent No. 11), o-mercaptobenzoic acid (British Patent No.
44481), aliphatic mercaptocarboxylic acids (
U.S. Pat. No. 3,262,8955), L-thiazolidine-4-carboxylic acid (J. Photogr. Sc.
i. 13, 233 (1965)), divalent sulfur compounds (
2-mercaptobenzoxazole, 2-mercaptobenzimidazole (Photogr. Sci. Eng., 20, 2)
20 (1976)) etc. are known. However, these methods inevitably have the effect of inhibiting the development itself, and have the disadvantage of being accompanied by a decrease in sensitivity. Moreover, the sensitivity to this compound differs depending on the characteristics of the photosensitive material.
It is not something that can be expected to be effective if used at once. In addition, a decrease in sensitivity is a serious drawback for a photosensitive material/development processing system that is intended to be used with as high a sensitivity as possible.

0004

[Problems to be Solved by the Invention] Therefore, the purpose of the present invention is to reduce the silver stains that occur in the developing tank and/or in the developing rack and rollers when rapidly developing silver halide photosensitive materials. Second, it facilitates the maintenance of automatic processors and developing equipment. Third, it reduces silver stains without affecting photographic properties at all. Fourth, it impairs the stability of the developer. The goal is to reduce silver stains without any stains.

[0005]

Means for Solving the Problems The present invention provides a method for developing a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on at least one side of a support. Achieved by containing core/shell type fine silver halide grains with an average grain size of less than 0.2 μm in the protective layer, and treating the silver halide photographic material with a developer containing a silver sludge inhibitor. It was done. Further, as the silver sludge inhibitor used in the present invention, any known compound may be used as appropriate, but it is particularly preferable to use a compound represented by the following general formula (I). General formula (I)

[0006]

[Case 2]

In the formula, X represents a hydrogen atom or a sulfonic acid group. M1 represents a hydrogen atom or an alkali metal atom, and M2 represents a hydrogen atom, an alkali metal atom or an ammonium group. The compound represented by the general formula (I) of the present invention has the following general formula (II) when M1 is a hydrogen atom:
It may also be a tautomer, such as. General formula (II)

[0008]

[Chemical formula 3]

(X and M2 each have the same meaning as in the general formula (I).) In the present invention, the general formula (
Especially when the compound represented by I) is added to a developer containing a relatively large amount of a compound having a silver halide dissolving action such as sulfite ion, thiosulfate ion, thiocyanate ion, thioether compound or thioamide compound, sludge It has a great prevention effect. Furthermore, when the developer of the present invention is used when photosensitive materials are processed in an automatic developing machine using a roller conveyance system or a belt conveyance system, it is particularly effective in preventing deterioration in the finished quality of photographs due to contamination or damage to the film surface. Examples of preferred compounds represented by general formula (I) are listed below.

0010

[C4]

[0011] The amount of the silver sludge inhibitor used in the present invention is preferably 1 x 10-5 to 1 x 10-1 mol, particularly 1 x 10-4 to 1 x 10 mol per liter of developer.
-2 moles.

The developing agent used in the developer of the present invention is mainly composed of hydroquinones, but a combination of hydroquinones and 1-phenyl-3-pyrazolidones, or a combination of hydroquinones and pyrazolidones is preferred since it is easy to obtain good properties. - Good combination with aminophenols. Hydroquinone-based developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone,
, 3-dibromohydroquinone, 2,5-dimethylhydroquinone, hydroquinone monosulfonate and the like, with hydroquinone being particularly preferred. 3 used in the present invention
- As a pyrazolidone developing agent, 1-phenyl-3-
Pyrazolidone, 1-phenyl-4,4-dimethyl-3-
Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4
-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p
-Tolyl-4,4-dimethyl-3-pyrazolidone, 1-
p-Tolyl-4-methyl-4-hydroxymethyl-3-
Pyrazolidone, etc. The hydroquinone type developing agent is generally used in an amount of 0.01 mol/liter to 1.5 mol/liter, preferably 0.05 mol/liter to 1.2 mol/liter. In addition, the p-aminophenol developing agent or 3-pyrazolidone developing agent is usually 0.0005 mol/liter to 0.2 mol/liter, preferably 0.001 mol/liter to 0.1 mol/liter. used in amounts of

Sulfites used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite,
These include ammonium sulfite, sodium bisulfite, potassium metabisulfite, etc. The amount of sulfite is preferably 0.1 mol/liter or more, particularly 0.3 mol/liter or more. Further, the upper limit is preferably up to 2.5 mol/liter in the developer concentrate. The pH of the developer used in the development process of the present invention is preferably in the range of 9 to 13. More preferably, the pH range is from 10 to 12. Alkaline agents used for setting pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate. Buffers such as JP-A-62-186259 (borates), JP-A-60-93433 (e.g., sucrose, acetoxime, 5-sulfosalicylic acid), phosphates, carbonates, etc. may be used. In the present invention, the developer preferably contains a chelating agent having a chelate stability constant of 8 or more with respect to iron ions. Here, the chelate stability constant is defined as L. G. Sillen A. E
．． Martell, H “Stabilty
Constants of Metal-ion C
complexes”, The Chemical So
City, London (1964). S. Ch
aberek・A. E. Written by Martell,
“Organic Sequestering Age
nts”, Wiley (1959). In the present invention, examples of chelating agents having a chelate stability constant of 8 or more for iron ions include organic carboxylic acid chelating agents and organic phosphoric acid chelating agents. , inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc.The above iron ion means ferric ion (Fe3+).In the present invention, the chelate stability constant with ferric ion is 8 or more. Specific examples of chelating agents include the following compounds,
It is not limited to these. Namely, ethylenediamine diorthohydroxyphenylacetic acid, triethylenetetraminehexaacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid,
1,3-diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine-N,N,N',N'tetrakismethylenephosphonic acid, nitrilo-N,N, N-trimethylenephosphonic acid,
1-hydroxyethylidene-1,1-diphosphonic acid, 1
, 1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid , sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. Further, a dialdehyde-based hardening agent or its bisulfite adduct may be used in the developer, and specific examples include glutaraldehyde or its bisulfite adduct.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide;
Organic solvents such as methyl cellosolve, hexylene glycol, ethanol, and methanol; mercapto compounds such as 1-phenyl-5-mercaptotetrazole and 2-mercaptobenzimidazole-5-sulfonic acid sodium salt; and indazole compounds such as 5-nitroindazole. compound, may contain an antifoggant such as a benztriazole compound such as 5-methylbenztriazole, and
EARCH DISCLOSURE Volume 176, No.
．． 17643, Section XXI (December issue, 1978) and, if necessary, toning agents,
Surfactant, antifoaming agent, water softener, JP-A-56-106
The amino compounds described in No. 244 may also be included. In the development process of the present invention, silver stain preventive agents other than the silver stain preventive agent of the present invention, such as the compounds described in JP-A-56-24347, can be used in the developer. The developer of the present invention contains amino compounds such as alkanolamines described in European Patent Publication No. 136582, British Patent No. 958678, U.S. Patent No. 3232761, and JP-A-56-106244 to promote development, increase contrast, and other effects. It can be used for any purpose. Other L. F. 22 of “Photographic Processing Chemistry” by A. Mason, Focal Press (1966).
pp. 6-229, U.S. Patent No. 2,193,015, No. 2
, 592,364, JP-A-48-64933, etc. may be used.

[0015] The fixing solution is an aqueous solution containing thiosulfate;
It has a pH of 3.8 or higher, preferably 4.2 to 7.0. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be varied as appropriate, and is generally about 0.1 to about 6 mol/liter. The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, aluminum sulfate, potassium alum, and the like. In the fixing solution, tartaric acid, citric acid, gluconic acid, or their derivatives can be used alone or in combination of two or more. 0.0 of these compounds per liter of fixer.
Those containing 0.05 mol or more are effective, particularly 0.01 mol/liter to 0.03 mol/liter. The fixing solution may optionally contain preservatives (e.g., sulfites, bisulfites), pH buffers (e.g., acetic acid, boric acid), pH adjusters (e.g., sulfuric acid), chelating agents with water softening ability, and The compound described in No. 62-78551 can be included.

In the present invention, the term "developing process time" or "developing time" refers to the time from when the leading edge of the photosensitive material to be processed is immersed in the developing tank solution of the automatic processing machine until it is immersed in the next fixing solution. "Fixing time" refers to the time from immersion in the fixing tank solution to immersion in the next washing tank solution (stabilizing solution), and "washing time" refers to the time during which it is immersed in the washing tank solution. In addition, "drying time" is usually 35℃ to 10℃ for automatic processors.
A drying zone is installed in which hot air of 0°C, preferably 40°C to 80°C is blown, and refers to the time spent in the drying zone. In the development process of the present invention, the development time is 5
seconds to 1 minute, preferably 5 seconds to 20 seconds, the developing temperature is 2
5°C to 50°C is preferable, and 25°C to 40°C is more preferable. Fixing temperature and time are approximately 20℃ to approximately 50℃ for 5 seconds to 1
minutes is preferred, and 5 seconds to 20 seconds at 25°C to 40°C is more preferred. The water washing or stabilization bath temperature and time are preferably 5 seconds to 1 minute at 0 to 50℃, and 5 seconds to 20 minutes at 15℃ to 40℃.
Seconds are more preferred. According to the method of the invention, the developed, fixed and washed (or stabilized) photographic material is dried by squeezing out the washing water, ie passing through a squeeze roller. Drying is carried out at a temperature of about 40°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but it is usually about 5 seconds to 1 minute, and particularly preferably about 5 seconds to 1 minute at 40°C to 80°C.
It is 30 seconds. The method for developing photosensitive materials of the present invention includes:
There are no particular restrictions on the photographic light-sensitive material, and general black and white light-sensitive materials are mainly used. In particular, photographic photosensitive materials for laser printers for medical images, scanner photosensitive materials for printing, medical direct photography X-ray photosensitive materials, medical indirect photography X-ray photosensitive materials, CRT image recording photosensitive materials, microphotosensitive materials, It is preferable to use it for general black and white negative film, black and white photographic paper, etc.

Next, the substantially non-photosensitive silver halide fine grains used in the present invention will be explained. As a means of preventing changes in photographic properties such as increased fog caused by iodine accumulated in the developer, many attempts have been made to improve performance by incorporating silver halide fine grains, which have virtually no sensitivity, into sensitive materials. It has been. For example, JP-A No. 50-23228,
No. 59-69754 and No. 59-160135 disclose techniques for incorporating fine grain emulsions. Therefore, it is not new to incorporate silver halide fine grains into a sensitive material. However, the effect of improving photographic properties and preventing silver sludge (silver stain) when a sensitive material containing core/shell type silver halide fine particles is developed with a developer containing a silver sludge inhibitor is exactly what was expected. It was an incredible and surprising fact.

The fine silver halide grains of the present invention are added to the protective layer. The fine silver halide grains used in the present invention must have an average size (volume equivalent spherical diameter) of less than 0.2 μm. If the thickness is 0.2 μm or more, optical scattering effects cannot be ignored, resulting in deterioration of image sharpness. Further, the smaller the average size is, the more preferable it is because sufficient development stability can be obtained with the addition of a smaller amount of fine silver halide. In the present invention, ultrafine particles of 0.10 μm or less are particularly preferred. The ultrafine grain emulsion of the present invention is a core/shell type silver halide emulsion in which the halogen composition differs between the core and shell parts. The halogen composition of the core part consists of silver iodobromide with a silver iodide content of 0 mol% (pure silver bromide) to 40 mol%, and the halogen composition of the shell part has a silver chloride content of 100 mol%.
(Pure silver chloride) Consists of ~30 mol% silver chlorobromide. Preferably, the iodine content in the silver iodobromide in the core part is 1 mol% to 10 mol%, and the chlorine content in the silver chlorobromide in the shell part is 50 mol% to 1 mol%.
00 mol%. Shell/core ratio (silver ratio) is 1/15
~3/1, preferably 1/10 to 1/1.

Particle size can be determined by a commonly used method using an electron microscope. The average value of particle size is determined by number averaging. Although there is no particular restriction on the particle size distribution, it is preferable for the present invention to use a so-called charcoal-dispersed emulsion having a narrow size distribution. A preferred size distribution has a coefficient of variation of 20% or less, more preferably 15% or less, particularly preferably 10% or less. The shape of the particle is (100
) faces, a cube consisting of (111) faces, an octahedron consisting of (111) faces, (
110) dodecahedron consisting of faces, further (hhl), (h
It may be any polyhedron with a high-order surface index such as a surface (h, k, l>1). Also (100) and (111)
Particles having a plurality of faces, such as tetradecahedral grains in which faces coexist, may also be used. Further, tabular grains having twin planes or potato-like grains having an amorphous shape may be used. The fine particles used in the present invention may have any shape.

Furthermore, the fine particles of the present invention may contain a compound represented by the following general formula (III) in order to suppress particle growth and physical ripening, and to maintain stable photographic performance of the sensitive material. preferable. General formula (III)

[0021]

[C5]

(wherein R2 is at least one -CO
It represents an aliphatic group, aromatic group or heterocyclic group substituted with OM or -SO3M, and M represents a hydrogen atom, an alkali metal atom, quaternary ammonium or quaternary phosphonium. ) The aliphatic group represented by R2 in the general formula (III) is specifically a linear or branched alkyl group having 1 to 20 carbon atoms (for example, a methyl group, a propyl group, a hexyl group, a dodecyl group, an isopropyl group, etc.). ), cycloalkyl groups having 1 to 20 carbon atoms (e.g. cyclopropyl group, cyclohexyl group, etc.), aromatic groups specifically include aryl groups having 6 to 20 carbon atoms (e.g. phenyl group,
naphthyl group, etc.), and the heterocyclic group specifically includes 5 atoms containing one or more nitrogen, oxygen, or sulfur atoms, etc.
It is a heterocycle of a membered ring, a 6-membered ring, or a 7-membered ring, and further includes those forming a condensed ring at an appropriate position (eg, a pyridine ring, a quinoline ring, a pyrimidine ring, an isoquinoline ring, etc.). Further, the above-mentioned straight chain or branched alkyl group, cycloalkyl group, aryl group and heterocyclic group may have a substituent in addition to -COOM or -SO3M. Specifically, these substituents include halogen atoms (F, Cl, Br, etc.), alkyl groups (methyl group, ethyl group, etc.), aryl groups (phenyl group, p-
chlorophenyl group, etc.), alkoxy group (methoxy group,
methoxyethoxy group, etc.), aryloxy group (phenoxy group, etc.), sulfonyl group (methanesulfonyl group, p
-toluenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (diethylsulfamoyl group, unsubstituted sulfamoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group) ), amide groups (acetamide groups, benzamide groups, etc.), ureido groups (methylureido groups, phenylureido groups, etc.),
Alkoxycarbonylamino group (methoxycarbonylamino group, etc.), aryloxycarbonylamino group (phenoxycarbonylamino group, etc.), alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), cyano group, hydroxy group, carboxy group, sulfo group, nitro group, amino group (unsubstituted amino group, dimethylamino group, etc.)
, an alkylsulfinyl group (such as a methoxysulfinyl group), an arylsulfinyl group (such as a phenylsulfinyl group), an alkylthio group (such as a methylthio group), and an arylthio group (such as a phenylthio group). The above may be substituted, and the substituents may be the same or different. General formula (II
Among the nitrogen-containing heterocyclic compounds (mercaptotetrazole derivatives) represented by I), those represented by general formula (IV) are particularly preferred. General formula (IV)

[0023]

[C6]

R3 in the general formula (IV) represents a phenyl group substituted with at least one -COOM or -SO3M;
In addition to 3M, it may be further substituted with other substituents. Specific examples of other substituents include the same substituents as those for the linear or branched alkyl group, cycloalkyl group, aryl group, and heterocyclic group represented by R2. Here, when there are two or more -COOM and -SO3M, they may be the same or different. M is the general formula (III
) means the same thing as expressed in . Preferred specific examples of the compound represented by the general formula (III) used in the present invention are listed below. However, the present invention is not limited to these specific examples.

[0025]

[C7]

[0026]

[Chemical formula 8]

[0027]

[Chemical formula 9]

The amount of the substantially non-photosensitive fine silver halide grains used in the present invention is preferably 0.01 to 1 g/m2, particularly 0.01 to 1 g/m2 of silver per square meter.
．． It is preferable that it is 03-0.3g/m2. In the light-sensitive material of the present invention, at least one photosensitive silver halide emulsion layer may be provided on one side of the support, or at least one photosensitive silver halide emulsion layer may be provided on both sides of the support. In the light-sensitive material of the present invention, the amount of gelatin on the side having the hydrophilic colloid layer including the photosensitive silver halide emulsion layer is in the range of 1.70 to 3.50 g/m<2>. If the light-sensitive emulsion layer is present on only one side of the support, the amount of gelatin on that side must be within the above range, and if the light-sensitive emulsion layer is present on both sides of the support, the amount of gelatin on that side must be within the above range. It is necessary that the amount of gelatin is within the above range. When there is no hydrophilic colloid layer other than the photosensitive emulsion layer, the amount of gelatin in the photosensitive emulsion layer is within the above range. The amount of gelatin is
More preferably in the range of 1.80 to 3.0 g/m2, especially 1
．． A range of 9 g/m2 to 2.5 g/m2 is preferred. The melting time of the present invention is preferably set to 8 minutes or more and 45 minutes or less. Melting time as used in the present invention refers to the melting time of a silver halide photographic light-sensitive material cut into 1 cm x 2 cm pieces when the silver halide photographic light-sensitive material is immersed in a 1.5% by weight aqueous solution of sodium hydroxide at 50°C. The time required for at least one silver halide emulsion layer to begin to melt.

Next, the photosensitive emulsion grains used in the present invention will be explained. The average particle size equivalent to a sphere in the same volume as the particles is preferably 0.4 μm or more. Especially from 0.5
Preferably, it is 2.0 μm. The narrower the particle size distribution, the better. The silver halide grains in the emulsion may have a regular crystal shape such as a cube or an octahedron, or may have an irregular crystal shape such as a spherical shape, a plate shape, a potato shape, etc. It may also consist of a mixture of particles of various crystalline forms, which may have . The silver halide composition is silver iodobromide because of its high sensitivity. The silver iodide content of the silver halide grains of the present invention must be 3.0 mol% or less based on the total silver amount as an average of individual grains, and preferably 2.0 mol% or less, based on the total silver amount.
It is preferably mol % or less, particularly 1.0 mol % or less. The silver iodide distribution among individual grains may be uniform or uniform. The silver halide grains of the present invention may contain a trace amount of silver chloride that does not affect photographic properties. When a monodisperse emulsion is used as an emulsion in carrying out the present invention, the rate of addition of water-soluble silver salt and water-soluble halide may be increased in preparation of the monodisperse emulsion as the silver halide grains grow. desirable. By increasing the addition rate, the particle size distribution can be made more monodisperse and the mixing time can be shortened, which is advantageous for industrial production. It is also preferable in that the chance of formation of structural defects inside the silver halide grains is reduced. As a method for increasing the addition rate, as described in Japanese Patent Publication No. 48-36890, Japanese Patent Publication No. 52-16364, and Japanese Patent Application Laid-Open No. 55-142329, the addition rate of the silver salt aqueous solution and the halide aqueous solution can be continuously increased. or may be increased in stages. The upper limit of the above addition rate may be the flow rate just before new grains are generated, and the value depends on temperature, pH, pAg, degree of stirring, composition of silver halide grains, solubility, grain size, distance between grains, or protection. It varies depending on the type and concentration of colloid. Methods for producing monodisperse emulsions are known, for example, as described in J. Photo. Sci. 12,
242-251 (1963), Special Publication No. 48-36890
No. 52-16364, JP-A-55-142329
It is described in Japanese Patent Application Publication No. 57-17983.
The technique described in No. 5 can also be adopted. The silver halide emulsion used in the present invention may be a core-shell type monodisperse emulsion, and these core-shell emulsions are known from, for example, JP-A-54-48521. When using a polydisperse emulsion as an emulsion in carrying out the present invention,
The polydisperse emulsion can be produced by a known method. For example, T. H. “The The
ory of the Photographic Pr
4th edition, published by Macmillan (19
1977) Neutral method, acidic method, ammonia method, forward mixing, back mixing, double jet method, controlled double jet method, conversion method, core/shell method described in literature such as pages 38 to 104 It can be manufactured by applying methods such as the following.

Further, tabular grains having a grain size of 5 times or more the grain thickness are preferably used in the present invention (in detail,
RESEARCH DISCLOSURE Volume 225
Item 22534 P. 20~P. 58, January issue, 1983, and JP-A-58-127921, same 5
8-113926). The tabular silver halide grains can be produced by appropriately combining methods known in the art. Tabular silver halide emulsions are produced by Cugnac and Chateau. Evolution of the Morphology of Silver Bromide Crystals During Physical Ripening・Dualing Physical Lightning)” Science・
E-Industrie Photography, Volume 33, No.
．． (1962), pp. 121-125, Duffin, “Photographic Emulsion Chemistry”
Focal Press, New York, 19
66, p. 66-p. 72, A. P. H. Trivelli, W. F. Smith
h) Photographic Journal (Photog)
rapic Journal), volume 80, page 285 (
1940), etc., but it was published in JP-A-58-127.
,921, JP-A-58-113,927, JP-A-58-
113,928, and the method described in US Pat. No. 4,439,520.

[0031] In order to effectively utilize the effects of the present invention,
During chemical sensitization during the emulsion preparation process as in JP-A-2-68539, it is preferable to include 0.5 mmol or more of a silver halide adsorbing substance per mol of silver halide. This silver halide adsorptive substance may be added at any time, such as during grain formation, immediately after grain formation, or before or after the start of after-ripening, but chemical sensitizers (for example, gold or sulfur sensitizers) are not added. It is preferable that it is added before chemical sensitization or at the same time as chemical sensitization, and it must be present at least during the process of chemical sensitization. As a condition for adding the silver halide adsorptive substance, the temperature may be any temperature in the range of 30°C to 80°C, but preferably in the range of 50°C to 80°C for the purpose of strengthening adsorption. Although the pH and pAg may be arbitrary, it is preferable that the pH is 6 to 10 and the pAg is 7 to 9 at the time of chemical sensitization. In the present invention, the silver halide adsorbing substance means a sensitizing dye or a photographic performance stabilizer. That is, azoles {for example, benzothiazolium salts, benzimidazolium salts, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc.}; mercapto compounds {for example, mercaptothiazoles , mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, mercaptotriazines, etc.}; for example, oxa Thioketo compounds such as drinthione; azaindenes {e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a,7
), tetraazaindenes), pentaazaindenes, etc.); many compounds known as antifoggants or stabilizers can be mentioned as silver halide adsorbents. Furthermore, purines or nucleic acids, or the polymer compounds described in Japanese Patent Publication No. 61-36213, Japanese Patent Application Laid-Open No. 59-90844, etc. are also usable adsorbent substances. Among them, azaindenes, purines, and nucleic acids are particularly preferred and can be used in the present invention. The amount of these compounds added is 300 to 1 mole of silver halide.
3000mg, preferably 500-2500mg.

The silver halide adsorptive substance of the present invention includes:
Sensitizing dyes can achieve favorable effects. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holophoric cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used. Useful sensitizing dyes for use in the present invention include, for example, U.S. Pat.
No. 197, No. 3,713,828, No. 3,615,6
No. 43, No. 3,615,632, No. 3,617,29
No. 3, No. 3,628,964, No. 3,703,377
No. 3,666,480, No. 3,667,960, No. 3,679,428, No. 3,672,897,
No. 3,769,026, No. 3,556,800, No. 3,615,613, No. 3,615,638, No. 3
, No. 615,635, No. 3,705,809, No. 3,
No. 632,349, No. 3,677,765, No. 3,7
No. 70,449, No. 3,770,440, No. 3,76
No. 9,025, No. 3,745,014, No. 3,713
, No. 828, No. 3,567,458, No. 3,625,
No. 698, No. 2,526,632, No. 2,503,7
No. 76, JP-A No. 48-76525, Belgian Patent No. 6
No. 91,807, etc. The amount of sensitizing dye added is 200 mg or more per mole of silver halide.
It is preferably less than 400 mg and less than 800 mg. Specific examples of sensitizing dyes useful in the present invention are shown below.

[0033]

[Chemical formula 10]

[0034]

[Chemical formula 11]

Tabular grains are particularly preferred as the photosensitive emulsion of the present invention. The projected area diameter of the tabular emulsion of the present invention is preferably 0.3 to 2.0 μm, particularly 0.5 to 1.2 μm. In addition, the distance between parallel planes (particle thickness) is 0.05 μm to 0.3 μm, especially 0.1 to 0.
．． 25 μm is preferable, and the aspect ratio is:
The number is preferably 3 or more and less than 20, particularly 4 or more and less than 8. In the tabular silver halide emulsion of the present invention, silver halide grains having an aspect ratio of 2 or more are present in at least 50% (projected area) of the total grains, particularly at least 70%, and the average aspect ratio of the tabular grains is It is preferably 3 or more, particularly 4 to 8. Among tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. Details of the structure and manufacturing method of the monodisperse hexagonal tabular grains referred to in the present invention are disclosed in Japanese Patent Application Laid-Open No.
151618.

Methods for chemically sensitizing the silver halide emulsion used in the present invention include sulfur sensitization, selenium sensitization, reduction sensitization, and gold sensitization in the presence of the silver halide adsorbing substance described above. Known methods can be used, such as the method used alone or in combination. Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and iridium. Specific examples include U.S. Patent No. 2,448,060 and British Patent No. 618,0.
It is described in No. 61, etc. In addition to the sulfur compounds contained in gelatin, sulfur sensitizers include various sulfur compounds such as thiosulfates, thioureas, thiazoles,
Rhodanines and the like can be used. Specific examples are U.S. Pat.
, No. 501,313 and No. 3,656,955. The combined use of sulfur sensitization using thiosulfate and gold sensitization can effectively exhibit the effects of the present invention. As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

The photographic emulsion used in the present invention contains silver halide in the chemical sensitization process for the purpose of preventing fog during the manufacturing process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. Various compounds can be included in addition to the adsorptive substance. Namely, azoles {e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.}; mercapto compounds {e.g. mercapto thiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, etc.}; thioketo compounds such as oxadorinthion; azaindenes {e.g. triazaindenes, Tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes)
, pentaazaindenes, etc.}; many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Especially JP-A-60-7
6743, nitrones and derivatives thereof as described in JP-A No. 60-87322, mercapto compounds as described in JP-A-60-80839, heterocyclic compounds and heterocyclic compounds as described in JP-A-57-164735. and silver complex salts (for example, 1-phenyl-5-mercaptotetrazole silver) can be preferably used. Even when a sensitizing dye is used in the chemical sensitization step, spectral sensitizing dyes in other wavelength ranges may be added as necessary.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (for example, development acceleration). , hardening agent, sensitization), etc., various surfactants may be included for various purposes. For example, saponin (
(steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene oxide adducts of silicones), and alkyl esters of sugars. Ionic surfactant; alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, N-acyl-N-
Anionic surfactants such as alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers; Ampholytic surfactants such as alkyl betaines and alkyl sulfobetaines; Aliphatic or aromatic quaternary ammonium Cationic surfactants such as salts, pyridinium salts, imidazolium salts, etc. can be used. Among these, saponin, dodecylbenzenesulfonic acid Na salt, di-2-ethylhexyl α
- Anions such as sulfosuccinic acid Na salt, p-octylphenoxyethoxyethanesulfonic acid Na salt, dodecyl sulfate Na salt, triisopropylnaphthalene sulfonic acid Na salt, N-methyl-oleoyl taurine Na salt, dodecyltrimethylammonium chloride, N -oleoyl-N',N',N'-trimethylammoniodiaminopropane bromide, cations such as dodecylpyridium chloride, N-dodecyl-N,N-dimethylcarboxybetaine, N-oleyl-N,N-dimethylsulfonate Betaine such as butyl betaine, poly(average degree of polymerization n = 1
0) Oxyethylene cetyl ether, poly(n=25)
Oxyethylene p-nonylphenol ether, bis(
1-poly(n=15)oxyethylene-oxy-2,4
Nonions such as -di-t-pentylphenyl)ethane can be particularly preferably used.

As the antistatic agent, perfluorooctanesulfonic acid K salt, N-propyl-N-perfluorooctanesulfonylglycine Na salt, N-propyl-N-perfluorooctanesulfonylaminoethyloxypoly(n=3)oxy Ethylene butane sulfonic acid Na salt, N
-perfluorooctanesulfonyl-N', N', N'
- trimethylammoniodiaminopropane chloride,
N-perfluorodecanoylaminopropyl-N',N
Fluorine-containing surfactants such as '-dimethyl-N'-carboxybetaine, JP-A Nos. 60-80848 and 61-1
No. 12144, No. 62-172343, No. 62-17
Nonionic surfactants described in No. 3459, nitrates of alkali metals, conductive tin oxide, zinc oxide, vanadium pentoxide, or composite oxides obtained by doping these with antimony or the like can be preferably used. In the present invention, as a matting agent, US Pat.
Homopolymers of polymethyl methacrylate or copolymers of methyl methacrylate and methacrylic acid as described in No. 245, No. 4142894, No. 4396706, organic compounds such as starch, inorganic compounds such as silica, titanium dioxide, sulfuric acid, barium strontium, etc. fine particles can be used. Particle size is 1.0~
It is preferably 10 μm, particularly 2 to 5 μm.

The surface layer of the photographic light-sensitive material of the present invention contains as a slipping agent US Pat. No. 3,489,576 and US Pat.
Silicone compounds described in No. 8 etc., Japanese Patent Publication No. 56-231
In addition to the colloidal silica described in Publication No. 39, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used. Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention.

As the binder or protective colloid that can be used in the emulsion layer or surface protective layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. . For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate, dextran, and starch derivatives; Various synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used.
Hydrolyzed gelatin and enzymatically decomposed products can also be used. Among these, it is preferable to use dextran or polyacrylamide with an average molecular weight of 50,000 or less together with gelatin. Japanese Patent Publication No. 63-68837, also 63-1
The method described in No. 49641 is also effective in the present invention.

The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glitaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis-[
β-(vinylsulfonyl)propionamide], etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazine, etc. Azinylated gelatin and the like can be used alone or in combination. Among them, JP-A-53-412
21, No. 53-57257, No. 59-162546, No. 60-80846 and active halides described in US Pat.

[0043] As the hardening agent of the present invention, polymeric hardening agents can also be effectively used. Examples of the polymeric hardening agent used in the present invention include dialdehyde starch, polyacrolein, polymers having aldehyde groups such as the acrolein copolymer described in U.S. Pat. No. 3,396,029, and U.S. Pat.
, 623,878, polymers having dichlorotriazine groups described in U.S. Patent No. 3,362,827, Research Disclosure Magazine 17333 (1978), etc., JP-A-56-66841 Polymers having active ester groups described in JP-A-56-142524, U.S. Patent No. 4,161,407, JP-A-54-65033, Research Disclosure Magazine 16725 (1978), etc. Examples include polymers having an active vinyl group or a group serving as a precursor thereof, and preferred are polymers having an active vinyl group or a group serving as a precursor thereof, and among them, polymers having an active vinyl group or a group serving as a precursor thereof are preferred. Particularly preferred are polymers in which the active vinyl group, or its precursor group, is attached to the polymer main chain by a long spacer.

The hydrophilic colloid layer in the photographic light-sensitive material of the present invention is preferably hardened with such a hardening agent so that the swelling ratio in water is 280% or less, particularly 200 to 280%. The swelling rate in water in the present invention is measured by a freeze-drying method. That is, the photographic material is heated to 25℃60
After 7 days under %RH conditions, the swelling ratio of the hydrophilic colloid layer is measured. Dry thickness (a) is determined by scanning electron microscopy of sections. The swelling film layer (b) is made of photographic material at 21
It is determined by immersing it in distilled water at ℃ for 3 minutes, freeze-drying it with liquid nitrogen, and then observing it with a scanning electron microscope. The swelling rate is determined as the value (%) obtained by dividing (b) - (a) by (a) and multiplying by 100. As the support, polyethylene terephthalate film or cellulose triacetate film is preferred.

In order to improve the adhesion with the hydrophilic colloid layer, the surface of the support is preferably subjected to corona discharge treatment, claw discharge treatment, or ultraviolet irradiation treatment, or styrene-butadiene-based latex, vinylidene chloride-based latex. Alternatively, a gelatin layer may be further provided on top of the undercoat layer. Further, an undercoat layer may be provided using an organic solvent containing a polyethylene swelling agent and gelatin. These undercoat layers can be surface-treated to further improve their adhesion to the hydrophilic colloid layer. The emulsion layer of the photographic material of the present invention may contain a plasticizer such as a polymer or an emulsion in order to improve pressure characteristics. For example, British Patent No. 73
U.S. Pat. No. 8,618 describes heterocyclic compounds, U.S. Pat. No. 738,637 describes alkyl phthalates, U.S. Pat. No. 3,121,060 contains carboxyalkylcellulose, JP-A No. 49-5017 contains paraffin and carboxylic acid salts, and JP-A No. 53-280
No. 86 discloses a method using an alkyl acrylate and an organic acid. There are no particular restrictions on other structures of the emulsion layer of the silver halide photographic material of the present invention.
Various additives can be used as necessary. For example, binders, surfactants, other dyes, ultraviolet absorbers, coating aids, thickeners, and the like described in Research Disclosure, Vol. 176, pp. 22-28 (December 1978) can be used. Hereinafter, the present invention will be specifically explained with reference to Examples.

[0046]

【Example】

Uniform halogen composition type fine silver chlorobromide grains A (
Preparation of silver nitrate aqueous solution (AgBr20Cl80) into gelatin aqueous solution (a) kept at 30°C.
b) and the aqueous halogen solution (c) were added over 6 minutes by a simultaneous mixing method. (a) Lime-treated gelatin
10g KBr
0.4gH2O
1000cc(b)AgNO
3 150
gH2O
600cc(c)KBr
20.6gNaCl
79gH2
O
After the addition of 600 cc was completed, a formalin condensate of sodium naphthalene sulfonate was added as a precipitant, and desalination was performed at pH 3.8. Then 30g of gelatin and H2
O was added to disperse the mixture, and the pH was adjusted to 6.8 with caustic soda. The average grain size of the resulting emulsion was 0.09 μm.

Uniform halogen composition type fine silver iodobromide grains B (
Preparation of silver nitrate aqueous solution (AgBr98I2) was added to gelatin aqueous solution (a) kept at 35°C.
b) and the aqueous halogen solution (c) were added over 9 minutes by a simultaneous mixing method. (a) Lime-treated gelatin
10g KBr
0.4gH2O
1000cc(b)AgNO
3 150
gH2O
600cc(c)KBr
108gKI

3gH2O
After adding 600 cc, a formalin condensate of sodium naphthalene sulfonate was added as a precipitant to pH 3.
．． Desalting treatment was performed in step 8. Then 30g gelatin
and H2O were added and dispersed, and the pH was adjusted to 6.8 with caustic soda. The average grain size of the resulting emulsion was 0.06 μm.

Preparation of core/shell type fine silver halide grains C A silver nitrate aqueous solution (
b-1) and the halogen aqueous solution (c-1) were added over 7 minutes and 30 seconds by a simultaneous mixing method. Then, silver nitrate aqueous solution (b
-2) and the halogen aqueous solution (c-2) were added over 1 minute and 30 seconds by a simultaneous mixing method. (a) Lime-treated gelatin
10g KBr
0.4gH2O
1000cc (b-
1) AgNO3
125gH2O
500cc (c-1) K
Br 8
5.4gKI
2.5gH2O
500cc (b-2)
AgNO3
25gH2O
100cc (c-2) KBr
3
．． 5g NaCl
13.5gH2O
After the completion of addition of 100 cc, a formalin condensate of sodium naphthalene sulfonate was added as a precipitant, and desalination was performed at pH 3.8. After that, add 30g of gelatin and H2O, disperse, and ply with caustic soda.
It was prepared at H6.8. The average grain size of the obtained emulsion was 0.0
It was 6 μm.

Preparation of fine silver halide grains D to F on which stabilizers have been adsorbed Immediately after the addition of silver nitrate and aqueous halogen solution to the preparation of fine silver halide grains A, a compound example of general formula (III) ( Emulsion D was prepared by adding 1.5 g of II) per mole of Ag. In the same manner, Compound Example (II) was added to the preparation of Emulsion B, and Compound Example (II) was added to the preparation of Emulsion E and Emulsion C to obtain Emulsion F. The amount added is the same as in Emulsion D.

Preparation of photosensitive silver halide emulsion G A photosensitive silver halide emulsion was prepared in the following manner. Potassium bromide 4.5g, gelatin 20g in 1 liter of water
．． 6g, thioether HO(CH2)2S(CH2)2
Add 2.5 cc of a 5% aqueous solution of S(CH2)2OH to 6
Add 37c of silver nitrate aqueous solution into a container kept at 0°C while stirring.
33 cc of an aqueous solution containing c (3.43 g of silver nitrate), 2.97 g of potassium bromide, and 0.363 g of potassium iodide was added in 37 seconds by a double jet method. Next, an aqueous solution of 0.9 g of potassium bromide was added, the temperature was raised to 70° C., and 53 cc of an aqueous silver nitrate solution (4.90 g of silver nitrate) was added over 13 minutes. Here, 25% ammonia aqueous solution 15c
c was added, and after physical ripening for 20 minutes at the same temperature, 14 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were brought to pA.
It was added over a period of 35 minutes using a controlled double jet method while maintaining the temperature at 8.5 g. Next, 10 cc of a 2N potassium thiocyanate solution and 0.05 mol % of AgI fine particles having a diameter of 0.07 μm based on the total amount of silver were added. After physical ripening at the same temperature for 5 minutes, the temperature was lowered to 35°C. In this way, monodisperse tabular grains having a total silver iodide content of 0.31 mol %, an average projected area diameter of 1.10 μm, a thickness of 0.165 μm, and a diameter variation coefficient of 18.5% were obtained. After this, soluble salts were removed by a sedimentation method. The temperature was raised to 40°C again, and 55 g of gelatin, 2.35 g of phenoxyethanol, and 0 sodium polystyrene sulfonate were added as a thickener.
．． Add 8g and adjust pH to 5.9 with caustic soda and silver nitrate solution.
0, pAg was adjusted to 8.25. This emulsion was chemically sensitized while being stirred and maintained at 56°C. First, 0.043 mg of thiourea dioxide was added and held for 22 minutes to perform reduction sensitization. Next, 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 500 mg of a sensitizing dye (sensitizing dye compound example S-(3))
was added. 1.1 g of calcium chloride aqueous solution was added to the colander. Subsequently, 3.3 mg of sodium thiosulfate, 2.6 mg of chloroauric acid, and 90 mg of potassium thiocyanate were added, and after 40 minutes, the mixture was cooled to 35° C. to prepare emulsion G. The following chemicals were added per mole of silver halide of Emulsion G to prepare a coating solution.・2,6-bis(hydroxyamino)-4-diethylamino-1,3,5-triazine

72mg trimethylolpropane

9g dextran (average molecular weight 39,000)
18.5g・Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8g・Hardening agent 1,2-bis(vinylsulfonylacetamide)ethane

So that the swelling rate is 230%.

Adjust the amount added.

[0052]

[Chemical formula 12]

[0053]

[Chemical formula 13]

Preparation of surface protective layer coating solution The surface protective layer was prepared so that each component was coated in the following amounts. Contents of surface protective layer

Application amount/gelatin

0.966g/m2・Sodium polyacrylate (average molecular weight 400,000) 0.023・
4-hydroxy-6-methyl-1,3,3a,7-
Tetrazaindene
0.015

[
0055

[Chemical formula 14]

- Polymethyl methacrylate (average particle size 3.7 μm)
0.087 Proxel (pH 7 with NaOH)
．． (adjusted to 4) 0.0005

[
Preparation of Support (1) Preparation of Dye D-1 for Undercoat Layer The following dye was ball milled by the method described in JP-A-63-197943.

[0058]

[Chemical formula 15]

434 ml of water and Triton X-
6.7% aqueous solution of 200 surfactant (TX-200) 7
91 ml was placed in a 2 liter ball mill. dye 2
0 g was added to this solution. Zirconium oxide (ZrO
) and add 400 ml of beads (2 mm diameter) to dilute the contents.
Grinded for days. After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. When the obtained dye dispersion was observed, the particle size of the pulverized dye had a wide range of diameters from 0.05 to 1.15 μm, and the average particle size was 0.37 μm. Furthermore, by performing a centrifugation operation, 0.9μ
Dye particles with a size of m or more were removed. In this way, dye dispersion D-1 was obtained. (2) Preparation of support A biaxially stretched polyethylene terephthalate film with a thickness of 183 μm was subjected to Conaro discharge treatment, and the first undercoating liquid having the following composition was applied to a wire so that the coating amount was 5.1 cc/m2. Apply with bar coater, 175
It was dried at ℃ for 1 minute. Next, do the same thing on the other side.
An undercoat layer was provided. The polyethylene terephthalate used contained 0.04 wt% of a dye having the following structure.

[0060]

[Chemical formula 16]

Butadiene-styrene copolymer latex solution
(Solid content 40% butadiene/styrene weight ratio
=31/69)

79cc 4% solution of 2,4-dichloro-6-hydroxy-s-triazine sodium salt

20.5cc distilled water

900.5 cc On top of the first undercoat layer on both sides, apply a second undercoat layer having the composition shown below, using a wire bar coater method on both sides to coat one side at a rate of 150 cc. It was applied and dried at ℃. ·gelatin

80mg/m2・Dye dispersion D-1 (20mg/m2 as dye solid content)

[0062]

[Chemical formula 17]

- Matting agent Polymethyl methacrylate with an average particle size of 2.5 μm 2.5 mg/m2

[0064]
Preparation of Photographic Material The emulsion layer and surface protective layer were coated on both sides of the prepared support by coextrusion. The amount of silver coated per side is 1
．． It was set to 65g/m2. The swelling ratio was adjusted to 230% by adjusting the amount of gelatin and hardener added to the emulsion layer. Photographic material 1 was thus obtained.

Preparation of Photographic Materials 2 to 7 Fine silver halide grains A to F are added to the surface protective layer of Photographic Material 1.
Contained. The amount of silver contained per side was 0.
It was set to 15g/m2. At this time, the amount of gelatin brought in by the fine particles was adjusted to be the same as that of Photographic Material 1 by reducing the amount of gelatin in the surface protective layer. The obtained photographic materials 2 to 7 are summarized in Table 1.

Evaluation of Photographic Performance Each sample of Photographic Materials 1 to 7 was exposed to light for 0.05 seconds from both sides using X-Ray Orthoscreen HR-4 manufactured by Fuji Photo Film Co., Ltd. to evaluate sensitivity. was carried out. After exposure, the following processing was performed. The sensitivity was expressed as the reciprocal of the ratio of the exposure amount giving a density of 1.0, taking the result of Processing I of Photographic Material 1 as 100. The average gradation G was expressed by the slope of a straight line connecting a point with fog+density of 0.25 and a point with fog+density of 2.0.

[Processing I] Automatic developing machine: The drive motor and gear section of SRX501 manufactured by KONICA Corporation were modified to increase the conveyance speed. <Developer concentrate> Potassium hydroxide

56.6g Sodium sulfite

200g diethylenetriaminepentaacetic acid
6.7g potassium carbonate

16.7g boric acid

10g hydroquinone
83
．． 3g diethylene glycol

40g 4-hydroxymethyl-4-
Methyl-1-phenyl-3-pyrazolidone

22.0g 5-methylbenzotriazole
2g water 1
liter (adjust to pH 10.60). <Fixer concentrate> Ammonium thiosulfate

560g sodium sulfite

60g Ethylenediaminetetraacetic acid, disodium, dihydrate
0.10g sodium hydroxide

24g Make up to 1 liter with water (adjust to pH 5.10 with acetic acid). When starting the developing process, each tank of the automatic developing machine was filled with the following processing solution. Developing tank: 333 ml of the above developer concentrate, 667 ml of water
10 ml of a starter containing 2 g of potassium bromide and 1.8 g of acetic acid were added to adjust the pH to 10.25. A developing tank was filled with a solution having this composition. Fixing tank: 200ml of the above fixer concentrate and 800ml of water
The composition was ml. Processing speed...Dry to Dry 35 seconds Development temperature...35℃ Fixing temperature...32℃ Drying temperature...55℃ Replenishment amount...Developer 22ml/10×12
Inch fixer 30ml/10 x 12 inches

006
8] [Processing II] Compound Example (I-1) of general formula (I) of the present invention was added to the developer concentrate of Processing I at 3×10 −3 mol/liter. The other points were the same as in Process I.

[0069] Silver sludge, silver stain evaluation automatic processing machine 6 times a week
The apparatus was operated for 1 day, and on the operating days, 100 sheets of 4-cut size (10 inches x 12 inches) exposed to a density of 1.0 were processed. The running experiment as described above was continued for a total of two weeks, and the total number of sheets processed was 1200 sheets.

The above results are summarized in Tables 1 and 2. In processing (I), a large amount of silver stain was generated in all of Photographic Materials 1 to 7, and the stain was so severe that the silver stain attached to the roller was transferred to the processed photosensitive material. On the other hand, Table 2 shows the results of treatment (II) containing a silver stain inhibitor. Although the effect of the silver stain preventive agent is noticeable in Photographic Material 1, it can also be seen that the decrease in sensitivity gradation is extremely large. However, in photographic materials 4 and 7 containing the core/shell type fine silver halide grains C of the present invention in the surface protective layer, almost no silver stain occurs, and furthermore, no decrease in photographic sensitivity or gradation is observed.

[0071]

[Table 1]

[0072]

[Table 2]

Treatment I with the following compound as a silver stain preventive agent
When 3 x 10-3 mol/liter was added to the developing concentrate, similar results were obtained as shown in Table 2. In the case of photographic materials 4 and 7, there was no decrease in sensitivity gradation and almost no silver staining occurred. Ta.

[0074]

[Chemical formula 18]

[0075]

[Chemical formula 19]

[0076]

[C20]

Claims (3)

[Claims] Claim 1: In a method for developing a silver halide photographic material having at least one photosensitive silver halide emulsion layer on at least one side of the support, a position remote from the silver halide emulsion layer as viewed from the support. A surface protective layer containing core/shell type fine silver halide grains with an average grain size of less than 0.2 μm, and processing the silver halide photographic material with a developer containing a silver sludge inhibitor. A method for developing a silver halide photographic material characterized by 2. The silver halide photographic photosensitive material according to claim 1, wherein the halogen composition of the core portion of the fine silver halide grains is silver iodobromide, and the halogen composition of the shell portion is silver chlorobromide. Material development method [Claim 3] The silver sludge inhibitor has the following general formula (I
) A method for developing a silver halide photographic light-sensitive material according to claim 1 or 2, characterized in that the general formula (I) is represented by the formula (I): In the formula, X represents a hydrogen atom or a sulfonic acid group. M1
represents a hydrogen atom or an alkali metal atom, M2
represents a hydrogen atom, an alkali metal atom or an ammonium group.