JPH04328541A - Silver halide photographic sensitive material and processing method thereof - Google Patents

Abstract

PURPOSE:To provide a high sensitivity in short-time exposing with high illuminance and excellent rapid processability by using a silver halide emulsion which is core/shell type silver halide particles contg. a silver chloride, has the higher silver bromide content in the shell part, contains a specific ratio of iridium in particler and is chemically sensitized with a selenium compd. CONSTITUTION:This photosensitive material has photosensitive emulsion layers contg. the silver halide particles on a base. The silver halide particles consist of the core part consisting of the silver halide having >=30mol% silver chloride and the shell part consisting of the silver halide having the higher silver bromide content covering the core part than in the core part. The emulsion layers contain the iridium compd. at <=10<-6>mol of the silver. Further, the silver halide particles are chemically sensitized with a selenium sensitizer. The higher effect is obtd. if the silver halide particles contain iron, rhenium, ruthenium, and osmium compds. at <=10<-3>mol of the silver.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material that has high sensitivity and excellent suitability for rapid processing in high-intensity, short-time exposure, and a developing processing method thereof. It is something.

0002

[Prior Art] One of the exposure methods for photographic light-sensitive materials is to scan an original image, and then expose the silver halide photographic light-sensitive material based on the image signal to create a negative or positive image corresponding to the image on the original image. An image forming method using a so-called scanner method is known. Although there are various recording apparatuses that utilize image forming methods using a scanner method, many of the so-called dot generator methods using halftone dot generators are currently in use. Conventionally, glow lamps, xenon lamps, mercury lamps, tungsten lamps, light emitting diodes, and the like have been used as recording light sources for these scanner type recording devices. However, all of these light sources have practical drawbacks of low output and short lifespan. To compensate for these drawbacks, He-Ne laser,
There are scanners that use a coherent laser light source such as an argon laser, a He-Cd laser, or a semiconductor laser as a light source for a scanner method. The photosensitive materials used in these scanners are required to have various properties, but in particular, they are exposed for a short time of 10-3 to 10-8 seconds, so even under such conditions, they must have high sensitivity and high performance. Contrast is an essential condition. In addition, highly sensitive photosensitive materials are more advantageous in reducing the output in order to prolong the life of the laser tube. Furthermore, in order to obtain good halftone dots, it is necessary to shape the laser beam using a slit or the like, and a highly sensitive photosensitive material is required to cope with the decrease in laser output.

Furthermore, in recent years, there has been a strong desire to improve the efficiency and speed of work in the printing industry, and there is a wide range of needs for faster scanning and shorter processing times for photosensitive materials. In order to meet these needs in the printing field, exposure machines (scanners, plotters) are required to speed up scanning, increase the number of lines and narrow the beam for higher image quality, and silver halide photographic sensitizers Materials are desired to have high sensitivity (low developer replenishment amount), excellent processing stability, and be capable of rapid development processing. What we mean by rapid processing is that after inserting the leading edge of the film into an automatic processing machine,
A process in which the leading edge of the film passes through a developing tank, a transition section, a washing tank, and a drying section and emerges from the drying section within 15 to 60 seconds.

Japanese Patent Publication No. 57-22090 discloses a method of sensitizing silver halide containing a water-soluble iridium compound with a selenium sensitizer. It is still unsatisfactory in that when the amount of developer replenishment is reduced, the sensitivity becomes softer.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material that is highly sensitive during high-intensity exposure. Still another object of the present invention is to provide a silver halide photographic material that exhibits high sensitivity and good image quality even when rapidly processed, and a developing processing method thereof. Still another object of the present invention is to provide a silver halide photographic material that is highly sensitive and stable even when the amount of replenishment of a developer is reduced, and a developing method thereof.

[0006]

[Means for Solving the Problems] The above object of the present invention is to provide a silver halide photographic material having at least one light-sensitive emulsion layer containing silver halide grains on a support, in which the silver halide grains are , a core which is a silver halide containing 30 mol % or more of silver chloride, contains an iridium compound of 10 −6 mol or less relative to silver, and has a higher silver bromide content in the shell part than in the core part. This was achieved by using a silver halide photographic light-sensitive material which is a shell-type silver halide and further has selenium-sensitized silver halide grains. Further, the object of the present invention can be more effectively achieved by incorporating iron, rhenium, ruthenium, or osmium compounds in an amount of 10@-3 mol or less relative to silver in the silver halide of the light-sensitive material. A specific configuration of the present invention will be explained in detail. The silver halide photographic emulsion according to the present invention contains silver chloride, silver chlorobromide or silver chloroiodobromide as silver halide. At this time, silver chloride is contained in an amount of 30 mol % or more, more preferably 60 mol % or more. The shape of the silver halide grains may be cubic, tetradecahedral, octahedral, amorphous, or plate-like, but cubic or plate-like is preferable. The average grain size of the silver halide grains is preferably 0.01 μm to 1 μm, more preferably 0.4 μm or less, and {(standard deviation of grain size)/(
It is preferable to have a narrow particle size distribution with a coefficient of variation expressed as (average particle size)}×100 of 15% or less, more preferably 10% or less.

The core/shell type silver halide grains according to the present invention include a core portion made of silver halide containing silver chloride, and a core portion made of silver halide having a higher silver bromide content than the core portion. The thickness of the shell portion is preferably 0.001 to 0.3 μm, more preferably 0.005 to 0.2 μm. The silver bromide content in the core part is preferably 0 to 70 mol%, more preferably 0 to 40 mol%, and the silver bromide content in the shell part is 10 to 100 mol%, and more preferably 40 to 100 mol%.
is preferred. Further, the silver iodide content is preferably 5 mol % or less, more preferably 2 mol % or less, and more preferably contained in the shell portion or the silver halide surface. The core/shell type silver halide in the present invention may have a core portion having a layered structure of two or more layers. When the core has a layered structure of two or more layers, at least one of the layers is made of silver halochloride having a lower silver bromide content than the shell (outermost layer). The difference in silver bromide content between the core and shell is 10
It is preferably mol% or more, particularly 20 mol% or more. The ratio (molar ratio) of the amount of silver in the core to the shell is preferably 0.05 to 9, particularly 0.1 to 2, in the shell to 1 in the core.

The photographic emulsion used in the present invention is P. Gl
Chimie et Physi by afkides
que Photographique (Paul M.
ontel, 1967), G. F. Duff
Written by in Photographic Emulsion
Chemistry (The Focal Pres.
s publication, 1966), V. L. Zelikman
Making and Coating by et al.
Photographic Emulsion (Th
e Focal Press, 1964). That is,
Any of the acidic method, neutral method, ammonia method, etc. may be used, and any one-sided mixing method, simultaneous mixing method, combination thereof, etc. may be used to form the reaction between the soluble silver salt and the soluble halogen salt. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. In addition, in order to make the particle size uniform, British Patent No. 1,535,
No. 016, Special Publication No. 48-36890, No. 52-1636
As described in No. 4, there is a method of changing the addition rate of silver nitrate or alkali halide depending on the grain growth rate, British Patent No. 4,242,445, and Japanese Patent Application Laid-open No. 1983-15.
It is preferable to use a method of varying the concentration of an aqueous solution as described in No. 8124 to grow rapidly within a range that does not exceed the critical saturation level. Grain formation of the silver halide emulsion of the present invention is preferably carried out in the presence of a silver halide solvent such as a tetrasubstituted thiourea or an organic thioether compound. Preferred tetrasubstituted thiourea silver halide solvents used in the present invention include JP-A-53-82408 and JP-A-53-82408;
-77737, etc., and is a compound represented by the following general formula (I). General formula (I)

[0009]

[Chemical formula 1]

General formula (I) will be explained. In the formula, R
1, R2, R3 and R4 represent a substituted or unsubstituted alkyl group, an alkenyl group (such as an allyl group), or a substituted or unsubstituted aryl group, which may be the same or different from each other, and each of R1 to R4 The total number of carbon atoms is preferably 30 or less. Also, R1 and R2,
R2 and R3 or R3 and R4 combine to form 5
or 6-membered heterocyclic imidazolidinethione, piperidine, morpholine, etc. can also be produced. Both straight chain and branched alkyl groups are used as the alkyl group. Examples of substituents for alkyl groups include hydroxy groups (-OH), carboxy groups, sulfonic acid groups, amino groups, alkoxy groups (o-alkyl) in which the alkyl residue has 1 to 5 carbon atoms, phenyl groups, It is a 5- or 6-membered heterocycle (such as furan). The substituent for the aryl group is a hydroxy group, a carboxy group or a sulfonic acid group. Particularly preferably, R1 to R4 have three or more alkyl groups, each alkyl group has 1 to 5 carbon atoms, the aryl group is a phenyl group, and the total number of carbon atoms in R1 to R4 is 20 or less. It is. Examples of compounds that can be used in the present invention include the following.

[0011]

[Case 2]

0012

[Chemical formula 3]

[0013]

[C4]

[0014]

[C5]

The organic thioether silver halide solvent preferably used in the present invention is disclosed in Japanese Patent Publication No. 47-11386, for example.
Compounds containing at least one group in which an oxygen atom and a sulfur atom are separated by ethylene (e.g. -O-CH2 CH2 -S-) described in JP-A No. 3,574,628, etc. No. 54-155828 (U.S. Pat. No. 4,276,374), an alkyl group at both ends (each alkyl group has at least two substituents selected from hydroxy, amino, carboxy, amide, or sulfone) ) is a chain-like thioether compound. Specifically, the following examples can be given.

[0016]

[C6]

The amount of silver halide solvent added varies depending on the type of compound used, the intended grain size, halogen composition, etc., but it is 10-5 per mol of silver halide.
~10 −2 mol is preferred. If the grain size exceeds the desired size due to the use of a silver halide solvent, the desired grain size can be achieved by changing the temperature during grain formation, the addition time of the silver salt solution, the halide salt solution, etc.

[0018] As the iridium compound used in the present invention, a water-soluble iridium compound can be used. For example, halogenated iridium (III) compounds, halogenated iridium (IV) compounds, and iridium complex salts having halogens, amines, oxalates, etc. as ligands, such as hexachloroiridium (III).
Or (IV) complex salt, hexaammineiridium (I
II) or (IV) complex salts, trioxalatoiridium (III) or (IV) complex salts, and the like. In the present invention, among these compounds, III-valent compounds and IV-valent compounds can be used in any combination. These iridium compounds are used after being dissolved in water or an appropriate solvent, but methods commonly used to stabilize solutions of iridium compounds include aqueous hydrogen halide solutions (e.g., hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.). , or alkali halides (e.g. KCl, NaCl,
KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve other silver halide grains doped with iridium in advance during the preparation of silver halide grains. The total amount of iridium compounds used in the present invention is 1×1 per mole of silver halide finally formed.
0-8 to 1 x 10-6 mol is appropriate, preferably 5
x10-8 to 1 x 10-6 mol. Adding more than 10@-6 mol is undesirable because of desensitization. These compounds can be added as appropriate during the production of the silver halide emulsion and at each stage before coating the emulsion, but in particular, they can be added during grain formation and incorporated into the silver halide grains. preferable. As a specific compound, first chloride
Iridium (III), Iridium (III) bromide
, iridium (IV) chloride, sodium hexachloroiridate (III), hexachloroiridium (
Preferred are halogen amines and oxalato complex salts such as III) salt, hexamine iridium (IV) salt, trioxalatoiridium (III) salt, and trioxalatoiridium (IV) salt.

The iron compound used in the present invention is a divalent or trivalent iron ion-containing compound, preferably an iron salt or iron complex salt that is water-soluble within the concentration range used in the present invention. Specifically, ferrous arsenate ferrous bromide ferrous carbonate ferrous chloride ferrous citrate ferrous fluoride ferrous formate ferrous gluconate hydroxide ferrous iodide Ferrous lactate Ferrous oxalate Ferrous phosphate Ferrous succinate Ferrous sulfate Ferrous thiocyanate Ferrous nitrate Ferrous nitrate Ammonium basic Ferric acetate Ferrous albumate Ferric acetate Ammonium Bromide Ferric chloride Ferric chlorate Ferric citrate Ferric fluoride Ferric formate Glycero phosphate Ferric hydroxide Ferric acid phosphate Ferric Nitrate Ferric Phosphate Ferric Pyrophosphate Ferric Pyrophosphate Sodium Thiocyanide Ferric Sulfate Ferric Ammonium Sulfate Ferric Sulfate Guanidine Ferric Ammonium Citrate Hexane Cyanoferrous Potassium (II) acid Potassium bentacyanoammine Ferrous potassium Ethylene dinitrilotetraacetic acid Ferrous sodium Sodium hexacyanoferrate(III) acid Tris(dipyridyl) ferric chloride Bentacyano nitrosyl Ferric potassium Hexarea Ferric chloride Especially hexacyano Iron (II) salt, hexacyanoferrate (I
II) Acid salts, ferrous thiocyanate and ferric thiocyanate exhibit remarkable effects.

[0020] The rhenium, ruthenium, and osmium compounds used in the present invention are disclosed in European published patent (EP) 0.
No. 336689A, No. 0336427A1, No. 033
The hexacoordination complexes described in No. 6425A1 and No. 0336426A1 are preferred, and those containing at least four cyanide ligands are particularly preferred. In preferred embodiments, these compounds can be represented by the following formulas. [M(Cn)6-yLy]n where M is rhenium, ruthenium, osmium, L is a bridging ligand, y is an integer 0, 1, or 2, and n is -2, -3 or -4. A specific example is [Re(CN)5]-4
[Ru(CN)5]-4 [Os(CN)
)5]-4 [ReF(C
N)5]-4 [RuF(CN)5]-4
[OsF(CN)5]-4
[ReCl(CN)5]-4
[RuCl(CN)5]-4 [OsC
l(CN)5]-4 [ReBr(
CN)5]-4 [RuBr(CN)5]-
4 [OsBr(CN)5]-4
[ReI(CN)5]-4
[RuI(CN)5]-4 [Os
I(CN)5]-4 [ReF
2 (CN)4]-4 [RuF2 (CN)
)5]-4 [OsF2 (CN)
5]-4 [ReCl2 (CN)4]-4
[RuCl2 (CN)4]-4
[OsCl2 (CN)4]-4
[RuBr2 (CN)4]-4 [O
sBr2 (CN)4]-4 [ReB
r2 (CN)4]-4 [RuI2 (C
N) 4]-4 [OsI2 (CN
)5]-4 [Ru(CN)5(OCN)]
-4 [Os(CN)5(OCN)]-4
[Ru(CN)5(SCN)]-4 [O
s(CN)5(SCN)]-4 [Ru(C
N)5(N3)]-4 [Os(CN)
5(N3)]-4 [Ru(CN)5(H2
O)]-3 [Os(CN)5(H2O)]
-3 can be mentioned.

The above-mentioned iron, rhenium, ruthenium, and osmium compounds are preferably added during the formation of silver halide grains. The addition position may be uniformly distributed in the particles or localized at the early, middle, or late stages of particle formation;
Preferably, it is added after 0%, more preferably 80%, has been formed. The amount added is 10-3 mol or less, preferably 10-6 to 10-4 mol, per 1 mol of silver. Adding more than 10@-3 mol is undesirable because fog increases. In the present invention, other metals included in Group VIII, such as cobalt, nickel, rhodium, palladium, and platinum, may be used in combination. In particular, the combination with rhodium salts such as rhodium chloride and ammonium hexachlorodate(III) is advantageous because a high-contrast emulsion can be obtained.

As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. That is, it is usually used by adding an unstable selenium compound and/or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably 40° C. or higher, for a certain period of time. As unstable selenium compounds, Japanese Patent Publication No. 44-15748, Japanese Patent Publication No. 43-13489,
It is preferable to use compounds described in Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-229300, and the like. Specific unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2-
selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (e.g., bis(3-chloro-2,6-dimethoxybenzoyl)selenide), selenophosphates, phosphine selenides, colloidal metal selenium, etc. can give. Although preferred types of unstable selenium compounds have been described above, these are not intended to be limiting. Those skilled in the art understand that when it comes to unstable selenium compounds used as sensitizers in photographic emulsions, the structure of the compound is not particularly important as long as selenium is unstable; It is generally understood that the moiety has no role other than to support the selenium and allow it to exist in an unstable form in the emulsion. In the present invention, unstable selenium compounds having such a broad concept are advantageously used. As the non-unstable selenium compound used in the present invention, the compounds described in Japanese Patent Publication No. 46-4553, Japanese Patent Publication No. 34492-1982, and Japanese Patent Publication No. 34491-1988 are used. Non-labile selenium compounds include, for example, selenite, potassium selenocyanide, selenazole compounds, quaternary salts of selenazole compounds, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, Examples include 2-selenoxazolidinethione and derivatives thereof. Among these selenium compounds, the following general formula (I
II) and (IV). General formula (III)

[0023]

[C7]

In the formula, Z1 and Z2 may be the same or different, and represent an alkyl group (for example, methyl group, ethyl group, t-butyl group, adamantyl group, t-octyl group), an alkenyl group (for example, vinyl group, propenyl group), aralkyl group (e.g. benzyl group, phenethyl group), aryl group (e.g. phenyl group, pentafluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoylphenyl group) ,
α-naphthyl group), heterocyclic group (e.g. pyridyl group, chenyl group, furyl group, imidazolyl group), -NR1 (
R2), -OR3 or -SR4. R1
, R2, R3 and R4 may each be the same or different and represent an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Alkyl group, aralkyl group,
Examples of the aryl group or heterocyclic group include the same examples as Z1. However, R1 and R2 are hydrogen atoms or acyl groups (e.g., acetyl group, propanoyl group, benzoyl group, heptafluorobutanoyl group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4-trifluoromethylbenzoyl group) (base) may be used. In general formula (III), preferably Z1 represents an alkyl group, an aryl group or -NR1 (R2), and Z2 represents -NR5 (R6). R1, R2, R5
and R6 may be the same or different,
Represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group. In general formula (III), more preferably N,N-
Dialkylselenourea, N,N,N'-trialkyl-
N'-acylselenourea, tetraalkylselenourea,
Represents N,N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide. General formula (IV)

[0025]

[Chemical formula 8]

In the formula, Z3, Z4 and Z5 may be the same or different, and are an aliphatic group, an aromatic group, a heterocyclic group, -OR7, -NR8 (R9), -S
R10, -SeR11, X represents a hydrogen atom. R7,
R10 and R11 are an aliphatic group, an aromatic group, a heterocyclic group,
represents a hydrogen atom or a cation, R8 and R9 represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom,
X represents a halogen atom. In general formula (IV), Z
3, Z4, Z5, R7, R8, R9, R1
The aliphatic group represented by 0 and R11 is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (e.g. methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group). , n-butyl group, n
-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, propargyl group, 3-pentynyl group, benzyl group, phenethyl group). In general formula (IV), Z3, Z4, Z5, R7
, R8, R9, R10 and R11 are monocyclic or condensed aryl groups (e.g., phenyl group, pentafluorophenyl group, 4-chlorophenyl group, 3-sulfophenyl group, α-naphthyl group). , 4-methylphenyl group). In general formula (IV), Z3
, Z4, Z5, R7, R8, R9, R10 and R11 are 3- to 10-membered saturated or unsaturated heterocyclic groups containing at least one of nitrogen, oxygen, or sulfur atoms. represents a group (eg, pyridyl group, chenyl group, furyl group, thiazolyl group, imidazolyl group, benzimidazolyl group). In the general formula (IV), the cations represented by R7, R10 and R11 represent an alkali metal atom or ammonium, and the halogen atom represented by X represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In general formula (IV),
Preferably Z3, Z4 or Z5 represents an aliphatic group, an aromatic group or -OR7, and R7 represents an aliphatic group or an aromatic group. In general formula (IV), more preferably it represents trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Below is the general formula (
Specific examples of the compounds represented by III) and (IV) are shown below, but the present invention is not limited thereto.

[0027]

[Chemical formula 9]

[0028]

[Chemical formula 10]

[0029]

[Chemical formula 11]

[0030]

[Chemical formula 12]

[0031]

[Chemical formula 13]

[0032]

[Chemical formula 14]

[0033]

[Chemical formula 15]

[0034]

[Chemical formula 16]

Regarding the selenium sensitization method, US Pat.
No. 74944, No. 1602592, No. 16234
No. 99, No. 3297446, No. 3297447, No. 3320069, No. 3408196, No. 34
No. 08197, No. 3442653, No. 34206
No. 70, No. 3591385, French Patent No. 269
No. 3038, No. 2093209, Special Publication No. 52-34
No. 491, No. 52-34492, No. 53-295,
No. 57-22090, JP-A No. 59-180536,
No. 59-185330, No. 59-181337, No. 59-187338, No. 59-192241, No. 6
No. 0-150046, No. 60-151637, No. 61
-246738, Japanese Patent Application Publication No. 3-4221, Patent Application No. 1-
No. 287380, No. 1-250950, No. 1-254
No. 441, No. 2-34090, No. 2-110558, No. 2-130976, No. 2-139183, No. 2
-229300 Furthermore, British Patent No. 255846, British Patent No. 861984 and H. E. Spencer et al., Journal of Photographic
It is disclosed in Science magazine, volume 31, pages 158-169 (1983).

These selenium sensitizers may be dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixture thereof, or as disclosed in Japanese Patent Application Nos. 2-264447 and 2-26.
It is added at the time of chemical sensitization in the form described in No. 4448. It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, but two or more of the above selenium sensitizers can be used in combination. An unstable selenium compound and a non-unstable selenium compound may be used together. The amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the temperature and time of ripening, and preferably silver halide 1 It is 1×10 −8 mole or more per mole. More preferably, it is 1×10 −7 mol or more and 1×10 −5 mol or less. When a selenium sensitizer is used, the temperature for chemical ripening is preferably 45°C or higher. More preferably 50°C or higher, 8
The temperature is below 0°C. pAg and pH are arbitrary. For example, the effects of the present invention can be obtained over a wide range of pH from 4 to 9. Selenium sensitization is more effective when carried out in the presence of a silver halide solvent.

The silver halide photographic emulsion of the present invention can achieve higher sensitivity and lower fog by combining sulfur sensitization and/or gold sensitization in chemical sensitization. Sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40° C. or higher, for a certain period of time. Further, gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40° C. or higher, for a certain period of time. For the above-mentioned sulfur sensitization, known sulfur sensitizers can be used. Examples include thiosulfate, thioureas, allyl isothiacyanate, cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. Patent No. 1,574,9
No. 44, No. 2,410,689, No. 2,278,
No. 947, No. 2,728,668, No. 3,501
, 313 and 3,656,955, German Patent No. 1,422,869, and Japanese Patent Publication No. 1983-24937.
Sulfur sensitizers described in JP-A-55-45016 and the like can also be used. The amount of sulfur sensitizer added may be sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, silver halide grain size, etc., but it is between 1 x 10-7 mol and 5 mol per mol of silver halide.
x10-4 mol or less is preferable.

As the gold sensitizer for the above-mentioned gold sensitization, the oxidation number of gold may be +1 or +3, and gold compounds commonly used as gold sensitizers can be used. Typical examples include chlorauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold, and the like. The amount of gold sensitizer added varies depending on various conditions, but as a rough guide, it is preferably from 1.times.10@-7 mol to 5.times.10@-4 mol per mol of silver halide. During chemical ripening, there is no need to set particular restrictions on the timing and order of addition of silver halide solvents and selenium sensitizers, or sulfur sensitizers and/or gold sensitizers that can be used in combination with selenium sensitizers. Rather, the above compounds can be added simultaneously or at different times, for example, at the beginning (preferably) of chemical ripening or during the progress of chemical ripening. Also, when adding
The above compound may be added after being dissolved in water or an organic solvent miscible with water, such as methanol, ethanol, acetone, etc., either alone or in a mixture.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptothiadiazoles, aminotriazoles,
benzothiazoles, nitrobenzotriazoles, etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1, 3,
3a, 7) tetrazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can. In particular, polyhydroxybenzene compounds
This is preferable in that it improves pressure resistance without impairing sensitivity. The polyhydroxybenzene compound is preferably a compound having one of the following structures. General formula (V)

[0040]

[Chemical formula 17]

Next, general formula (V) will be explained. X and Y are -H, -OH, halogen atom, -OM (M
is an alkali metal ion), -alkyl group, phenyl group,
Amino group, carbonyl group, sulfone group, sulfonated phenyl group, sulfonated alkyl group, sulfonated amino group,
A sulfonated carbonyl group, a carboxyphenyl group, a carboxyalkyl group, a carboxyamino group, a hydroxyphenyl group, a hydroxyalkyl group, an alkyl ether group, an alkylphenyl group, an alkylthioether group, or a phenylthioether group. Specific examples of the compound of general formula (V) are shown below.

[0042]

[Chemical formula 18]

[0043]

[Chemical formula 19]

[0044]

[C20]

The polyhydroxybenzene compound may be added to the emulsion layer of the sensitive material, or may be added to a layer other than the emulsion layer. The amount added is preferably in the range of 10-5 to 1 mol, and particularly effective in the range of 10-3 to 10-1 mol.

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. As a sensitizing dye,
Cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holoholic cyanine dye, styryl dye, hemicyanine dye,
Oxonol dyes, hemioxonol dyes, etc. can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE Item
17643 Section IV-A (December 1978 p.
23), Item 1831X (August 1979, p. 437) or in the literature cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, for A) argon laser light source, Japanese Patent Application Laid-Open Nos. 60-162247 and 2-48653
No. 2,161,331, West German Patent No. 936,
For the simple merocyanine described in No. 071, B) helium-neon laser light source, JP-A-50-6242
5, No. 54-18726, trinuclear cyanine dyes shown in No. 59-102229; C) For LDE light sources, Japanese Patent Publications No. 48-42172, No. 51-9609;
55-39818, thiacarbocyanines described in JP-A No. 62-284343;
Tricarbocyanines described in No. 0-80841,
Dicarbocyanines containing a 4-quinoline nucleus as described in JP-A-59-192242 are advantageously selected. Representative compounds of those sensitizing dyes are shown below.

[0047]

[C21]

[0048]

[C22]

[0049]

[C23]

[0050]

[C24]

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes,
Included are hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or promoting development,
For example, polyalkylene oxide or its ether,
Derivatives such as esters and amines, thioether compounds,
It may also contain developing agents such as thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and aminophenols. Among them, 3-pyrazolidones (1-phenyl-
3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, etc.) are preferred,
Usually used at 5g/m2 or less, 0.01-0.2g/
m2 is more preferred. The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl) methyl ether, N,N-methylenebis-[β-(vinylsulfonyl)propionamide], etc.), active halides (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (such as mucochloric acid), N-carbamoylpyridinium salts (
1-morpholy)carbonyl-3-pyridinio)methanesulfonate, etc.), haloamidinium salts (1-(1-
Chloro-1-pyridinomethylene)pyrrolidinium, 2-
naphthalene sulfonate, etc.) can be used alone or in combination. Among them, JP-A-53-412
No. 20, No. 53-57257, No. 59-162546
Preferred are the active vinyl compounds described in No. 60-80846 and the active halides described in U.S. Pat. No. 3,325,287. A coating aid, a coating aid,
Various surfactants may be included for various purposes such as antistatic, improving slipperiness, emulsification and dispersion, preventing adhesion, and improving photographic properties (for example, promoting development, increasing contrast, and sensitizing). For example, saponins (steroids), alkylene oxide derivatives (
For example, polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, addition of silicone to polyethylene oxide products), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides)
, fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc.; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl Phosphate esters, N
-carboxy groups, sulfo groups, such as acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as phospho groups, sulfate ester groups, and phosphate ester groups; amphoteric interfaces such as amino acid salts, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters, alkyl betaines, and amine oxides. Activators: Cationic surfactants such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. can be used. Further, in order to prevent static electricity, it is preferable to use a fluorine-containing surfactant described in JP-A-60-80849.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide or polymethyl methacrylate in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion. The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example alkyl (meta)
Polymers containing as monomer components acrylate, alkoxy acrylic (meth) acrylate, glycidyl (meth) acrylate, etc. alone or in combination, or a combination of these and acrylic acid, methacrylic acid, etc. can be used. Gelatin is advantageously used as a condensing agent or protective colloid in photographic emulsions, 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 sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., single or copolymers thereof. Can be done. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used. The silver halide emulsion layer used in the present invention can contain a polymer latex such as an alkyl acrylate. As the support for the photosensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate paper, baryta-coated paper, polyolefin-coated paper, etc. can be used.

There is no particular restriction on the developing agent used in the developer used in the present invention, but it preferably contains dihydroxybenzenes, and dihydroxybenzenes and 1-phenyl are preferred since they facilitate obtaining good halftone quality. A combination of -3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may also be used. The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
, 5-dimethylhydroquinone, etc., and hydroquinone is particularly preferred. 1-phenyl-3 used in the present invention
- As a developing agent for pyrazolidone or its derivative, 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 and so on. Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-
(β-hydroxyethyl)-p-aminophenol, N
-(4-hydroxyphenyl)glycine, 2-methyl-
Among them, p-aminophenol, p-benzylaminophenol and the like are preferred, among which N-methyl-p-aminophenol is preferred. The developing agent is preferably used in an amount of usually 0.05 mol/liter to 0.8 mol/liter. Further, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols, the former should be mixed at 0.05 mol/liter - 0.05 mol/liter.
5 mol/l, the latter preferably in an amount of up to 0.06 mol/l. Sulfite preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The amount of sulfite is preferably at least 0.3 mol/liter, particularly preferably at least 0.4 mol/liter. Further, the upper limit is preferably up to 2.5 mol/liter, particularly up to 1.2 mol/liter. Alkaline agents used to set pH include pH adjusters such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, tribasic potassium phosphate, sodium silicate, and potassium silicate. Contains buffering agent. Additives used in addition to the above ingredients include compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, and methyl cellosolve. , organic solvents such as hexylene glycol, ethanol, and methanol; mercapto compounds such as 1-phenyl-5-mercaptotetrazole and 2-mercaptobenzimidazole-5-sulfonic acid sodium salt; indazole compounds such as 5-nitroindazole; It may contain an antifoggant such as a benztriazole compound such as 5-methylbenztriazole, and may further contain a toning agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, etc. as necessary. . In particular, the amino compounds described in JP-A-56-106244 and the imidazole compounds described in JP-B-48-35493 are preferred from the standpoint of accelerating development or increasing sensitivity. The developer used in the present invention contains a compound described in JP-A-56-24347 as a silver stain preventive agent, and a compound described in JP-A-62-212,65 as a development unevenness preventive agent.
The compound described in No. 1), as a solubilizing agent, JP-A-61-2
Compounds described in No. 67759 can be used.

The fixing solution is an aqueous solution containing, in addition to the fixing agent, a hardening agent (for example, a water-soluble aluminum compound), acetic acid, and a dibasic acid (for example, tartaric acid, citric acid, or a salt thereof) as necessary. , pH. 8 or more, more preferably 4.0 to 5.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, with ammonium thiosulfate being particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be changed as appropriate, and is generally about 0.1 to
It is about 5 mol/liter. The water-soluble aluminum salt used mainly as a hardening agent in the fixing solution is a compound generally known as a hardening agent for acidic hardening fixing solutions, such as aluminum chloride, aluminum sulfate, and potassium alum. As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. It is effective to use these compounds in an amount of 0.005 mol or more per liter of the fixing solution, particularly 0.01 mol/liter to 0.03 mol/liter. Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, ammonium potassium tartrate, and the like. Examples of citric acid or its derivatives that are effective in the present invention include citric acid, sodium citrate, and potassium citrate. The fixer further contains a preservative (e.g. sulfite, bisulfite), if desired.
A pH buffering agent (eg, acetic acid, boric acid), a pH adjusting agent (eg, ammonia, sulfuric acid), an image preservation improving agent (eg, potassium iodide), and a chelating agent can be included. Here, since the pH of the developer is high, the pH buffer is used in an amount of about 10 to 40 g/liter, more preferably about 18 to 25 g/liter. The photosensitive material of the present invention exhibits excellent performance in rapid processing using an automatic processor in which the preprocessing time is 15 seconds to 60 seconds. In the rapid development process of the present invention, the temperature and time of development and fixing are each about 25 DEG C. to 50 DEG C. and 25 seconds or less, preferably 30 DEG C. to 40 DEG C. and 4 seconds to 15 seconds.

In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed. Here, in the water washing step, water can be saved by using a two to three stage countercurrent washing method. Further, when washing with a small amount of washing water, it is preferable to provide a squeeze roller washing tank. Furthermore, part or all of the overflow liquid from the washing bath or stabilizing bath can be used as a fixing solution as described in JP-A-60-235133. By doing so, the amount of waste liquid is also reduced, which is more preferable. In addition, the washing water contains anti-mold agents (for example, the compounds described in Horiguchi's "Chemistry of Bacteria and Mildew Prevention", Japanese Patent Application Laid-open No. 115154/1983), washing accelerators (such as sulfites), chelating agents, etc. May contain. The temperature and time of the water washing or stabilization bath in the above method are 0°C to 50°C for 5 seconds to 30 seconds, preferably 4 seconds to 20 seconds at 15°C to 40°C. In the present invention, the developed, fixed, and water-washed photosensitive material is dried using a squeeze roller. Drying at 40°C to 80°C for 4 seconds to 3
It takes 0 seconds. The total processing time in the present invention is defined as the time after the leading edge of the film is inserted into the insertion slot of the automatic processor, the film passes through the developing tank, transfer section, fixing tank, transfer section, washing tank, transfer section, and drying section. This is the total time from the tip of the dryer until it emerges from the drying outlet. There are no particular limitations on the reducing fluid used in the present invention, and for example, those described in "The Theory of the Photographic Process" by Mies mentioned above can be effectively used. That is, a reducing component such as permanganate, persulfate, ferric salt, cupric salt, ceric salt, red blood salt, dichromate, etc. is used alone or in combination, and if necessary, sulfuric acid, etc. A reducing solution containing inorganic acids and alcohols, or reducing ingredients such as red blood salt, ferric ethylenediaminetetraacetic acid salt, and thiosulfate,
A reducing solution containing a silver halide solvent such as rhodan salt, thiourea or a derivative thereof, and, if necessary, an inorganic acid such as sulfuric acid, is used. The reducing liquid used in the present invention may further contain a compound having a mercapto group as described in JP-A No. 52-68419, if necessary. There are no particular restrictions on the composition of the power-reducing liquid used in the power-reducing treatment of the present invention and the processing conditions (temperature, time, etc.), and can be appropriately determined by those skilled in the art. Regarding the force reducing liquid and the force reducing method, the descriptions in the following patents can be referred to. JP-A No. 51-140733, No. 52-68419, No. 53-14901, No. 54-119236, No. 54-119237, No. 55-2245, No. 55-
No. 2244, No. 55-17123, No. 55-7944
No. 4 and No. 55-81344, the present invention will be described in more detail with reference to Examples.

[0057]

【Example】

Example 1 1 liquid H2O

1.0 liter gelatin


20g NaCl

20g 1,3
-dimethylimidazolidine-2-thione
20mg sodium benzenethiosulfonate
6mg 2
liquid H2O

600ml AgNO
3

150g 3 liquid H2O

600ml NaCl

(Amounts in Table 2) KBr

(Amounts in Table 2) K3 I
rCl6 (0.001% aqueous solution)
23ml
(NH4)3 RhCl6 (0.001%) aqueous solution 2.3ml 38℃,
Solutions 2 and 3 were simultaneously added to Solution 1, which was kept at pH 4.5, over a period of 10 minutes while stirring, to form core particles of 0.16 μm. Subsequently, the following liquids 4 and 5 were added over 10 minutes. Furthermore, 0.15 g of potassium iodide was added to complete particle formation. 4 liquid H2O

200ml AgNO
3

50g 5 liquid H2O

200ml NaCl

(Amounts in Table 2) KBr

(Amounts shown in Table 2) Thereafter, the mixture was washed with water by the flocculation method according to a conventional method, and 30 g of gelatin was added. Divide this into two equal parts and divide one half into two at pH 5.
．． 5. Adjust the pAg to 7.5 and add sodium thiosulfate.3.
7 mg and 6.2 mg of chloroauric acid were added, and gold-sulfur sensitization was carried out at 65° C. to achieve optimal sensitivity. The other emulsion is
Adjust the pH to 5.3 and pAg to 7.5, and add 2.6 mg of sodium thiosulfate and 1.0 N,N-dimethylselenourea.
mg and 6.2 mg of chloroauric acid were added thereto, and gold-sulfur-selenium sensitization was carried out at 55° C. to achieve optimal sensitivity. Preparation of coating sample B-2 was added as a sensitizing dye to the above emulsion at 10% per mole of Ag.
0 mg and as a supersensitizer, 4,4'-bis(4,6
-dinaphthoxy-pyrimidin-2-ylamino) 30
Spectral sensitization was performed by adding 0 mg. Furthermore, as an antifoggant, 4-hydroxy-6-methyl-1,3,3a,7
-Tetrazaindene, hydroquinone, 1-phenyl-
5-mercaptotetrazole was added at 500 mg, 2.5 g, and 50 mg per mole of Ag, and the particle size was 10 μm.
Colloidal silica of 30% as a gelatin binder, polyethyl acrylate latex as a plasticizer as a gelatin binder ratio of 25%, and 2-bis(vinylsulfonylacetamido)ethane as a hardening agent were added, and 3.0 g of Ag was placed on a polyester support. /m2, gelatin 1.0g
/m2. On top of this, the lower protective layer and upper protective layer shown in Table 1 were simultaneously coated.

[0058]

[Table 1]

Note that the polyester support has a back layer containing an antihalation dye.

Evaluation of the sample The obtained sample was exposed to xenon flash light with a light emission time of 10-5 seconds through an interference filter having a peak at 488 nm, and then processed using an automatic processor FG-710NH manufactured by Fuji Photo Film Co., Ltd. Sensitometry was performed at the temperature and time shown below. However, the developer and fixer are LD8 manufactured by Fuji Photo Film Co., Ltd.
35 and LF308 were used. Development 38℃ 14 seconds fixing 37℃ 9.7 seconds washing with water
26℃ 9 seconds squeeze 2.4 seconds dry
55℃ 8.3 seconds total
The reciprocal of the exposure amount giving a density of 3.0 in 43.4 seconds was taken as the sensitivity, and the relative sensitivity is shown in Table 1. Table 2 also shows the slope of the straight line connecting the points of density 0.1 and 3.0 on the characteristic curve as the gradation.

[0061]

[Table 2]

As can be seen from Table 2, the present invention has high contrast and is suitable for rapid processing.

Example 2 Table 3 shows the photographic performance when iron, rhenium, ruthenium, and osmium compounds were added to the 5 liquid in Example 1 as shown in Table 3.

[0064]

[Table 3]

From Table 3, iron, rhenium, ruthenium,
It is understood that the sensitivity becomes higher when an osmium compound is added.

Example 3 The following developing solution and fixing solution were placed in an automatic processor FG710NH, and a silver chlorobromide film with a coated silver amount of 3.6 g/m2 and a halogen composition of 70 mol% chlorine was processed under conditions of a blackening rate of 50%. 150 cc/m2 while replenishing the following developer and fixer at 180 cc/m2.
m2 running processing was performed. Using the samples used in Examples 1 and 2, the difference between the photographic performance with the Fr solution (before running treatment) and the photographic performance after running treatment will be shown. (Developer)
g/liter (working liquid) Potassium hydroxide

24 Potassium sulfite

70 Diethylenetriaminepentaacetic acid

2.4 Boric acid


10 Hydroquinone

35 Diethylene glycol
11
．． 2 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone

2.5 5-methylbenzotriazole
0.06 pH


10.05 (Fixer) Fixer Ammonium Thiosulfate
150g/liter Compound (VII-1)
0.2
5 mol/liter sodium bisulfite

30g/liter Ethylenediaminetetraacetic acid disodium dihydrate 0.025g/liter Adjust pH to 6.0 with sodium hydroxide

0
067]

[C25]

[0068]

[Table 4]

It is clear from Table 4 that the present invention exhibits stable performance even when running processing is performed with a small amount of developer replenishment.

Claims (4)

[Claims] 1. A silver halide photographic material having at least one light-sensitive emulsion layer containing silver halide grains on a support, wherein the silver halide grains contain a halogen compound containing 30 mol % or more of silver chloride. It is a core/shell type silver halide containing 10-6 mol or less of an iridium compound relative to silver, and has a higher silver bromide content in the shell part than in the core part, and further contains the halogen A silver halide photographic material characterized in that silver oxide grains are selenium-sensitized. Claim 2: The silver halide grains have a particle size of 10% based on silver.
2. The silver halide photographic material according to claim 1, containing -3 mol or less of an iron, rhenium, ruthenium, or osmium compound. 3. The method for developing a silver halide photographic material according to claim 1, wherein the processing is carried out using an automatic processor having a total processing time of 15 seconds to 60 seconds. 4. The method for developing a silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein the processing is carried out using an automatic developing machine with a developer replenishment amount of 200 cc/m 2 or less.