JPH10274824A - Silver halide photographic sensitive material and its treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material and its treatment to obtain a silver image with pure black tone even when the photosensitive material is stored for a long time or the photosensitive material is subjected to rapid treatment with a small amt. of a replenisher. SOLUTION: The coating liquid for a silver halide emulsion layer shows 0 to 70 mV silver potential at 40 deg.C, and the emulsion layer contains a leuco compd. which produces a blue dye by the reaction with an oxide as essential in a developing agent. The silver halide emulsion layer contains a compd. expressed by the formula Z-SM. In the formula, Z represents a heteroring directly or indirectly having groups selected from -So3 M1 , -OSO3 M1 , -PO4 M1 , -COOR1 , -OH and -NHR2 , M and M1 are hydrogen atoms, alkali metals or ammonium groups, and R1 is a hydrogen atom, alkali metal or 1 to 6C alkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material. The present invention relates to a silver halide photographic light-sensitive material having a good silver tone even when the above method is performed, and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, with respect to the development processing of silver halide photographic light-sensitive materials, it has been desired to reduce processing wastewater for shortening the processing time and environmental purification. For example, in the medical field, regular medical examinations, the spread of medical checkups, etc., and the number of examinations including diagnosis in general medical care have increased sharply, which has led to an increase in the number of X-ray photographs taken, further speeding up and processing development after imaging. Demands for further reduction of waste liquid are increasing.

In order to perform development processing in a short time, developability is required.
There is a demand for a photosensitive material having excellent fixability and drying in a short time after washing with water. It is known that tabular silver halide grains are effective for increasing the sensitivity of a light-sensitive material and improving covering power, and these tabular silver halide grains are so-called normal crystal halides such as hexahedral and octahedral. Compared to silver particles, the surface area is large in the same volume, so it is possible to increase the amount of spectral sensitizing dye adsorbed on the particle surface,
As a result, there is an advantage that high sensitivity can be achieved.

However, when the grain size or grain thickness is reduced, as in the case of tabular silver halide grains, the light scattering of the blue light component of silver formed by development is increased, and the silver image becomes strong yellow light. It has the disadvantage of yellowing.

[0005] In the case of a medical X-ray photosensitive material, the color tone of a silver image is preferably pure black or bluish black from the viewpoint of image diagnosis, and a silver image having a yellow tint is difficult and uncomfortable for an observer. It has disadvantages such as.

Conventionally, many studies have been reported on silver color tone improvement techniques from the light-sensitive material and development processing side. For example, a specific mercapto compound is well known as a representative color tone agent, but the desensitization is remarkable. Has disadvantages.

More recently, a technique disclosed in JP-A-5-165147, in which a specific dye is dissolved in a water-insoluble high-boiling organic solvent, dispersed in a small size in an aqueous solvent and contained in a light-sensitive material, is disclosed. Was done.

However, this technique has the disadvantage that the sensitivity fluctuates greatly when the photosensitive material is stored over time. Further, when applied to medical X-ray photosensitive materials, the intensifying screen that comes into contact with the photosensitive material at the time of exposure may cause stains. There was a problem of sticking. Further, this technique also has a disadvantage that the fog density increases because the unexposed portion contains the same amount of dye as the exposed portion.

To solve this disadvantage, Japanese Patent Laid-Open Publication No.
No. 7645 proposes a technique using a diffusion-resistant compound which emits a diffusible dye corresponding to a silver image, but the effect of improving the color tone of image silver and the effect of reducing fog are insufficient.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a pure black tone silver image even when the light-sensitive material is stored over time or processed with low replenishment speed, and a method of processing the same. On offer.

[0011]

The object of the present invention has been solved by the following constitution.

(1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer coating solution has a silver potential of 40 ° C.
A silver halide photographic light-sensitive material, characterized in that the emulsion layer contains a leuco compound which gives a blue dye by reacting with an oxidized form of a developing agent in the emulsion layer.

(2) The silver halide photographic material as described in (1), wherein the silver halide emulsion layer contains at least one compound represented by the following general formula (A).

General formula (A) Z-SM In the formula, Z is -SO ₃ M ₁ , -OSO ₃ M ₁ , -PO ₄ M ₁ ,-
COOR ₁ , represents a heterocyclic ring having directly or indirectly a group selected from —OH and —NHR ₂ , M and M ₁ represent a hydrogen atom, an alkali metal atom or an ammonium group,
R ₁ is a hydrogen atom, an alkali metal atom or a C 1-6
Represents an alkyl group.

(3) The silver halide photographic material as described in the above item (1) or (2), wherein the silver halide emulsion layer contains at least one polyhydroxybenzene compound.

(4) Any one of the above items (1) to (3)
The total processing time of the silver halide photographic light-sensitive material described in item 1 is 1
It was treated with 0-45 seconds, and method for processing a silver halide photographic material replenishment rate of the developing solution and fixing solution, characterized in that the treatment with an automatic developing machine respectively 30~180ml / m ^2.

Hereinafter, the present invention will be described in detail.

The silver halide photographic light-sensitive material of the present invention has at least one light-sensitive silver halide emulsion layer on one or both sides of a support, and at least one of the light-sensitive silver halide emulsion layers is When the emulsion coating solution is measured at a temperature of 40 ° C., the silver potential is 0 to 70 mV, preferably 6 to 70 mV.
A silver halide emulsion of 0 mV or less, more preferably 50 mV, is used.

The term "silver potential (unit: mV)" as used herein means a saturated silver-silver chloride electrode at a temperature of 40.degree.
It refers to the value measured with a silver ion selective electrode.

The silver potential of the emulsion can be adjusted at any time after chemical ripening, but preferably at the time of preparing an emulsion coating solution.

The silver halide emulsion of the present invention whose silver potential has been adjusted contains a leuco compound capable of giving a blue dye by reacting with an oxidized form of a developing agent. The leuco compounds used in the present invention include the following general formulas (I) to (VI)
Compounds represented by I) are mentioned.

[0022]

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[0023] In the formula, R ₁ represents an aryl group, a heterocyclic group, R ₂ represents a hydrogen atom, an alkyl group, a halogen atom, R ₃ represents a hydrogen atom, an alkyl group, an acylamino group, Z ₁ is - NHCO-, -CONH-, -NHCON
Represents H-, Z ₂ is _{-OH, -NHSO 2 R 12 (R} 12 represents an alkyl group, an aryl group) represents, CD represents a group represented by the following formula 2. R ₉ , R ₁₀ and R ₁₁ each represent a hydrogen atom or a non-metallic atomic group, and R ₁₀ and R ₁₁ may be linked to each other to form a ring structure.

[0024]

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Wherein R ₄ is a hydrogen atom, —COR ₁₃ , —S
O ₂ R ₁₃ (R ₁₃ is an alkyl group, an aryl group) represents, R _5, R ₆ are each a hydrogen atom, an alkyl group, an alkoxy group, an acylamino group, a halogen atom, R _7,
R ₈ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or a 5- or 6-membered nitrogen-containing heterocycle linked to each other or linked to R ₆ .

The leuco compound capable of giving a blue dye by reacting with the oxidized form of the developing agent in the present invention includes indoaniline leuco dye, indamine leuco dye, triphenylmethane leuco dye, and triarylmethane dye. Leuco dye, styryl leuco dye, N-acyl oxazine leuco dye, N-acyl thiazine leuco dye,
N-acyl diazine leuco dyes and xanthene leuco dyes can be exemplified. Particularly preferred are the compounds represented by the general formulas (I) to (VII).

In the general formulas (I) to (VII), the aryl group represented by R ₁ is an aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl) and a substituent (eg, an alkyl group, a dialkylamino group). Group, alkoxy group, aryloxy group, halogen atom such as fluorine, chlorine, bromine, alkoxycarbonyl group, acylamino group, carbamoyl group,
Alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group,
(Sulfamoyl group, alkylsulfamoyl group, alkylsulfonyl group, cyano group, nitro group).

The heterocyclic group represented by R ₁ (for example, a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group) may have the substituents listed for the aryl group. good.

The alkyl group represented by R ₂ or R ₃ is preferably an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, etc.). Preferred examples of the case of the ring formed by R ₂ and R _3, include those that form a benzene ring by R ₂ and R _3.

Z ₁ is -NHCO-, -CONH-, -N
HCONH—, wherein Z ₂ is —OH, —NHSO ₂ R
₁₂ (R ₁₂ represents an alkyl group or an aryl group).

[0031] CD represents a group represented by the chemical formula 2, R ₄
Represents a hydrogen atom, —COR ₁₃ , —SO ₂ R ₁₃ (R ₁₃ represents an alkyl group or an aryl group), and R ₅ and R ₆ represent a hydrogen atom, an alkyl group, an alkoxy group, an acylamino group, and a halogen atom, respectively. And R ₇ and R ₈ each represent a hydrogen atom, an alkyl group, an aryl group, an acyl group, or a 5- or 6-membered nitrogen-containing heterocycle linked to each other.

Among the halogen atoms represented by R ₂ , R ₅ or R ₆ (eg, F, Cl, Br, I), Cl is preferred.

The alkyl group represented by R ₅ , R ₆ , R ₇ , R ₈ , R ₁₂ or R ₁₃ is a linear or branched alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n -Butyl,
t-butyl, n-octyl, n-hexadecyl) and a substituent (for example, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a hydroxyl group, an acylamino group, a carbamoyl group, a sulfamoyl group, a sulfone) Amide group, cyano group)
May be provided.

The aryl group represented by R ₇ , R ₈ , R ₁₂ or R ₁₃ is an aryl group having 6 to 10 carbon atoms and has the same meaning as the aryl group defined for R ₁₁ .

The alkoxy group represented by R ₅ or R ₆ is a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms (eg, methoxy, ethoxy, n-butoxy, n-hexyloxy, n-decyloxy, isopropyl) Oxy, 2-
Methoxyethoxy, 2-chloroethoxy) are preferred.

The acylamino group represented by R ₃ , R ₅ or R ₆ is an acylamino group having 2 to 30 carbon atoms (eg, acetylamino, propionylamino, butyrylamino, myristoylamino, stearoylamino, pivaloylamino, benzoylamino). Preferably, it may have a substituent (for example, an alkoxy group, a phenoxy group, an alkyl-substituted phenoxy group).

The acyl group represented by R ₇ or R ₈ is an acyl group having 2 to 20 carbon atoms (eg, acetyl, propionyl, butyryl, benzoyl, lauroylisobutyryl)
Is preferred.

Examples of the 5- or 6-membered nitrogen-containing heterocycle formed by linking R ₇ and R ₈ include a piperidine ring, a pyrrolidine ring and a morpholine ring. Also, R ₇
And R ₆ are linked to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring, but R ₇ and R ₆ and R ₈ and R ₆ each share a nitrogen atom and are independently linked to form a 5- or 6-membered May be formed.

In the general formula (I), preferably, R ₁
Represents an aryl group, R ₂ represents a hydrogen atom, and R ₃ represents an acylamino group.

R ₉ , R ₁₀ and R ₁₁ represent a hydrogen atom or a nonmetallic substituent. More specifically, R ₉ , R ₁₀ and R ₁₁ represent a hydrogen atom, an aryl group, a heterocyclic group, an alkyl group, a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, an alkoxycarbonyl group. Amino group, aryloxycarbonylamino group, sulfonylamino group, aminocarbonylamino group, sulfamoylamino group, amino group (including anilino group), alkoxy group, aryloxy group, silyloxy group, heteryloxy group, alkylthio group, arylthio Group, hetenylthio group, halogen atom,
It represents a hydroxy group, nitro group, sulfamoyl group, sulfonyl group, azo group, acyloxy group, carbamoyloxy group, imide group, sulfinyl group, phosphoryl group, azolyl group and the like.

Preferred specific examples of R ₉ , R ₁₀ and R ₁₁ include a hydrogen atom and an aryl group (preferably having 6 to 6 carbon atoms).
20, for example phenyl, m-acetylaminophenyl,
p-methoxyphenyl), an alkyl group (preferably having 1 to 20 carbon atoms, for example, methyl, ethyl, isopropyl, t
-Butyl, n-octyl, n-dodecyl), a cyano group,
An acyl group (preferably having 1 to 20 carbon atoms, for example, acetyl, pivaloyl, benzoyl, furoyl, 2-pyridylcarbonyl), a carbamoyl group (preferably having 1 to 20 carbon atoms)
20, for example, methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, n-octylcarbamoyl), an alkoxycarbonyl group (preferably having 1 to 1 carbon atoms)
20, for example, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl), an aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, for example, phenoxycarbonyl, p-methoxyphenoxycarbonyl, m
-Chlorophenoxycarbonyl, o-methoxyphenoxycarbonyl), an acylamino group (preferably having 1 carbon atom)
To 20 alkylcarbonylamino groups (eg, formylamino, acetylamino, propionylamino, cyanoacetylamino), preferably an arylcarbonylamino group having 7 to 20 carbon atoms (eg, benzoylamino,
p-toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino), preferably a hetenylcarbonylamino group having 4 to 20 carbon atoms (for example, 2
-Pyridylcarbonylamino, 3-pyridylcarbonylamino, furoylamino)], an alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, methoxyethoxycarbonylamino), an aryloxycarbonylamino group (preferably Has 7 to 20 carbon atoms, for example, phenoxycarbonylamino, p-methoxyphenoxycarbonylamino, p-methylphenoxycarbonylamino,
m-chlorophenoxycarbonylamino, o-chlorophenoxycarbonylamino), sulfonylamino group (preferably having 1 to 20 carbon atoms, for example, methanesulfonylamino, benzenesulfonylamino, toluenesulfonylamino), aminocarbonylamino group (preferably having 1 to 20, for example, methylaminocarbonylamino, ethylaminocarbonylamino, anilinocarbonylamino, dimethylaminocarbonylamino), a sulfamoylamino group (preferably having 1 to 20 carbon atoms, for example, methylaminosulfonylamino, ethylaminosulfonylamino) , Anilinosulfonylamino), an amino group (including an anilino group, preferably having 0 to 20 carbon atoms, for example, amino,
Methylamino, dimethylamino, ethylamino, diethylamino, n-butylamino, anilino), alkoxy group (preferably having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropoxy, n-butoxy, methoxy, n-
Dodecyloxy), an aryloxy group (preferably having 6 to 20 carbon atoms such as phenoxy, m-chlorophenoxy, p-methoxyphenoxy, o-methoxyphenoxy), a silyloxy group (preferably having 3 to 20 carbon atoms such as trimethylsilyloxy, t-butyldimethylsilyloxy, cetyldimethylsilyloxy, phenyldimethylsilyloxy), a heteryloxy group (preferably having 3 to 20 carbon atoms, for example, tetrahydropyranyloxy, 3
-Pyridyloxy, 2- (1,3-benzimidazolyl) oxy), an alkylthio group (preferably having 1 to carbon atoms)
20, e.g., methylthio, ethylthio, n-butylthio, t-butylthio), an arylthio group (preferably having 6 to 20 carbon atoms, e.g., phenylthio), a heterylthio group (preferably having 3 to 20 carbon atoms, e.g., 2-pyridylthio, 2- ( 1,3-benzoxazolyl) thio, 1-hexadecyl-1,2,3,4-tetrazolyl-5-thio, 1- (3-N-octadecylcarbamoyl) phenyl-1,2,3,4-tetrazolyl -5-thio), a heterocyclic group (preferably having 3 to 20 carbon atoms, for example, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-
2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1-pyrrolyl, 2-furanyl, 2-pyridyl, 3-
Pyridyl), a halogen atom (fluorine, chlorine, bromine), a hydroxy group, a nitro group, a sulfamoyl group (preferably having 0 to 20 carbon atoms, for example, methylsulfamoyl and dimethylsulfamoyl), a sulfonyl group (preferably having 1 carbon atom) To 20, for example, methanesulfonyl, benzenesulfonyl, toluenesulfonyl), an azo group (preferably having 3 to 20, for example, p-nitrophenylazo), an acyloxy group (preferably having 1 to 20, for example, formyloxy, acetyloxy) , Benzoyloxy), a carbamoyloxy group (preferably having 1 to 20 carbon atoms, for example, methylcarbamoyloxy, diethylcarbamoyloxy), and an imide group (preferably having 4 to 20 carbon atoms, for example,
Succinimide, phthalimide), sulfinyl group (preferably having 1 to 20 carbon atoms, for example, diethylaminosulfinyl), phosphoryl group (preferably having 0 to 20 carbon atoms,
Examples thereof include diaminophosphoryl) and an azolyl group (preferably having 2 to 20 carbon atoms, for example, 3-pyrazolyl).

The following are the general formulas (I) to (VII) of the present invention.
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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In the present invention, the amount of the leuco compound to be added is from 1 × 10 ^-6 mol to 5 × 1 per mol of silver halide.
It is preferably contained in an amount of 0 ^-2 mol, and particularly preferably in the range of 1 x 10 ^-5 mol to 2 x 10 ^-2 mol.

The leuco compound is a suitable water-miscible organic solvent,
For example, it can be used by dissolving in alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. Also, by using an oil dispersion such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexane by a well-known emulsification dispersion method, the mixture is mechanically emulsified and dispersed. A liquid can be prepared and used. Alternatively, the leuco dye powder can be dispersed in water by a ball mill, a colloid mill or ultrasonic waves by a method known as a solid dispersion method.

The leuco compound capable of giving a blue dye by reacting with the oxidized form of the developing agent of the present invention comprises an emulsion layer and / or
Alternatively, it can be added to an adjacent hydrophilic colloid layer.

The timing of adding the compound to the emulsion is not particularly limited, but it is preferably added to any step from the end of chemical ripening to coating.

The silver halide emulsion of the present invention containing the above-mentioned leuco compound contains a compound represented by the following general formula (A).

General formula (A) Z-SM In the formula, Z is -SO ₃ M ₁ , -COOR ₁ , -OH and -N
Heterocyclic group having a substituent selected from HR ₂ directly or indirectly, such as an oxazole ring, a thiazole ring, an imidazole ring, a selenazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, an oxadiazole ring, a pyrimidine ring, a thiazine ring, Triazine ring, thiodiazine ring or a ring bonded to another carbon ring or hetero ring, such as benzothiazole ring, benzotriazole ring, benzimidazole ring, benzoxadiazole ring, benzoselenazole ring, naphthoxazole ring, triazaindolizine A ring, a diazaindolizine ring or a tetraazaindolizine ring (these rings are substituted with at least one of the above groups).

Preferred are an imidazole ring, a tetrazole ring, a benzoxazole ring and a triazole ring. Particularly preferred is a tetrazole ring.

M and M ₁ in the general formula (A) represent a hydrogen atom, an alkali metal atom or a quaternary ammonium group,
R ₁ is a hydrogen atom, an alkali metal atom or a carbon number of 1 to 6
Wherein R ₂ is a hydrogen atom, having 1 to 6 carbon atoms.
Alkyl group, -COR _3, -COOR ₃ or -SO ₂ R ₃
R ₃ represents a hydrogen atom, an aliphatic group (for example, having 1 to 1 carbon atoms)
20 alkyl groups, specifically, a methyl group, an ethyl group, n
-Propyl group, i-propyl group, t-butyl group, n-octyl group, dodecyl group, cyclohexyl group and the like, or aromatic group (for example, aryl group having 6 to 20 carbon atoms, specifically phenyl group, naphthyl) And these groups may further have a substituent.

The number of hydrophilic groups in the compound represented by formula (A) is not limited as long as it is one or more, and a compound having two or more hydrophilic groups is also preferably used. Further, the pKa of the hydrophilic groups may be any number, but one having at least one hydrophilic group having a pKa of 7 or more is preferably used. Particularly hydrophilic group -SO ₃ M _1, it shall preferably -COOR _1.

Further, so-called precursor-type compounds which release the compound represented by the general formula (A) over time and / or into a treatment solution can also be preferably used.

Among the heterocyclic mercapto compounds represented by the general formula (A), particularly preferred are those represented by the following general formula [A-a].

[0065]

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In the formula, X and Y represent a nitrogen atom or CR ₄ (R ₄
Is a hydrogen atom or a substitutable group. ) And R ₄
Is a substituted or unsubstituted organic group, and the organic group is an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group,
n-propyl group, i-propyl group, t-butyl group, n-
An octyl group, a dodecyl group, a cyclohexyl group, etc.), an aryl group having 6 to 20 carbon atoms (e.g., phenyl group, naphthyl group, etc.), a heterocyclic group (5 or more containing at least one nitrogen atom, oxygen atom or sulfur atom) A 6-membered ring, a 6-membered ring, or a 7-membered ring, including those that form a condensed ring at an appropriate position, such as a pyridine ring, a quinoline ring, a pyrimidine ring, etc.) or an alkyl group, an aryl group, or a hetero ring group -S -, - O -, - NR 5 -, - CO -, - SO
—, —SO ₂ — represents a group constituted via a linking group composed of, for example. (R ₅ represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms.) Examples of the substituent of the alkyl group, the aryl group and the heterocyclic group or the substitutable group represented by R ₄ include a group represented by the general formula (A )
It has the same meaning as the substituent represented by the heterocyclic residue therein, and may be different when there are two or more substituents.

Preferred compounds in the general formula [A-a] are
X and Y are nitrogen atoms, and R ₅ is an aryl group having two or more groups selected from an anion group or a group capable of dissociating into an anion. Particularly preferred aryl group is ortho-position to mercaptotetrazole group. Is an aryl group having a hydroxyl group. M ₂ represents a hydrogen atom, an alkyl metal, or a quaternary ammonium group, and at least one of R ₄ and R ₅ has a group selected from an anion group and a group capable of dissociating into an anion.

The general formula (A) and the general formula [A-
Specific examples of the compound represented by a) are shown below, but the present invention is not limited to these compounds.

[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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The compound represented by the formula (A) is known and is described, for example, in US Pat. A. Burgess et al., "Journal of Heterocyclic Chemistry" (DA Berges et.a.
l. , Journal of Heterocyclic
c Chemistry) Vol. 15 No. 981 (1978)
No.), “The Chemistry of Heterocyclic.
Compound "Imidazole and Derivatives, Part 1 (The Chemistry of He
terocyclic Compound, Imida
zole and Derivatives part
1) Pages 336-339, Chemical Abstracts (C
Chemical Abstract) 58, 7921 (1963), p. 394, or the like.

In the present invention, the amount of the compound represented by the above general formula (A) may be 1 to 1 mol per mol of silver halide.
It is preferably contained in an amount of from 10 ^-5 mol to 1 x 10 ^-2 mol, and particularly preferably from 1 x 10 ^-4 mol to 1 x 10 ^-3 mol.

The compound may be added alone or in combination with a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide. And methylcellosolve.

Further, it may be added by the same emulsification dispersion method or solid dispersion method as described above for the well-known leuco compound.

The timing of adding the compound to the emulsion is not particularly limited, but it is preferably added to any step from the end of chemical ripening to coating.

The silver halide emulsion according to the present invention contains a polyhydroxybenzene compound. Less than,
The polyhydroxybenzene compound used in the present invention will be described. The polyhydroxybenzene compound preferably used in the present invention is a compound represented by the following general formula.

[0080]

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In the formula, X is -H, -OH, a phenyl group,-
Cl, -Br, -I, -COOH, -CH 2 CH 2 COO
_{H, -CH (CH 3) 2} , -CH 3, -C (CH 3) 3, -
OCH _3, -CHO, represents a -SO ₃ Na.

In the above general formula, X is Cl, B
r and I are preferred, and particularly preferably Br. Specific examples of particularly preferred compounds among the polyhydroxybenzenes used in the present invention are shown below.

[0083]

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The place of addition of the polyhydroxybenzene compound is preferably a silver halide emulsion layer, but may be another hydrophilic colloid layer adjacent to the silver halide emulsion layer.

The timing of adding the polyhydroxybenzene compound of the present invention may be selected at any time during the emulsion production process, but is generally preferably immediately before coating the emulsion up to 6 hours before, specifically, 1 m ² of the light-sensitive material. It is preferably from 3 × 10 ⁻² mol to 3 × 10 ⁻⁶ mol, more preferably from 3 × 10 ⁻³ mol to 3 × 10 ⁻⁵ mol per mol.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (1
(December 978), page 22-23, 1. Emulsion manufacturing method "E
mulsion Preparation and T
types (RD) No. 18
716 (November 1979), p. 648.

Emulsions used in the silver halide photographic light-sensitive material of the present invention include, for example, T.I. H. James T
he Theory of the Photogra
phy Process "4th edition Macmilla
n, published by Company (1977), pp. 38-104,
G. FIG. F. "Photographic Emulsion Chemistry" by Dauffin, "Photo
optic Emulsion Chemist
ry "Focal Press (1966),
P. "The Physics and Chemistry of Photography" by Glafkids, "Ch
imie et Physique Photogra
phique "Paul Montel (196
7 years). L. "Manufacture and Coating of Photographic Emulsions," Zelikman et al., "Making and Coating"
Photographic Emulsion "Foc
It is prepared by the method described in al Press (1964).

That is, under solution conditions such as an acidic method, an ammonia method and a neutral method, mixing conditions such as a forward mixing method, a reverse mixing method, a double jet method and a controlled double jet method, a conversion method, and a core / shell method. The particles can be produced using particle preparation conditions such as those described above, and a combination method thereof.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains.

The monodispersed emulsion referred to here means that the average grain diameter is measured from a micrograph of silver halide grains or the like.
At least 95% of the grains by number or weight are silver halide grains within ± 30%, preferably ± 20%, of the average grain size. The term “monodispersity” as used herein refers to a method disclosed in
0-162244, wherein the coefficient of variation with respect to particle size is 20% or less.

The crystal structure of the silver halide may be different from the silver halide composition inside and outside. That is, the core and the core have at least one different silver halide composition.
It has a core / shell structure composed of shells of layers or more. The silver iodide content of the high iodine part is 5 to 40 mol%, particularly preferably 5 to 30 mol%.

A method for producing such a monodisperse emulsion is known.
As a method for obtaining the above-mentioned monodispersed emulsion, for example, a method of using a seed crystal and supplying silver ions and halide ions with the seed crystal as a growth nucleus to perform growth is particularly preferable.

The method of producing the core / shell type emulsion is well known, for example, British Patent 1,027,146, US Pat. No. 3,505,068, US Pat. No. 4,444,877 or JP-A-60-143331. And the like.

The silver halide grains in the silver halide emulsion layer are preferably tabular silver halide grains. Tabular silver halide grains refer to grains having two opposing parallel main planes and have an average aspect ratio of 2 or more and less than 20,
Preferably it is 3 or more and less than 15. The average aspect ratio is represented by the ratio of the average particle diameter to the average particle thickness. Here, the grain size means an average projected area diameter (hereinafter referred to as a grain size), and is a circle equivalent diameter of a projected area of the tabular silver halide grains (a diameter of a circle having the same projected area as the silver halide grains). ), And the thickness refers to the distance between two parallel main planes forming tabular silver halide grains.

The edge ratio (long side edge length / short side edge length) of the tabular silver halide grains is from 1 to 2, preferably from 1 to 1.6, and more preferably from 1 to 1.2. is there.

In the present invention, the emulsion layer containing tabular silver halide grains has an aspect ratio of 2 or more and an edge ratio (long side edge length / short side edge length) of 50% or more of the total projected area. Consisting of 1 to 2 tabular silver halide grains,
It is preferably at least 70%, more preferably at least 90%.

The tabular silver halide grains are silver chloroiodobromide or silver bromoiodide, and have an average silver iodide content of from 0 to 0.
It is preferably less than 2 mol%, more preferably 0.1 to 1.0 mol%.

The average grain size of the tabular silver halide grains is 0.1.
It is preferably from 15 to 5.0 μm, and from 0.4 to 3.0 μm.
More preferably, it is 0 μm, most preferably 0.1 μm.
4 to 2.0 μm.

The tabular silver halide grains are preferably monodisperse emulsions having a narrow grain size distribution, specifically, (standard deviation of grain size / average grain size) .times.100 = width (%) of grain size distribution. When the area is defined, it is preferably 25% or less, more preferably 20% or less.

The emulsion may be subjected to a water washing method such as a Nudel washing method or a flocculation sedimentation method to remove soluble salts (desalting treatment step). As a preferred water washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or a coagulated polymer agent described in JP-A-2-7037, exemplified by G-
3, a method using G-8 or the like is a particularly preferred desalting method.

The temperature for chemical ripening of the silver halide emulsion can be arbitrarily determined, but is in the range of 20 to 90 ° C., preferably 3 to 90 ° C.
It is 0-80 degreeC, More preferably, it is 35-70 degreeC.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention can be spectrally sensitized. The spectral sensitizing dye may be any of commonly used sensitizing dyes such as cyanine, merocyanine or complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl dye, and hemioxonol dye.

These sensitizing dyes can be used alone or in combination. Spectral sensitizing dyes
It is preferably added as a solution dissolved in an organic solvent such as methanol.

The addition amount of the spectral sensitizing dye is not uniform depending on the kind of the dye and the emulsion conditions, but is preferably from 10 to 900 mg, more preferably from 200 to 600 mg, per mol of silver halide.
Is particularly preferred. The spectral sensitizing dye is preferably used after the step of growing silver halide grains and before the end of the chemical ripening step, and particularly preferably before the start of chemical ripening.

In the emulsion, various photographic additives can be used before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure (RD) No. 17643 (December 1978
No.) and the same No. No. 18716 (November 1979) and the same No. 308119 (December 1989).

The silver halide photographic light-sensitive material of the present invention has at least one light-sensitive layer on a support, and may have an undercoat layer, an antihalation layer, an intermediate layer and a protective layer, if necessary. Good. As the support, for example, the aforementioned RD-1
7643 and RD-308119, page 1009. As a suitable support, a polyethylene terephthalate film or the like may be used, and an undercoat layer may be provided on the surface of the support to improve the adhesion of the coating layer, or corona discharge, ultraviolet irradiation or the like may be applied.

The processing of the silver halide photographic light-sensitive material of the present invention can be carried out, for example, by the above-mentioned RD-17643 XX to XXI, 29 to
XX to XXI of page 30 or 308119, 1011 to 10
The treatment with the treatment liquid as described on page 12 may be performed.

As the developer, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-P-aminophenol) and the like can be used alone or in combination. Can be used. In the developer, for example, known preservatives, alkali agents, pH buffering agents, antifoggants, hardeners, development accelerators, surfactants,
An antifoaming agent, a color tone agent, a water softener, a dissolution aid, a viscosity imparting agent, and the like may be used as necessary.

The fixing solution contains a fixing agent such as thiosulfate and thiocyanate, and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

The method for developing a silver halide photographic light-sensitive material of the present invention is performed by an automatic developing machine. The total processing time in the present invention means that (Dry to Dry) is 10 to 45 seconds.

Here, Dry to Dry refers to the time from when the tip of the photosensitive material starts to be immersed in the developing solution to when the tip comes out of the drying zone through a processing step, and more preferably 15 to 30. Seconds.

The development temperature is preferably 25 to 50 ° C.
-40 ° C is more preferred. The development time is 5 to 45 seconds, preferably 8 to 30 seconds.

The fixing temperature and time are about 20 to 50 ° C.
For 6 to 20 seconds, more preferably 6 to 15 seconds at 30 to 40 ° C.

In the present invention, the replenishment amounts of the developing solution and the fixing solution are each preferably 180 ml / m ² or less, and more preferably 30 to 160 ml / m ^2.
m ² , particularly preferably 30 to 100 ml / m ² .

The drying time may be generally 35 to 100 ° C., preferably 40 to 80 ° C., or a drying zone provided with heating means by far infrared rays may be provided in the automatic developing machine.

The automatic developing machine is provided with a mechanism for applying water or a rinsing solution of an acidic solution having no fixing ability to the photosensitive material during the respective steps of developing, fixing and washing with water (Japanese Unexamined Patent Publication No.
-264953) may be used. Further, a device capable of adjusting a developing solution and a fixing solution may be incorporated.

[0117]

The present invention will be described below in more detail with reference to examples.

Example 1 (Preparation of particles) Emulsion A In a reaction vessel having a volume of 4 liters, an average molecular weight of 15 was prepared.
An aqueous solution containing 1200 000 gelatin (1200 ml of water, 7 g of gelatin, 4.5 g of KBr) was added.
1.9M A by double jet method with stirring
A gNO ₃ aqueous solution and a 1.9 M KBr aqueous solution were simultaneously added at 25 ml / min for 25 seconds, respectively, to obtain nuclei of tabular grains. 350 ml of this emulsion was used as a seed crystal, and 650 ml of an inert gelatin aqueous solution (gelatin 20 g, KBr
1.2 g) and the temperature was raised to 75 ° C. for aging for 80 minutes.

Next, the pH of the emulsion was adjusted to 7 with HNO ₃ (3N), 1 g of KBr was added, and then 405 ml of a 1.9 M AgNO ₃ aqueous solution and a KBr aqueous solution were added while maintaining the pAg at 8.3. At the beginning of the addition, the addition was performed at 2.6 ml / min, and the addition was performed while accelerating the flow rate so that the ratio between the initial speed and the final speed became 10 times.

After lowering the temperature to 55 ° C., 0.6M AgN
O ₃ aqueous solution 40ml and 0.6M KBr aqueous solution 40ml
Was added over 10 minutes. Add KBr and add pA
g was adjusted to 8.9, and 157 ml of a 1.9 M AgNO ₃ aqueous solution and 157 ml of a 1.9 M KBr aqueous solution were added to 26 g.
Emulsion A was obtained by adding over a period of minutes.

The preparation method of Emulsion A referred to the examples in JP-A-2-838.

The resulting emulsion A had an average aspect ratio of 7.0 and a coefficient of variation in grain size of 10%. The average particle size was 0.75 μm in sphere equivalent diameter.

(Chemical Sensitization) The obtained emulsion A was 60
The following chemical sensitization was performed under the conditions of ° C, pH 6.20, and pAg 8.4. First, sensitizing dye A described later was added in an amount of 2.0 × 10 ⁻³ mol per mol of silver. Subsequently, 3.0 × 10 ⁻³ mol of potassium thiocyanate per mol of silver, 8 ×
10 ^-6 mol of potassium chloroaurate, 1 × 10 ^-5 mol of sodium thiosulfate and 3 × 10 ^-6 mol of selenium compound-1
Was added.

[0124]

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(Preparation of Emulsion Coating Solution) A coating solution was prepared by adding the following chemicals per mole of silver halide to Emulsion A subjected to chemical sensitization.

2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 mg trimethylolpropane 9 g dextran (average molecular weight 39,000) 18.5 g potassium polystyrene sulfonate (average molecular weight 60 1.81 g Snowtex C (Nissan Chemical Co., Ltd.) 29.1 g Gelatin (adjusted so that the total amount applied to one side is 2.4 g / m ² ) Rubber rubber (1,2-bis ( (Vinylsulfonylacetamide) ethane) The swelling ratio was adjusted to 230%.

The leuco compound according to the present invention, the compound of the formula (1) and the polyhydroxybenzene compound were added as shown in Table 1.

(Adjustment of Emulsion Potential) In preparing an emulsion coating solution, a 0.1 mol solution of potassium bromide was used to adjust the potential as shown in Table 1.

(Preparation of Surface Protective Layer Coating Solution) The following additives were added to the surface protective layer coating solution. The amount of addition was indicated by the amount of application per m ² .

Gelatin 0.966 g Sodium polyacrylate (average molecular weight 400,000) 0.023 g Compound (P-1) 0.013 g Compound (P-2) 0.045 g Compound (P-3) 0.0065 g Compound (P -4) 0.003 g compound (P-5) 0.001 g polymethyl methacrylate (average particle size 3.7 μm) 0.087 g proxel 0.0005 g (adjusted to pH 7.4 with NaOH)

[0131]

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

[0133]

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434 ml of water and Triton X20
791 ml of a 6.7% aqueous solution of a 0® surfactant (TX-200®) was placed in a 2 liter ball mill. 20 g of the dye were added to this solution.
400 ml of zirconium oxide (ZrO) beads (2 m
m diameter) and the contents were ground for 4 days. After this, 1
160 g of 2.5% gelatin was added. After decontamination, the ZrO beads were removed by filtration. Observation of the obtained dye dispersion revealed that the particle size of the crushed dye was 0.37 μm.
Met. Furthermore, by performing a centrifugation operation, 0.9 μ
m or more of the dye particles were removed. Thus, a dye dispersion K was obtained.

(2) Preparation of Support A corona discharge was carried out on a biaxially stretched polyethylene terephthalate film having a thickness of 183 μm, and a first undercoating liquid having the following composition was applied in an amount of 5.1 cc / m ² . It was applied by a wire bar coater and dried at 175 ° C. for 1 minute.

Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used contained a dye having the following structure at 0.04% by weight.

[0137]

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Composition Butadiene-styrene copolymer latex solution 79 cc (solid content 40% butadiene / styrene polymerization ratio = 31/69) Emulsifier / dispersant Sodium dihexylsuccinate-1-sulfonate was added at 0.4 wt. % Containing 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20.5 cc distilled water 900.5 cc
The undercoat layer is coated on both sides by a wire bar coater method in such a manner that the coating amount is as described below.
Coated and dried at ℃.

Gelatin 160 mg / m ² Dye dispersion K 26 mg / m ² as dye solids

[0140]

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(Preparation of photographic material) The emulsion layer and the surface protective layer were coated on both sides of the support prepared as described above by a simultaneous extrusion method. The amount of silver applied per side was 1.75.
g / m ² . Thus, the sample No. 1-14 were obtained.

The following samples were evaluated for the following photographic characteristics (sensitivity). The compositions of the developing solution and the fixing solution used in the present invention are shown below.

Developer Composition Part-A (for finishing 12 liters) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetriaminepentaacetic acid 120 g Sodium bicarbonate 132 g Boric acid 40 g 5-Methylbenzotriazole 1.4 g 1-phenyl -5-mercaptotetrazole 0.25 g 4-hydroxymethyl-4-methyl-1-phenylpyrazolidone 102 g hydroquinone 390 g diethylene glycol 550 g Water is added to make up to 6000 ml.

Part-B (for finishing 12 liters) Glacial acetic acid 70 g 5-Nitroindazole 0.6 g Glutaraldehyde (50% solution) 8.0 g N-acetyl-DL-penicillamine 1.2 g Starter Glacial acetic acid 120 g HO (CH ₂ 1) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH 1 g Potassium bromide 225 g CH ₃ N (C ₃ H ₆ NHCONHC ₂ HSC ₂ H ₅ ) ₂ 1.0 g Pure water is added to make up to 1 liter.

Fixer Formulation Part-A (for 18.3 liter finishing) Ammonium thiosulfate (70 wt / vol%) 4500 g Sodium sulfite 450 g Sodium acetate 450 g Boric acid 110 g Tartaric acid 60 g Sodium citrate 10 g Gluconic acid 70 g 1- (N, N -Dimethylamino) -ethyl-5-mercaptotetrazole 18 g Glacial acetic acid 330 g Aluminum sulfate 62 g Finish up to 7200 ml with pure water The developer is prepared by adding Part-A, Par to about 5 liters of water.
t-B was added at the same time, water was added while stirring and dissolving, and the pH was adjusted to 12 liters and the pH was adjusted to 10.53.

This is used as a developing replenisher.

The above-mentioned starter was added to 1 liter of the developing replenisher at 20 ml / l to adjust the pH to 10.30, thereby obtaining a working solution.

The fixing solution was prepared by adding Part 5 to about 5 liters of water.
-A was added, water was added while stirring and dissolving, and the mixture was adjusted to 18.3 liters and the pH was adjusted to 4.6 using sulfuric acid and NH ₄ OH.

This is used as a fixing replenisher.

Evaluation <Evaluation of Silver Tone> The obtained sample was subjected to 23 ° C., RH 40%
After being allowed to stand for 3 days, the mixture was sandwiched between fluorescent intensifying screens KO-250 (manufactured by Konica Corporation) and the transmission density after the development processing was 1.2.
X-rays were applied to develop. In the development, an automatic developing machine SRX-503 (manufactured by Konica Corporation) was modified, and Dry to Dry (all processing steps) was processed in a 25-second mode in the following steps. However, each sample was used after running from a new solution so that the activity of the treatment solution was in an equilibrium state.
The replenishment amounts of the developing solution and the fixing solution during the running process were 100 ml / m ² respectively.

The obtained developed sample was observed on a Schaukasten, and the silver tone due to transmitted light was visually evaluated according to the following criteria.

A: Pure black B: Slightly reddish black C: Slightly yellowish black D: Yellowish black Also, a sample stored at 50 ° C. and RH 50% for 1 week is similarly treated. Exposure and development were performed and evaluated. Table 1 shows the obtained results.

(Processing Step) Step Processing Temperature (° C.) Processing Time (Second) Development + Cover 35 7.8 Fixation + Cover 33 5.4 Rinse + Cover 18 4.3 (7 liters of flush water / minute supply) Squeeze 40 3.1 Drying 50 4.4 Total 25.0 The results obtained are shown in Table 1.

[0154]

[Table 1]

As is clear from the table, the sample of the present invention was excellent in that the color tone of the image silver was a pure black tone even in the low replenishment ultra-rapid processing. Further, the silver halide photographic material is heated to a high temperature.
Even when stored for a long time under high humidity, the sample of the present invention did not deteriorate in silver tone.

[0156]

As has been demonstrated in the examples, according to the present invention, a silver halide photograph in which a light-sensitive material can be stored over time and the color tone of the image silver can be obtained as a pure black tone even when subjected to low replenishment ultra-rapid processing. A photosensitive material and a processing method thereof were obtained.

Claims (4)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The silver potential of the silver halide emulsion layer coating solution was 0 at a temperature of 40 ° C.
a silver halide photographic light-sensitive material, wherein the emulsion layer contains a leuco compound which gives a blue dye by reacting with an oxidized form of a developing agent in the emulsion layer. 2. The silver halide photographic material according to claim 1, wherein the silver halide emulsion layer contains at least one compound represented by the following general formula (A). In the general formula (A) Z-SM formula, Z is _{-SO 3 M 1, -OSO 3 M} 1, -PO 4 M 1, -
COOR ₁ , represents a heterocyclic ring having directly or indirectly a group selected from —OH and —NHR ₂ , M and M ₁ represent a hydrogen atom, an alkali metal atom or an ammonium group,
R ₁ is a hydrogen atom, an alkali metal atom or a C 1-6
Represents an alkyl group. 3. The silver halide photographic material according to claim 1, wherein the silver halide emulsion layer contains at least one polyhydroxybenzene compound. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the total processing time is 10 to 45.
Seconds, and the replenishment amounts of the developing solution and the fixing solution are 3
Method for processing a silver halide photographic material which comprises treating with an automatic developing machine is 0~180ml / m ^2.