JPH09265156A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive material handleable in a light room by incorporating the fine solid particles of a specified dye in a disperson in a hydrophilic colloidal layer. SOLUTION: The silver halide photographic sensitive material has photosensitive silver halide emulsion layer and nonphotosensitive hydrophilic colloidal layers and at least one hydrophilic colloidal layers contains the dispersed fine solid particles of the dye represented by the formula in which each of Za-Zc is -N=or-C(R<2> )=; each of R<1> and R<2> is an H atom or a univalent substituent; each of L<1> -L<3> is a methine group; B<1> is an N-containing 6-membered ring; and (n) is 0 or 1. This photosensitive material is processed, preferably, by using an automatic developing machine and at that time, it is processed while replenishing each specified amount of developing solution and a fixing solution in proportion to the area of the photosensitive material.

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 (hereinafter also simply referred to as a light-sensitive material) and a processing method thereof, and more specifically, a silver halide photographic light-sensitive material which can be handled in a bright room and a processing thereof. More specifically, the present invention relates to a silver halide photographic light-sensitive material for printing plate making that can be handled in a bright room, and a processing method thereof.

[0002]

2. Description of the Related Art Conventionally, silver halide photographic light-sensitive materials have been widely used because they can obtain images with high sensitivity and high resolution. On the other hand, for printing plate making, from the viewpoint of improving workability, there is a demand to reduce fogging due to safety light in a bright room, and JP-A-55-120030.
No. 55-155350, No. 55-155351
No. 56-12639, No. 63-27838, No. 63-197943, JP-A-3-167546, No. 5-11382, International Application Publication No. 88/06794,
In European Patent Nos. 489973 and 524594, it is proposed to incorporate a specific dye into a light-sensitive material. However, the inclusion of these dyes deteriorates the residual color at the time of processing, and also makes it clear that the photographic performance such as sensitivity varies when the photosensitive material is used after long-term storage.

[0003]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a silver halide photographic light-sensitive material which can be handled in a bright room and a processing method thereof. A second object of the present invention is to provide a silver halide photographic light-sensitive material having less residual color and a processing method thereof. A third object of the present invention is to provide a silver halide photographic light-sensitive material in which the photographic performance of the light-sensitive material hardly changes with time and a processing method thereof.

[0004]

The above object of the present invention is achieved by the following constitution.

[0005] 1. In a silver halide photographic light-sensitive material having a silver halide photographic emulsion layer on a support and a non-photosensitive hydrophilic colloid layer, at least one hydrophilic colloid layer is represented by the following general formula (1). A silver halide photographic light-sensitive material comprising a solid fine particle dispersion of a dye.

[0006]

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In the formula, Za, Zb and Zc each represent -N = or -C (R ² ) =, R ¹ and R ² represent a hydrogen atom or a monovalent substituent, and L ¹ , L ² and L ³ represents a methine group, B ¹ represents an oxygen-containing 6-membered ring, and n represents 0 or 1.

2. In a silver halide photographic light-sensitive material having a light-sensitive silver halide photographic emulsion layer on a support and a non-light-sensitive hydrophilic colloid layer, at least one hydrophilic colloid layer has the following general formula (2) or A silver halide photographic light-sensitive material comprising a solid fine particle dispersion of a dye represented by formula (3).

[0009]

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In the formula, G ₁ and G ₂ are cyano groups, --COR ³ ,
^{-CONR 3 R 4, -OCOR 3,} -SO 2 R 3, -SO 2 N
R ³ represents R ⁴ , R ³ and R ⁴ represent an alkyl group, an aryl group, a heterocyclic group or an alkenyl group, G ₁ and G ₂ may be the same or different, and R ³ and R ⁴ are linked to each other. To form a 5- or 6-membered ring. L ¹ , L ² and L ³ each represent a methine group, B ¹ represents an oxygen-containing 6-membered ring, n is 0 or 1
Represents

[0011]

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In the formula, A represents the following structure. R ¹² , R ¹³ and R ^{14 in the} structures below represent a hydrogen atom or a substituent.
R ¹² and R ¹³ may combine with each other to form a 5- or 6-membered ring. L ¹ , L ² and L ³ each represent a methine group, B ₁ represents an oxygen-containing 6-membered ring, and n represents 0 or 1.

[0013]

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3. The silver chloride content is 70 mol% or more, and a salt of a transition metal selected from rhodium, ruthenium, iridium, rhenium, chromium, osmium, and copper is added from 1 × 10 ^-9 to 1 × 10 ^-2 per mol of silver halide. At least one hydrophilic colloid layer in a silver halide photographic light-sensitive material which has at least one mol-containing silver halide photographic emulsion layer and which has a non-photosensitive hydrophilic colloid layer and can be used in a bright room environment A silver halide photographic light-sensitive material comprising a solid fine particle dispersion of a dye represented by the following general formula (4).

[0015]

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In the formula, A ¹ represents pyrazolotriazole or an acidic nucleus. L ¹ , L ² and L ³ each represent a methine group,
B ¹ represents an oxygen-containing 6-membered ring, and n represents 0 or 1.

4. 4. The silver halide photographic light-sensitive material described in 1, 2, or 3 above, which contains a hydrazine derivative.

5. 4. The silver halide photographic light-sensitive material described in 1, 2 or 3 above, which contains a pyridinium salt derivative.

6. 4. The silver halide photographic light-sensitive material described in 1, 2, or 3 above, which contains a tetrazolium salt derivative.

[7] FIG. 3. The above-mentioned 3, which contains a hardening agent that acts by activating a carboxyl group,
The silver halide photographic light-sensitive material as described in 4, 5, or 6.

8. 8. The silver halide photographic light-sensitive material as described in 7 above, wherein the hardener is represented by the following general formula (5).

[0022]

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In the formula, R ⁶ and R ⁷ represent an alkyl group or an aryl group, and R ⁶ and R ⁷ may form a ring. R ⁸
Represents a hydrogen atom or a substituent. L ⁴ represents a single bond or a divalent group. X ¹ represents a single bond or —O—, —N (R ⁹ ) —, and R ⁹ represents a hydrogen atom, an alkyl group or an aryl group.

9. In the above general formula (4), B ¹ has a structure represented by the following general formula (6) or general formula (6 ′).

[0025]

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In the formula, R ₁₂ , R ₁₃ and R ₁₄ represent a hydrogen atom or a non-metal substituent.

10. 1, 2, 3, 4, 5, 6, 7,
The silver halide photographic light-sensitive material described in 8 or 9 has dihydroxybenzenes as a developing agent and has a pH of 9.5 or more and a pH of 1 or more.
A method of processing a silver halide photographic light-sensitive material, which comprises processing with a developing solution of 1.0 or less.

11. 1, 2, 3, 4, 5, 6, 7,
The silver halide photographic light-sensitive material described in 8 or 9 contains at least one compound selected from ascorbic acid (salt) and / or erythorbic acid (salt), and does not contain hydroquinone and has a pH of pH 9.5 or more 11 A method of processing a silver halide photographic light-sensitive material, which comprises processing with a developing solution of 0.0 or less.

The present invention will be described in detail below.

First, the solid fine particle dispersion of the dye represented by the general formula (1) of the present invention will be described in detail.

[0031]

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Za, Zb and Zc in the above general formula (7) representing the partial structure of the general formula (1) are each -N = or -C.
(R ² ) = and R ¹ and R ² represent a hydrogen atom or a non-metal substituent. Among those represented by the general formula (7),
Those represented by the following general formulas (7-1) to (7-6) are more preferable.

[0033]

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R in the general formulas (7-1) to (7-6)
¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ represent a hydrogen atom or a non-metal substituent.

In the general formula (7) and the general formulas (7-1) to (7-6), R ¹ , R ² , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ ,
R ¹⁵ and R ¹⁶ represent a hydrogen atom or a non-metal substituent (for example, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, an alkenyl group, a carboxylic acid group or a sulfonic acid group is preferable), and R ¹¹ and R ¹¹ R ¹² , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵
Alternatively, R ¹⁵ and R ¹⁶ may combine with each other to form a 5- or 6-membered ring.

In the general formula (1), B ¹ represents a 6-membered oxygen-containing heterocycle.

General formula (7), general formulas (7-1) to (7-
6) In, R ¹ , R ² , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R
^The alkyl group represented by ¹⁶ is a chain or cyclic alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, benzyl, phenethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, nonyl, cyclopropyl,
Each group such as cyclopentyl and cyclohexyl) is preferable and may have a substituent.

General formula (7), general formulas (7-1) to (7-
6) In, R ¹ , R ² , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R
^The aryl group represented by ¹⁶ is preferably an aryl group having 6 to 10 carbon atoms (for example, each group such as phenyl and naphthyl) and may have a substituent.

General formula (7), general formulas (7-1) to (7-
6) In, R ¹ , R ² , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R
^The heterocyclic group represented by ¹⁶ is a 5- or 6-membered heterocyclic group (for example, an oxzonyl ring, a benzoxazole ring, a thiazole ring, an imidazole ring, a pyridine ring, a furan ring, a thiophene ring, a sulfolane ring, a pyrazole ring, a pyrrole Each group such as a ring, a chroman ring, and a coumarin ring) is preferable and may have a substituent.

General formula (7), general formulas (7-1) to (7-
6) Medium, R¹, R^Two, R¹¹, R¹², R ¹³, R¹⁴, R^Fifteen, R
¹⁶The alkenyl group represented by is an alkene having 2 to 10 carbon atoms.
Nyl groups (eg vinyl, allyl, 1-propenyl, 2
-Pentenyl, 1,3-butadienyl and the like) are preferred.
New

In the general formulas (7-1) to (7-6), R ¹³ ,
The halogen atom represented by R ¹⁴ , R ¹⁵ and R ¹⁶ is preferably a fluorine atom, a chlorine atom or a bromine atom.

In the general formula (1), the methine groups represented by L ¹ , L ² and L ³ are preferably unsubstituted methine groups.

There is no particular limitation as long as the substituents that each of the above-mentioned groups may have are those which dissolve the compound of the general formula (1) in water of pH 5 to pH 7. For example, a carboxylic acid group, a sulfonamide group having 1 to 10 carbon atoms (for example, each group such as methanesulfonamide, benzenesulfonamide, butanesulfonamide, n-octanesulfonamide), a sulfamoyl group having 0 to 10 carbon atoms ( For example, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, butylsulfamoyl, and other groups), sulfonylcarbamoyl groups having 2 to 10 carbon atoms (eg, methanesulfonylcarbamoyl, propanesulfonylcarbamoyl, benzenesulfonylcarbamoyl) Etc.), an acylsulfamoyl group having 1 to 10 carbon atoms (for example, acetylsulfamoyl, propionylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl, etc. groups), a carbon number of 1 to 1 8 chain or cyclic alkyl (For example, methyl, ethyl, isopropyl, butyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, benzyl, phenethyl, 4-carboxybenzyl, 2-diethylaminoethyl, etc. Each group), an alkenyl group having 2 to 8 carbon atoms (for example, each group such as vinyl and acryl), an alkoxy group having 1 to 8 carbon atoms (for example, each group such as methoxy, ethoxy, butoxy), and a halogen atom (for example, , F, Cl, Br, etc.), an amino group having 0-10 carbon atoms (for example, unsubstituted amino, dimethylamino, diethylamino, carboxyethylamino, etc. groups), an ester group having 2-10 carbon atoms (Eg, methoxycarbonyl group, etc.), carbon number 1 to 10
Amide group (for example, each group such as acetylamino and benzamide), a carbamoyl group having 1 to 10 carbon atoms (for example,
Unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, etc. groups), aryl groups having 6 to 10 carbon atoms (eg, phenyl, naphthyl, 4-carboxyphenyl, 3-carboxyphenyl, 3,5-dicarboxyphenyl, 4 -Methanesulfonamidophenyl, 4-butanesulfonamidophenyl, etc.), carbon number 6-10
Aryloxy groups (for example, phenoxy, 4-carboxyphenoxy, 4-methylphenoxy, naphthoxy, and other groups), C1-C8 alkylthio groups (for example, methylthio, ethylthio, octylthio, and other groups), and carbon numbers 6-10 arylthio groups (eg, phenylthio,
Each group such as naphthylthio), an acyl group having 1 to 10 carbon atoms (for example, each group such as acetyl, benzoyl, propanoyl), a sulfonyl group having 1 to 10 carbon atoms (for example, each group such as methanesulfonyl, benzenesulfonyl, etc.) , Carbon number 1
To 10 ureido groups (for example, groups such as ureido and methylureido), and urethane groups having 2 to 10 carbon atoms (for example,
Each group such as methoxycarbonylamino and ethoxycarbonylamino), cyano group, hydroxyl group, nitro group, heterocyclic group (for example, 5-carboxybenzoxazole ring, pyridine ring, sulfolane ring, furan ring, pyrrole ring, pyrrolidine ring, morpholine) Ring, piperazine ring, pyrimidine ring and the like) and the like.

In the general formulas (7-1) to (7), R ¹¹
And R ¹² , R ¹³ and R ¹⁴ , R ¹⁴ and R ^15, or R ¹⁵ and R ¹⁶ are linked to each other to form a 5- or 6-membered ring, which includes a pyrrolidine ring, a piperidine ring, a benzene ring, and a morpholine ring. Can be mentioned.

Particularly preferred in formula (1) are those having at least one carboxylic acid group, sulfonamide group, sulfonylcarbamoyl group or acylsulfamoyl group in the formula.

Next, the solid fine particle dispersion of the dye represented by the general formulas (2) and (3) of the present invention will be described in detail.

In the general formulas (2) and (3), G ₁ and G ₂ are cyano groups, —COR ³ , —CON (R ³ ) R.
_{^{4, -OCOR 3, -SO 2 R}} 3, represents a ^{_{-SO 2 N (R 3) R}} 4, R 3, R 4 represents an alkyl group, an aryl group, a heterocyclic group or an alkenyl group, G _1, G _Two may be the same or different, and R ³ and R ⁴ may be connected to each other to form a 5- or 6-membered ring. R ¹² , R ¹³ and R ¹⁴ represent a hydrogen atom or a substituent. R ¹² and R ¹³ or R ¹³ and R ¹⁴ may combine with each other to form a 5- or 6-membered ring.

The alkyl group represented by G ₁ and G ₂ is a chain or cyclic alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, benzyl, phenethyl, propyl, butyl, isobutyl, pentyl, hexyl, (Octyl, nonyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.) are preferable and may have a substituent.

The aryl group represented by R ³ and R ⁴ is preferably an aryl group having 6 to 10 carbon atoms (for example, each group such as phenyl and naphthyl) and may have a substituent.

The heterocyclic group represented by R ³ and R ⁴ is 5 or 6
Membered heterocyclic groups (eg, oxazoline ring, benzoxazole ring, thiazole ring, imidazole ring, pyridine ring, furan ring, thiophene ring, sulfolane ring, virazol ring, pyrrole ring, chroman ring, coumarin ring, etc.)
Is preferable, and may have a substituent.

The alkenyl group represented by R ³ and R ⁴ is an alkenyl group having 2 to 10 carbon atoms (for example, vinyl, allyl,
Each group such as 1-propenyl, 2-pentenyl and 1,3-butadienyl) is preferable.

The methine groups represented by L ¹ , L ² and L ³ are
Unsubstituted methine groups are preferred. B ¹ represents an oxygen-containing 6-membered ring.

Substituents which each of the above groups may have include compounds represented by the general formula (2) and the general formula (3) at pH 5 to 5.
There is no particular limitation as long as it is a substituent that can be dissolved in water of pH 7.

For example, a carboxylic acid group, a sulfonamide group having 1 to 10 carbon atoms (for example, each group such as methanesulfonamide, benzenesulfonamide, butanesulfonamide, n-octanesulfonamide) and 0 to 10 carbon atoms. Sulfamoyl group (for example, each group of unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, butylsulfamoyl, etc.), a sulfonylcarbamoyl group having 2 to 10 carbon atoms (eg, methanesulfonylcarbamoyl, propanesulfonylcarbamoyl, Each group such as benzenesulfonylcarbamoyl), an acylsulfamoyl group having 1 to 10 carbon atoms (for example, each group such as acetylsulfamoyl, propionylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl), carbon Number 1 to 8 chain or ring Alkyl group (e.g., methyl,
Ethyl, isopropyl, butyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, benzyl, phenethyl, 4-carboxybenzyl,
2-diethylaminoethyl, etc.), C2-C8 alkenyl (eg, vinyl, acryl, etc. groups), C1-C8 alkoxy group (eg, methoxy, ethoxy, butoxy groups, etc.) , A halogen atom (eg, F,
Cl, Br, etc. each atom), an amino group having 0-10 carbon atoms (for example, unsubstituted amino, dimethylamino, diethylamino, carboxyethylamino, etc. groups), carbon number 2
-10 ester group (eg, methoxycarbonyl group, etc.), C 1-10 amide group (eg, acetylamino, benzamide, etc.), C 1-10 carbamoyl group (eg, unsubstituted carbamoyl) , Methylcarbamoyl, ethylcarbamoyl, etc.), carbon number 6
10 aryl groups (eg phenyl, naphthyl, 4
-Carboxyphenyl, 3-carboxyphenyl, 3,
5-dicarboxyphenyl, 4-methanesulfonamidophenyl, 4-butanesulfonamidophenyl, etc.), aryloxy groups having 6 to 10 carbon atoms (for example, phenoxy, 4-carboxyphenoxy, 4-methylphenoxy, naphthoxy). Etc.), alkylthio groups having 1 to 8 carbon atoms (eg, groups such as methylthio, ethylthio, octylthio, etc.), arylthio groups having 6 to 10 carbon atoms (eg, groups such as phenylthio, naphthylthio, etc.), carbon number 1-10 acyl groups (eg acetyl, benzoyl,
Each group such as propanoyl), a sulfonyl group having 1 to 10 carbon atoms (for example, each group such as methanesulfonyl and benzenesulfonyl), an ureido group having 1 to 10 carbon atoms (each group such as ureido and methylureido), Urethane group having 2 to 10 carbon atoms (for example, each group of methoxycarbonylamino, ethoxycarbonylamino, etc.), cyano group, hydroxyl group, nitro group, heterocyclic group (for example, 5-carboxybenzoxazole ring, pyridine ring, sulfolane ring) , Furan ring, pyrrole ring, pyrrolidine ring, morpholine ring, piperazine ring, pyrimidine ring) and the like.

5 formed by connecting R ¹² and R ¹³ to each other
Alternatively, examples of the 6-membered ring include a pyrrolidine ring, a piperidine ring, a benzene ring, and a morpholine ring.

Particularly preferred among the general formulas (2) and (3) are at least one carboxylic acid group in the formula,
It has a sulfonamide group, a sulfonylcarbamoyl group or an acylsulfamoyl group.

Next, the solid fine particle dispersion of the dye represented by the general formula (4) of the present invention will be described in detail.

The pyrazolotriazole ring residue in the general formula (4) is the same as that represented by the general formula (7).

In the general formula (4), the acidic nucleus represented by A ¹ is a cyclic ketomethylene group or a methylene group having an electron withdrawing group, and specific examples are shown below.

[0060]

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In the above specific examples, R ¹⁰ and R ¹¹ are cyano groups,
COR ¹⁵ , -CONR ¹⁵ R ¹⁶ , -OCOR ¹⁵ , -SO ₂
R ^15, represents a _{^{-SO 2 NR 15 R 16, R}} 15, R 16 is an alkyl group, an aryl group, a heterocyclic group or an alkenyl group, R ^10, R ¹¹ may be the same or different, R ¹⁵ And R ¹⁶ may combine with each other to form a 5- or 6-membered ring.
In the above specific examples, R ¹² , R ¹³ and R ¹⁴ represent a hydrogen atom or a substituent. R ¹² and R ¹³ or R ¹³ and R ¹⁴ may combine with each other to form a 5- or 6-membered ring.

The alkyl group represented by R ¹⁵ and R ¹⁶ above is
A chain or cyclic alkyl group having 1 to 10 carbon atoms (for example,
Methyl, ethyl, benzyl, phenethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, nonyl, cyclopropyl, cyclopentyl, cyclohexyl) are preferable and may have a substituent.

The aryl group represented by R ¹⁵ and R ¹⁶ above is
An aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl) is preferable, and may have a substituent.

The heterocyclic group represented by R ¹⁵ and R ¹⁶ is 5
Alternatively, a 6-membered heterocyclic ring (for example, oxazonyl ring, benzoxazole ring, thiazole ring, imidazole ring, pyridine ring, furan ring, thiophene ring, sulfolane ring, virazol ring, pyrrole ring, chroman ring, coumarin ring, etc.) is preferable, It may have a substituent.

The alkenyl group represented by R ¹⁵ and R ¹⁶ is an alkenyl group having 2 to 10 carbon atoms (for example, vinyl,
Allyl, 1-propenyl, 2-pentenyl, 1,3-butadienyl) are preferred. The halogen atom represented by R ¹ is preferably each atom such as fluorine, chlorine or bromine.

More specific examples of the above specific examples are shown below, but the present invention is not limited to these.

[0067]

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[0068]

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[0069]

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[0070]

[Chemical 21]

In the general formula (4), the methine groups represented by L ¹ , L ² and L ³ are preferably unsubstituted methine groups.
B ¹ represents an oxygen-containing 6-membered ring, and preferably has the structure of the general formula (6) or the general formula (6 ′).

In the general formula (6) and the general formula (6 '), R ₁₂ , R ₁₃ and R ₁₄ represent a hydrogen atom or a non-metal substituent.

Specific examples represented by the general formula (6) are shown below, but the present invention is not limited thereto.

[0074]

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The substituent which each of the above groups may have is not particularly limited as long as it is a substituent capable of dissolving the compound of the general formula (4) in water of pH 5 to pH 7.

For example, a carboxylic acid group, a sulfonamide group having 1 to 10 carbon atoms (for example, each group such as methanesulfonamide, benzenesulfonamide, butanesulfonamide, n-octanesulfonamide) and 0 to 10 carbon atoms. Sulfamoyl group (for example, each group of unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, butylsulfamoyl, etc.), a sulfonylcarbamoyl group having 2 to 10 carbon atoms (eg, methanesulfonylcarbamoyl, propanesulfonylcarbamoyl, Each group such as benzenesulfonylcarbamoyl), an acylsulfamoyl group having 1 to 10 carbon atoms (for example, each group such as acetylsulfamoyl, propionylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl), carbon Number 1 to 8 chain or ring Alkyl group (e.g., methyl,
Ethyl, isopropyl, butyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, benzyl, phenethyl, 4-carboxybenzyl,
2-diethylaminoethyl, etc.), C2-C8 alkenyl (eg, vinyl, acryl, etc. groups), C1-C8 alkoxy group (eg, methoxy, ethoxy, butoxy groups, etc.) , A halogen atom (eg, F,
Cl, Br, etc. each atom), an amino group having 0-10 carbon atoms (for example, unsubstituted amino, dimethylamino, diethylamino, carboxyethylamino, etc. groups), carbon number 2
An ester group of 10 (eg methoxycarbonyl),
An amide group having 1 to 10 carbon atoms (eg, acetylamino,
Each group such as benzamide), a carbamoyl group having 1 to 10 carbon atoms (for example, an unsubstituted carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, etc.), and 6 to 10 carbon atoms.
Aryl groups (for example, phenyl, naphthyl, 4-carboxyphenyl, 3-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamidophenyl, 4-butanesulfonamidophenyl, etc.), carbon number 6 10 aryloxy groups (for example, phenoxy, 4-carboxyphenoxy, 4-methylphenoxy, naphthoxy, and other groups), C1-8 alkylthio groups (for example, methylthio, ethylthio, octylthio, and other groups), Arylthio group having 6 to 10 carbon atoms (for example, each group such as phenylthio and naphthylthio), 1 carbon atom
-10 acyl group (for example, each group such as acetyl, benzoyl, propanoyl, etc.), sulfonyl group having 1-10 carbon atoms (for example, each group such as methanesulfonyl, benzenesulfonyl, etc.), ureido group having 1-10 carbon atoms ( For example, ureido, each group such as methylureido), a urethane group having 2 to 10 carbon atoms (for example, each group such as methoxycarbonylamino, ethoxycarbonylamino), a cyano group, a hydroxyl group, a nitro group, a heterocyclic group (for example, 5-carboxybenzoxazole ring, pyridine ring, sulfolane ring, furan ring, pyrrole ring, pyrrolidine ring, morpholine ring, piperazine ring,
Pyrimidine ring) and the like.

In the specific examples of A ^1, the 5- or 6-membered ring formed by connecting R ¹⁵ and R ¹⁶ , R ¹² and R ¹³ or R ¹³ and R ¹⁴ to each other is a pyrrolidine ring, a piperidine ring, Examples thereof include a benzene ring and a morpholine ring. Particularly preferred in general formula (4) are those having at least one carboxylic acid group, sulfonamide group, sulfonylcarbamoyl group or acylsulfamoyl group in the formula.

Specific examples of the dyes represented by the general formulas (1), (2), (3) and (4) are shown below, but the invention is not limited thereto.

[0079]

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[0080]

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Further, the dye of the present invention is an international patent WO88 / 0.
4,794, European Patent EP 0,274,723
A1, No. 276,556, No. 299,435, JP-A No. 52-92716, No. 55-155350, No. 55-155351, No. 61-205934, No. 4
8-68623, US Pat. Nos. 2,527,583, 486,897, 3,746,539, and 3,9.
33,798, 4,130,429, 4,04
It can be easily synthesized by the method described in No. 0,841 or the like and a method according to the method.

The layer containing the fine particle dispersion of the dye of the present invention is contained in the non-photosensitive hydrophilic colloid layer (hereinafter, also simply referred to as hydrophilic colloid layer).

The addition amount of the fine dye particle dispersion of the present invention is not particularly limited, but the addition amount is preferably such that the effective transmission density is 0.3 or more and 2 or less.

[0084] Non-light-sensitive hydrophilic colloid layer containing a dye fine particle dispersion of the present invention preferably has a coating amount is less than 0.05 g / m ² or more 0.5 g / m ^2, more preferably 0. It is 18 g / m ² or more and less than 0.42 g / m ² . In order to further enhance the effect of the present invention, it is preferable that the ratio of the average particle diameter of the fine particle dispersion of the dye to the film thickness of the hydrophilic colloid layer containing the dye is 0.2 to 2.0. . In the present invention, the hydrazine derivative is preferably a compound represented by the following general formula (H).

[0085]

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In the formula, E represents an aryl group or a heterocycle containing at least one sulfur atom or oxygen atom, and G represents a-(CO) n ₁ -group, a sulfonyl group, a sulfoxy group,-.
P (= O) R ²² - represents a group or an iminomethylene group,
n ₁ represents an integer of 1 or 2, both E ¹ and E ² represent a hydrogen atom or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group, and R ²¹ Represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group, carbamoyl group, or oxycarbonyl group. R ²² represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, amino group or the like.

Of the compounds represented by the general formula (H), the compounds represented by the following general formula (Ha) are more preferred.

[0088]

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In the formula, R ²³ is an aliphatic group (eg, octyl group, decyl group, etc.), aromatic group (eg, phenyl group, 2-
It represents a hydroxyphenyl group, a chlorophenyl group or the like) or a heterocyclic group (for example, a pyridyl group, a thienyl group, a furyl group or the like), and those groups further substituted with an appropriate substituent are preferably used. Further, R ²³ preferably contains at least one ballast group or silver halide adsorption promoting group. As the anti-diffusion group, a ballast group which is commonly used in a non-moving photographic additive such as a coupler is preferable, and as the ballast group, an alkyl group or an alkenyl group having a carbon number of 8 or more and relatively inactive for photographic properties is preferable. Group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula (Ha), Xa represents a group capable of substituting for a phenyl group, ma represents an integer of 0 to 4, and when ma is 2 or more, Xa may be the same or different. .

In the general formula (Ha), E ³ and E ⁴ have the same meanings as E ¹ and E ² in the general formula (H), and both are preferably hydrogen atoms.

In the general formula (Ha), G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula (Ha), R ²⁴ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group,
Represents a carbamoyl group or an oxycarbonyl group. The most preferable R ²⁴ is —COOR ₂₅ group and —CON.
(R ₂₆ ) (R ₂₇ ) group, R ₂₅ represents an alkynyl group or a saturated heterocyclic group, R ₂₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ₂₇ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group.

Specific examples of the compound represented by formula (H) are shown below, but the invention is not limited thereto.

[0096]

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Specific examples of other preferable hydrazine derivatives are (1) to (252) described in US Pat. No. 5,229,248, columns 4 to 60.

The hydrazine derivative preferably used in the present invention can be synthesized by a known method, for example, the method described in US Pat. No. 5,229,248, column 59 to column 80. You can

The addition amount may be any amount as long as it gives a high contrast (amount of high contrast), and the grain size of the silver halide grains, the halogen composition,
Although the optimum amount varies depending on the degree of chemical sensitization and the type of the inhibitor, it is generally 10 ^-6 to 10 per mol of silver halide.
It is in the range of ^-1 mol, preferably in the range of ^10-5 to ^10-2 mol.

The hydrazine derivative is added to the silver halide emulsion layer and / or its adjacent layer.

The hydrazine compound can be used in any layer as long as it is on the silver halide photographic emulsion layer side, but is preferably used in the silver halide photographic emulsion layer and / or its adjacent layer.

Further, in the present invention, three or more kinds of hydrazine compounds can be contained in any layer in any state.

The pyridinium salt derivative preferably used in the present invention includes compounds represented by the following general formula (Pa), (Pb) or (Pc).

[0104]

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In the formula, A ¹¹ , A ¹² , A ¹³ , A ¹⁴ and A
¹⁵ represents a non-metal atom group for completing the nitrogen-containing heterocycle, which may contain an oxygen atom, a nitrogen atom or a sulfur atom, and the benzene ring may be condensed. A ¹¹ , A ¹² ,
The heterocycle composed of A ¹³ , A ¹⁴ and A ¹⁵ may have a substituent and may be the same or different.

As the substituent and the substituent atom, an alkyl group,
Aryl group, aralkyl group, alkenyl group, alkynyl group, halogen atom, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, carboxy group, hydroxy group, alkoxy group, aryloxy group, amide group, sulfamoyl group, carbamoyl Represents a group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group, arylthio group.

Examples of preferred heterocycles composed of A ¹¹ , A ¹² , A ¹³ , A ¹⁴ and A ¹⁵ include a 5- or 6-membered ring (eg, pyridine, imidazole, thiazole, oxazole, pyrazine, pyrimidine and the like). Ring), and a pyridine ring can be mentioned as an example of a more preferable hetero ring.

Bp represents a divalent linking group, and the divalent linking group is alkylene, arylene, alkenylene or (poly).
_{Alkyleneoxy, -SO 2 -, - SO -} , - O -, -
S-, -CO-, -N (R ³³ )-, (R ³³ represents an alkyl group, an aryl group, a hydrogen atom) are used alone or in combination. A preferred example is Bp
Can include alkylene, alkenylene, and (poly) alkyleneoxy.

R ³¹ , R ³² and R ³⁵ represent a substituted or unsubstituted aryl group or substituted alkyl group. R ³¹ and R ³² may be the same or different. As a substituent, A ¹¹ , A
It is synonymous with the group mentioned as a substituent of ¹² , A ¹³ , A ¹⁴ and A ¹⁵ . Preferred examples of R ³¹ , R ³² and R ³⁵ include saturated and unsaturated alkyl groups having 1 to 20 carbon atoms. A more preferred example is a saturated or unsaturated alkyl group having 4 to 10 carbon atoms.

[0110] Xp ^- is a counter ion necessary to refer balancing the charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, the Oki The alert ions. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an intramolecular salt.

Specific examples of the pyridinium salt derivative are shown below, but the invention is not limited thereto.

[0112]

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The optimum amount of the pyridinium salt derivative added varies depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is generally 10 ⁻ per mol of silver halide. The range of ⁶ to 10 ^-1 mol is preferable, and the range of 10 ^-5 to 10 ^-2 mol is particularly preferable. The pyridinium salt derivative can be used in any layer as long as it is on the silver halide photographic emulsion layer side, but it is preferably contained in the silver halide photographic emulsion layer and / or its adjacent layer. Further, in the present invention, three or more kinds of pyridinium salt derivatives can be contained in any layer in any state.

The tetrazolium compound preferably used in the present invention can be represented by the following general formula (T).

[0115]

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R ⁴¹ , R ⁴² , and R ⁴³ in the above formula are hydrogen atoms or Hammett's sigma value (σp) indicating electron withdrawing degree.
Is preferably negative or 0. Hammett's sigma value for phenyl substitution is well documented, for example in Journal of Medical Chemistry.
Medical Chemistry) Volume 20, 30
Page 4, page 1977, C.I. C. Hansc
h) and the like, which are particularly preferable negative or 0
Examples of the group having a sigma value of (a numerical value is described after each group below) include, for example, a methyl group (-0.17), an ethyl group (-0.15), a cyclopropyl group (-0.21),
n-propyl group (-0.13), iso-butyl group (-
0.11), n-pentyl group (-0.15), cyclohexyl group (-0.22), amino group (-0.66), acetylamino group (0), hydroxyl group (-0.3).
7), a methoxy group (-0.27), an ethoxy group (-0.
24), propoxy group (-0.25), butoxy group (-
0.32), a pentoxy group (-0.34) and the like, all of which are useful as a substituent of the compound of the general formula (T). a represents 1 or 2, as the anion represented by X _T ^a-, such as chloride, bromide, halide ions such as iodide ions, nitric acid, sulfuric acid, of acid radical of an inorganic acid such as chloric acid, sulfonic Acid radicals of organic acids such as acids and carboxylic acids, anionic activators, specifically lower alkylbenzene sulfonate anions such as p-toluene sulfonate anion, higher alkylbenzene sulfonate anions such as p-dodecylbenzene sulfonate anion, Higher alkyl sulfate anions such as lauryl sulfate anion, borate anions such as tetraphenylboron, dialkylsulfosuccinate anions such as di-2-ethylhexylsulfosuccinate anion, and polyether alcohol sulfates such as acetylpolyethenoxysulfate anion. Beauty salon Anion include the higher aliphatic anion, those with a acid radical in a polymer of polyacrylic acid anion such as stearic acid anion.

Particularly preferred tetrazolium compounds are listed below, but the present invention is not limited thereto.

(1) 2,3-di (p-methoxyphenyl) -5-phenyltetrazolium chloride (2) 2,3-di (p-methylphenyl) -5-phenyltetrazolium chloride (3) 2,3- Di (m-methylphenyl) -5-phenyltetrazolium chloride (4) 2,3,5-Tri (p-methylphenyl) tetrazolium chloride (5) 2,3,5-Tri (p-methoxyphenyl) tetrazolium chloride and others The tetrazolium compound described in JP-B-5-58175 can be used.

The silver halide photographic light-sensitive material of the present invention preferably contains a redox compound capable of releasing a development inhibitor by being oxidized. The redox compound has hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, reductones and the like as redox groups. A preferred redox compound is a redox group-
A compound having an NHNH- group and the following general formula (11),
(12), (13), (14), (15) or (1
It is a compound represented by 6).

The compound having a --NHNH-- group as a redox group is represented by the following general formula (RE-a) or (R
E-b).

General formula (RE-a) T-NHNHCO-V- (Time) -PUG General formula (RE-b) T-NHNHCOCO-V- (Time) -PUG General formula (RE-a) and general formula (RE-a) In RE-b),
T and V each represent an optionally substituted aryl group or an optionally substituted alkyl group.

Examples of the aryl group represented by T and V include a benzene ring and a naphthalene ring, and these rings may be substituted with various substituents, and a preferable substituent is a linear or branched alkyl group. Group (preferably having 2 to 20 carbon atoms such as methyl group, ethyl group, isopropyl group and dodecyl group), alkoxy group (preferably having 2 to 21 carbon atoms such as methoxy group and ethoxy group), aliphatic Acylamino group (preferably having 2 to 2 carbon atoms)
Having one alkyl group, such as an acetylamino group,
Heptyl amino group, etc.), aromatic acylamino group, and the like, these other, for example, a substituted or unsubstituted aromatic rings, such as described above -CONH -, - O -, - SO 2 NH
Also included are those linked by a linking group such as-, -NHCONH-, and -NHCOO-.

As PUG, 5-nitroindazole ring, 4-nitroindazole ring, 1-phenyltetrazole ring, 1- (3-sulfophenyl) tetrazole ring,
Examples thereof include a 5-nitrobenzotriazole ring, a 4-nitrobenzotriazole ring, a 5-nitroimidazole ring, and a 4-nitroimidazole ring. The development inhibitory compound of these rings is further N-containing at the CO site of T-NHNH-CO- directly through a hetero atom such as N or S or through an alkylene group, an arylene group (for example, a phenylene group), an aralkylene group or the like. And S heteroatoms.

In addition, a development inhibitor such as a triazole group, an indazole group, an imidazole group, a thiazole group or a thiadiazole group may be introduced into a hydroquinone compound having a ballast group.

For example, 2- (dodecylethylene oxide thiopropionic amide) -5- (5-nitroindazol-2-yl) hydroquinone, 2- (stearylamide) -5- (1-phenyltetrazole-5-thio) Hydroquinone, 2- (2,4-di-t-amylphenoxypropionamide) -5- (5-nitrotriazol-2-yl) hydroquinone, 2-dodecylthio-5- (2-mercaptothiothiadiazole-5-thio ) Hydroquinone and the like can be mentioned.

Redox compounds are described in US Pat.
It can be synthesized with reference to the synthesis method described in No. 9,929.

The redox compound can be contained in the emulsion layer, in the hydrophilic colloid layer adjacent to the emulsion layer, or in the hydrophilic colloid layer via the intermediate layer.

The above redox compound is added by adding alcohols such as methanol and ethanol, glycols such as ethylene glycol, triethylene glycol and propylene glycol, ether, dimethylformamide,
It can be added after being dissolved in esters such as dimethyl sulfoxide, tetrahydrofuran and ethyl acetate, and ketones such as acetone and methyl ethyl ketone.

For those which are difficult to dissolve in water or an organic solvent, the average particle diameter is 0.01 to 6 μm by high speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion or the like.
Can be arbitrarily distributed. For dispersion, a surfactant such as an anion or nonion, a thickener, a latex, or the like can be added and dispersed.

The addition amount of the redox compound is preferably from 10 ^-6 to 10 ^-1 mol, and more preferably from 10 ^-4 to 10 ^-2 mol, per 1 mol of silver halide.

General formula (RE-a) or general formula (RE-
Among the compounds represented by b), particularly preferable compounds are listed below.

[0132]

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[0133]

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Specific examples of other preferable redox compounds include 236 of JP-A-4-245243.
(8) page “0053” to 250 (22) page “0068”
R-1 to R-50 described in 1.

Further, the above general formulas [11], [12] and [1]
The redox compound represented by 3], [14], [15] or [16] will be described.

[0136]

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General formulas [11], [12], [13],
In [14], [15] or [16], R ⁵¹ represents an alkyl group, an aryl group or a heterocyclic group. R ⁵² and R ⁵³ represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group. R ⁵⁴ represents a hydrogen atom. R
^{55 to} R ⁵⁹ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. r ¹ , r ² and r ³ represent a substituent capable of substituting on the benzene ring.

X ¹¹ and X ¹² represent O or NH. Z ¹ represents an atomic group necessary for forming a 5- or 6-membered heterocycle.
W represents -N (R ⁶⁰⁾ R ⁶¹ or -OH,, R ⁶⁰ and R ⁶¹ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

COUP represents a coupler residue capable of causing a coupling reaction with an oxidized product of an aromatic primary amine developing agent, and * represents a coupling site of the coupler.

Tm represents a timing group. m ¹ and p ¹ represent an integer of 0 to 3. q ¹ represents an integer of 0 to 4.
n ₂ represents 0 or 1. PUG represents a development inhibitor.

The above general formulas [11], [12] and [1]
3], [14], [15] or [16], R
Preferable examples of the alkyl group, aryl group and heterocyclic group represented by ⁵¹ and R ^{55 to} R ⁶¹ include a methyl group, a p-methoxyphenyl group and a pyridyl group.

Among the acyl group, carbamoyl group, cyano group, nitro group, sulfonyl group, aryl group, oxalyl group, heterocyclic group, alkoxycarbonyl group and aryloxycarbonyl group represented by R ⁵² and R ⁵³ , acyl group is preferable. Group, carbamoyl group, and cyano group. The total number of carbon atoms in these groups is preferably 1 to 20.

R ^{51 to} R ⁶¹ may further have a substituent atom or a substituent. As the substituent atom and the substituent, for example,
Halogen atom (chlorine atom, bromine atom etc.), alkyl group (eg methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group etc.), cycloalkyl group (eg cyclopentyl) Group, cyclohexyl group etc.), aralkyl group (eg benzyl group, 2-phenethyl group etc.), aryl group (eg phenyl group, naphthyl group, p-tolyl group, p
-Chlorophenyl group etc.), alkoxy group (eg methoxy group, ethoxy group, isopropoxy group, butoxy group etc.), aryloxy group (eg phenoxy group etc.), cyano group, acylamino group (eg acetylamino group, propionylamino group etc.) ), An alkylthio group (eg, methylthio group, ethylthio group, butylthio group, etc.), an arylthio group (eg, phenylthio group, etc.), a sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), an ureido group (eg, 3-methyl). Ureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group) Base etc.) A sulfamoyl group (e.g., ethyl sulfamoyl group, dimethylsulfamoyl group),
Alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), sulfonyl group (eg methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group etc.), acyl group (eg acetyl) Group, propanoyl group, butyroyl group, etc.), amino group (eg methylamino group, ethylamino group, dimethylamino group etc.), hydroxyl group, nitro group, imide group (eg phthalimido group etc.), heterocyclic group (eg pyridyl group) Group, benzimidazolyl group, benzthiazolyl group, benzoxazolyl group and the like).

Examples of the coupler residue represented by COUP include the following.

Examples of cyan coupler residues include phenol couplers and naphthol couplers. Examples of magenta couplers include 5-pyrazolone couplers, pyrazolone couplers, cyanoacetylcoumarone couplers, open chain acylacetonitrile couplers, and indazolone couplers.
Examples of the yellow coupler residue include a benzoylacetanilide coupler, a pivaloylacetanilide coupler, and a malondianilide coupler. Examples of non-colored coupler residues include open-chain or cyclic active methylene compounds (eg, indanone, cyclopentanone, malonic diester, imidazolinone, oxazolinone, thiazolinone, etc.).

Further, among the coupler residues represented by Coup, those which are preferably used in the present invention can be represented by the general formula (Coup-1) to the general formula (Coup-8).

[0147]

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In the formula, R ⁷⁰ represents an acylamido group, anilino group or ureido group, and R ⁷¹ represents a phenyl group which may be substituted with one or more halogen atoms, alkyl groups, alkoxy groups or cyano groups.

[0149]

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General formula (Coup-2) and general formula (Co
up-3), R ⁷² and R ⁷³ represent a halogen atom, an acylamido group, an alkoxycarbonylamido group, a sulfoulide group, an alkoxy group, an alkylthio group, a hydroxy group or an aliphatic group, and R ⁷⁴ and R ⁷⁵ are each a fat Represents a group, an aromatic group or a heterocyclic group. Further, one of R ⁷⁴ and R ⁷⁵ may be a hydrogen atom. a represents an integer of 1 to 4; b represents an integer of 0 to 5; When a and b are plural,
R ⁷² may be the same or different, and R ⁷³ may be the same or different.

[0151]

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General formula (Coup-4) and general formula (Co
In up-5), R ⁷⁶ represents a tertiary alkyl group or an aromatic group, and R ⁷⁷ represents a hydrogen atom, a halogen atom or an alkoxy group. R ⁷⁸ is an acylamide group, an aliphatic group,
It represents an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, an alkoxy group, a halogen atom or a sulfonamide group.

[0153]

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In the formula, R ⁷⁹ represents an aliphatic group, an alkoxy group, an acylamino group, a sulfonamide group, a sulfamoyl group, a diacylamino group, and R ⁸⁰ represents a hydrogen atom, a halogen atom or a nitro group.

[0155]

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The general formula (Coup-7) and the general formula (Co
up-8), R ⁸¹ and R ⁸² are each a hydrogen atom, an aliphatic group,
Represents an aromatic group or a heterocyclic group.

The 5- or 6-membered heterocycle represented by Z ¹ may be a single ring or a condensed ring, and is a 5- or 6-membered heterocycle having at least one of O, S and N atoms in the ring. Is mentioned. These rings may have a substituent, and specific examples thereof include the above-mentioned substituents.

The timing group represented by Tm is preferably —OCH ₂ — or another divalent timing group, for example, US Pat. Nos. 4,248,962 and 4,40.
9,323, or 3,674,478, Rese
rch Disclosure 21228 (December 1981) or JP-A-57-56837 and JP-A-4-
Examples thereof include those described in Japanese Patent No. 438, etc.

Preferred development inhibitors for PUG include, for example, US Pat. No. 4,477,563 and JP-A-60-218.
No. 644, No. 60-221750, No. 60-2336
No. 50, or the development inhibitor described in No. 61-11743.

Specific examples of the compounds represented by the general formulas [11] to [16] which are preferably used in the present invention are listed below, but the present invention is not limited thereto.

[0161]

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General formula [1] preferably used in the present invention
1] of the compounds represented by - [16], per mol of silver halide 1 × 5 × 10 ^-2 mol preferably contains from 10 ^-6 moles, especially 1 × 10 ^-4 mol 2 × 10 ^{- Two} moles are preferred.

The compounds represented by the above general formulas [11] to [16] are used by dissolving them in a suitable water-miscible organic solvent such as alcohols, ketones, dimethylsulfoxide, dimethylformamide, methylcellosolve and the like. it can. It is also possible to add it as an emulsified dispersion using a known oil. Further, the compound powder can be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or an ultrasonic wave by a method known as a solid dispersion method.

The redox compound preferably used in the present invention is a silver halide photographic emulsion layer, a layer adjacent to the emulsion layer,
It can be present in another layer or the like via an adjacent layer.
Particularly preferred is an emulsion layer and / or a hydrophilic colloid layer adjacent to the emulsion layer. Most preferably, a hydrophilic colloid layer is provided between the emulsion layer and the emulsion layer closest to the support, and the hydrophilic colloid layer is added to the hydrophilic colloid layer. Further, the redox compound may be contained in a plurality of different layers.

In the present invention, generally known sulfur sensitization, reduction sensitization and noble metal sensitization methods may be used in combination with chemical sensitization using a compound such as Se or Te.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, rhodanins and polysulfide compounds can be used in addition to the sulfur compounds contained in gelatin.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained.

Examples of the reduction sensitizer include stannous salt, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

In the present invention, the halogen composition of the silver halide in the silver halide emulsion is pure silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride or chloroiodo containing 60 mol% or more of silver chloride. It is preferably silver bromide.

The average grain size of silver halide is preferably 0.7 μm or less, and particularly preferably 0.5 to 0.1 μm. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood.

The above particle size means the particle diameter when the particles are spherical or particles which can be approximated to spheres. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details on how to find the average particle size, see Mies,
James: The Theory of the Photographic Process (CE Mees & TH James)
Written by: the theory of the photo
graphic process), 3rd edition, 36-4
See page 3 (1966 (published by Macmillan "Mcmillan")).

The shape of silver halide grains is not limited,
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Also, a narrower particle size distribution is preferable, and a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is particularly preferable.

As the method of reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Thus, a silver halide emulsion having a nearly uniform grain size can be obtained.

The silver halide grains used in the silver halide emulsion are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, ruthenium salt in at least one of the grain forming process and the growing process. It is preferable to add an osmium salt or a complex salt containing these elements.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Res).
(Earth Disclosure) 176 No. 1764
3, pages 22 to 23 (December 1978) or cited therein.

In the present invention, it is preferable to use a nucleation accelerator in order to effectively promote the high contrast when the hydrazine derivative is used. Examples of the nucleation accelerator include compounds described in Japanese Patent Application No. 6-103982, pages 28 to 29, and specific examples thereof include Japanese Patent Application No. 6-
103982 pages 30-35 (Na-1)-(Na
Examples thereof include, but are not limited to, the compounds described as -20).

Preferred examples of the nucleation accelerator are shown below, but the invention is not limited thereto.

[0178]

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[0179]

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[0180]

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The amount of the nucleation accelerator used in the light-sensitive material is preferably 5 × 10 ^{−7 to} 5 × 10 ⁻¹ mol, and particularly 5 × 10 ^{−6 to} 5 × 10 5 mol per mol of silver halide. It is preferably in the range of ^-2 mol.

The hydrazine compound and nucleation accelerator preferably used in the present invention are any layers on the silver halide emulsion layer side,
Although it can be used in the hydrophilic colloid layer, it is preferably used in the silver halide photographic emulsion layer and / or its adjacent layer.

The light-sensitive material of the present invention is preferably processed using an automatic processor. At this time, processing is performed while replenishing a fixed amount of a developing solution and a fixing solution in proportion to the area of the photosensitive material. The developing replenishing amount and the fixing replenishing amount are preferably 300 ml or less per 1 m ² in order to reduce the amount of waste liquid, and more preferably 75 to 1 per ² m ² .
200 ml.

In order to shorten the developing time, the present invention provides a total processing time (Dry to Dry) of 10 days from the time when the leading edge of the film is inserted into the automatic developing machine to the time when it comes out of the drying zone when the processing is performed using the automatic developing machine. It is preferably -60 seconds. The total processing time as used herein includes all process times required for processing the light-sensitive material, and specifically, steps such as development, fixing, bleaching, washing with water, stabilization processing, and drying necessary for processing. Time including all of the time, that is, Dry t
o Dry time.

If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 15 to 50 seconds.

In the automatic processor, a heat transfer material at 90 ° C. or higher (for example, a heat roller at 90 ° C. to 130 ° C.) or a radiation object at 150 ° C. or higher (for example, tungsten, carbon, nichrome, zirconium oxide / yttrium oxide /
A substance that emits infrared rays by directly generating heat through a mixture of thorium oxide or silicon carbide and radiating heat, or transferring heat energy from a resistance heating element to a radiator such as copper, stainless steel, nickel, or various ceramics to generate heat and generate infrared rays ) And those having a zone for drying.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazain Denes, tetrazaindenes (especially 4-
Hydroxy-substituted-1,3,3a, 7-tetrazaindenes), pentazaindenes, etc .; known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Many compounds can be added.

In the present invention, in addition to desensitization by metal doping, desensitization by using an organic desensitizer can be used together.

The organic desensitizers that can be used in the present invention are shown below.

(1) Phenosafranine (2) Pinacryptol Green (3) 2,3-Dimethyl-6-nitro-benzothiazolium paratoluenesulfonate (4) 2- (paranitrostyryl) quinoline paratoluene Sulfonate (5) 1,3-diethyl-1'-methyl-2'-phenylimidazo (4,5-b) quinoxaline-3'-indolocarbocyanine iodide (6) pinacryptol yellow (7) 1, 1,3,3'-hexamethyl-5,5'-dinitroindocarbocyanine paratoluenesulfonate (8) 5,5'-dichloro-3,3'-diethyl-6
6'-dinitrocarbocyanine iodide (9) 1,1'-dimethyl-2,2'-diphenyl-
3.3'-Indolocarbocyanine bromide The amount of the organic desensitizer used is 10 per mole of silver halide.
It is preferably from 5 mg to 5 g, more preferably from 50 mg to 3 g. The addition method may be an aqueous solution, or may be a solution dissolved in an organic solvent. Further, it can be added as fine particles by a sand mill, a ball mill, or an impeller dispersion. The size of fine particles is 0.001
A size of μm to 20 μm is suitable, but a particularly preferable condition is 0.01 μm to 1 μm.

Organic desensitizers are characterized by polarographic half-edge potentials. That is, the sum of the anode potential and the cathode potential of the polarograph is positive. This measuring method is described in US Pat. No. 3,501,307.

In the present invention, the silver halide photographic emulsion layer and the non-photosensitive hydrophilic colloid layer may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide]
Etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, phenoxymucochloric acid etc.) isoxazoles, dialdehyde starch, 2-chloro-6- Hydroxytriazinylated gelatin and the like can be used alone or in combination.

As the hardener, the above-mentioned general formula (5) is used.
The compound represented by is particularly preferably used.

In the general formula (5), R ⁶ and R ⁷ are linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms (eg, methyl group, ethyl group, butyl group, cyclohexyl group, 2-ethylhexyl group). Group, dodecyl group, etc.), and an aryl group having 6 to 30 carbon atoms (eg, phenyl group, naphthyl group, etc.). Further, R ⁶ and R ⁷ may have a substituent, and examples of the substituent are listed as the substituents which may be substituted on each group of the general formula (1) or the general formula (2) described above. There are things.

It is also preferred that R ⁶ and R ⁷ combine to form a ring together with the nitrogen atom, and particularly preferred examples are the case of forming a morpholine ring or a pyrrolidine ring. R ⁸ represents a hydrogen atom or a substituent, and the substituent is the above aryl group,
Examples of the substituent for substituting the heterocycle are mentioned, and a hydrogen atom is particularly preferable.

L ⁴ represents a single bond, an alkylene group having 1 to 20 carbon atoms (for example, methylene group, ethylene group, trimethylene group, propylene group, propylene group, etc.), and 6 carbon atoms.
To 20 arylene groups (for example, phenylene group) and divalent groups (for example, para-xylene group) obtained by combining them, acylamino groups (for example, -NHCOCH _2- ).
Group), a sulfonamide group (for example, —NHSO ₂ CH ₂ —)
Represents a divalent group such as Among them, preferred are a single bond, an alkylene group such as a methylene group and an ethylene group, and an acylamino group.

X ¹ is a single bond or --O--, --N (R ⁹ ).
- represents, R ⁹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (e.g., methyl group, ethyl group, benzyl group, etc.), an aryl group having 6 to 20 carbon atoms (e.g., phenyl group), 1 carbon atoms To 20 alkoxy groups (eg, methoxy group), but a hydrogen atom is particularly preferable.

Specific examples of the compound represented by the general formula (5) include, but are not limited to, the compounds (1) to (17) described in Japanese Patent Application No. 6-144823, pages 11 to 13. Not done.

Preferred examples of the compound represented by the general formula (5) include the following.

[0200]

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The silver halide photographic emulsion and / or the non-photosensitive hydrophilic colloid layer of the present invention are used for various purposes such as a coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. Various known surfactants may be used. It is advantageous to use gelatin as the binder or protective colloid of the photographic emulsion, 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, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives. A variety of synthetic hydrophilic polymeric substances such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers; Can be used.

As the gelatin, other than lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The silver halide photographic emulsion for use in the present invention can contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth)
Acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene and the like alone or in combination, or acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, A polymer having a combination of hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

Various other additives are used in the light-sensitive material of the present invention. For example, desensitizers, plasticizers, slip agents,
Examples include development accelerators and oils. Regarding these additives and the above-mentioned additives, specifically, research
Those described in Disclosure No. 176 (supra), pages 22 to 31 can be used.

In the light-sensitive material of the present invention, the emulsion layer and the protective layer may be a single layer or multiple layers composed of two or more layers.
In the case of a multilayer, an intermediate layer or the like may be provided therebetween.

In the light-sensitive material of the present invention, the silver halide photographic emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for light-sensitive materials.

Useful as the flexible support is a film made of a synthetic polymer such as cellulose acetate, cellulose acetate butyrate, polystyrene, or polyethylene terephthalate.

The developing agents that can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone), 3-pyrazolidones (eg 1
-Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-
3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), pyrogallol,
Ascorbic acid (salt) and / or erythorbic acid (salt), 1-aryl-3-pyrazolines (eg 1-
(P-hydroxyphenyl) -3-aminopyrazoline,
1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-
Aminopyrazoline, etc.), transition metal complex salts (Ti, V, C)
It is a complex salt of a transition metal such as r, Mn, Fe, Co, Ni or Cu, and these may be in a form having a reducing power to be used as a developing solution. For example, Ti ³⁺ , V ²⁺ , Cr ²⁺ , F
It takes the form of a complex salt such as e ²⁺ , and as the ligand, an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and salts thereof, hexametapolyphosphoric acid, tetrapolyphosphoric acid, etc. Examples thereof include phosphoric acid and salts thereof. ) Or the like can be used alone or in combination, but a combination of 3-pyrazolidones and dihydroxybenzenes, or a combination of aminophenols and dihydroxybenzenes or 3-pyrazolidones and ascorbic acid (salt) and And / or erythorbic acid (salt), aminophenols and ascorbic acid, 3-pyrazolidones and transition metal complex salts, aminophenols and transition metal complex salts. preferable.

The developing agent is preferably used usually in an amount of 0.01 to 1.4 mol / liter.

In the present invention, as a silver sludge-preventing agent, Japanese Examined Patent Publication No. 62702/1987, JP-A-3-51844,
4-26838, 4-362942, 1-3
Examples thereof include compounds described in No. 19031.

A compound represented by the following general formula (17) is particularly preferable.

[0213]

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In the formula, R ⁹¹ , R ⁹² , and R ⁹³ are each a hydrogen atom,
-SM ¹ group, hydroxy group, lower alkoxy group, -CO
An OM ² group, an amino group, a —SO ₃ M ³ group or a lower alkyl group, wherein at least one of R ⁹¹ , R ⁹² and R ⁹³ is —S
Represents an M ¹ group. M ¹ , M ² and M ³ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different. The lower alkyl group and lower alkoxy group represented by R ⁹¹ , R ⁹² , and R ⁹³ are groups having 1 to 5 carbon atoms, and the amino group represented by R ⁹¹ , R ⁹² , and R ⁹³ is a substituted or non-substituted group. It represents a substituted amino group, and a preferred substituent is a lower alkyl group. In formula (17), the ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.
Specific examples of the compound represented by the general formula (17) are shown below, but the invention is not limited thereto.

[0215]

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The developing waste liquid can be regenerated by energizing it. Specifically, a cathode (for example, an electric conductor or a semiconductor such as stainless steel wool) is placed in a developing waste solution, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) is put in an electrolyte solution, and anion exchange is performed. The developer waste solution tank and the electrolyte solution tank are brought into contact with each other via the membrane, and both electrodes are energized for regeneration. The light-sensitive material according to the present invention can be processed while energizing. At that time, various additives added to the developer, for example, a preservative, an alkali agent, a pH buffer, a sensitizer, an antifoggant, a silver sludge inhibitor which can be added to the developer are additionally added. You can do it. In addition, there is a method of processing the photosensitive material while supplying electricity to the developing solution. In this case, an additive that can be added to the developing solution as described above can be added. When the waste developer is regenerated and used, transition metal complex salts are preferable as the developing agent of the developer used.

Examples of sulfites and metabisulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l. Particularly preferably, it is at least 0.4 mol / liter. If necessary, the developer may contain an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg, carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.), and a solubilizing agent. Agents (for example, polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (for example, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.),
Surfactants, defoamers, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), and a development accelerator (for example, US Pat.
No. 025, JP-B-47-45541, etc.), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent.

Developer when the developing agent is a dihydroxybenzene, and when the developer contains at least one compound selected from ascorbic acid (salt) and / or erythorbic acid (salt) and does not contain hydroquinone. PH of
Is 9.5 or more and 11.0 or less.

The total processing time (Dry to Dry) is set to 6
The pH of the developer is 8.5 to 10.5 in order to set it to 0 seconds or less.
Is preferably adjusted to

The compounds of the present invention, as a special form of development processing, include a developing agent in a light-sensitive material, for example, an emulsion layer,
You may use it for the activator processing liquid which makes a photosensitive material process in alkaline aqueous solution and develops. Such development processing is often used as one of the rapid processing methods for photosensitive materials in combination with silver salt stabilization processing using thiocyanate, and can be applied to such processing solutions.
In the case of such rapid processing, the effect of the present invention is particularly large.

As the fixing solution, those having a generally used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and other components, and has a pH of usually 3.8 to 5.8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur capable of forming a soluble stable silver complex salt. A compound known as a fixing agent can be used. A water-soluble aluminum salt that acts as a hardening agent, such as aluminum chloride, aluminum sulfate, and potassium alum, can be added to the fixing solution.

If desired, the fixer may contain preservatives (eg sulfite, bisulfite), pH buffers (eg acetic acid),
Compounds such as a pH adjuster (for example, sulfuric acid) and a chelating agent capable of softening water can be included.

The developing solution may be a mixture of solid components, an organic aqueous solution containing glycol or amine, or a viscous liquid with a high viscosity in a semi-kneaded state. Further, it may be used after being diluted at the time of use, or may be used as it is.

In the development processing of the present invention, the development temperature can be set in the usual temperature range of 20 to 30 ° C. or in the high temperature processing range of 30 to 40 ° C.

[0225]

EXAMPLES The effects of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 <Preparation of Gelatin Lower Layer Coating Liquid U1> Gelatin 12% (W / V) aqueous solution 250 ml Saponin 33% (W / V) aqueous solution 10 ml Sodium dodecylbenzenesulfonate 20% (W / V) aqueous solution 10 ml Styrene Water-soluble copolymer of sulfonic acid and maleic acid 4% (W / V) aqueous solution 20 ml After adding the above additives, 250 ml of a fine particle dispersion of the dye compound of the present invention for comparison and 250 ml of gelatin liquid G was added as shown in Table 1 and The gelatin lower layer coating solution was prepared by adding the ingredients as shown in Table 2 and adjusting the total amount to 1414 ml with pure water.

<Preparation of silver halide emulsion E1> Temperature 40
The silver potential EAg is set to 1 in a nitric acid acidic atmosphere with a pH of 3.0.
The solution B and the solution C were mixed with the following solution A for 11 minutes by the double jet method while maintaining at 170 mV with N.NaCl.

Solution A Gelatin 5.6 g HO (CH ₂ CH ₂ O) n (CH ₂ CH ₂ CH ₂ O) ₁₇ (CH ₂ CH ₂ O) mH (however, n + m = 6) 10% ethanol solution 0.56 ml Sodium chloride 0.12 g Concentrated nitric acid 0.43 ml Distilled water 445 ml Solution B Silver nitrate 60 g Concentrated nitric acid 0.208 ml Distilled water 85.2 ml Solution C Gelatin 3.0 g HO (CH ₂ CH ₂ O) n (CH ₂ CH ₂ CH ₂ O ) ₁₇ (CH ₂ CH ₂ O) mH (however n + m = 6) in 10% ethanol 0.3 ml Sodium chloride 20.2 g 6 Rhodium chloride complex Rhodium 8 × 10 ⁻⁵ mol / Ag mol Distillation water 85.61ml solution D gelatin _{1.4g HO (CH 2 CH 2 O} ) n (CH 2 CH 2 CH 2 O) 17 (CH 2 CH 2 O) mH (but n + m = 6) The average particle size of from 0% ethanol solution 0.14ml of distilled water 48.8ml resulting silver halide grains 0.12μm
The monodispersity was 8 to 15%. Solution D was added to the emulsion thus prepared, the pH was adjusted to 6.0 with sodium carbonate and then 4-hydroxy-6-methyl-
200 mg of 1,3,3a, 7-tetrazaindene was added. After that, each silver halide emulsion was washed with water according to a conventional method,
After desalting, the following solution J was added as a preservative.

Solution J 2-Methyl-5-chloroisothiazol-3-one 15 mg Pure water 0.3 ml 4-hydroxy-6-methyl- as a stabilizer for the above emulsion.
200 mg of 1,3,3a, 7-tetrazaindene and 8.6 g of gelatin were added to obtain a silver halide emulsion E1.
Further, the following coating additives were added to prepare a silver halide emulsion coating solution E2 for forming an exposed visible image.

Gelatin 12% aqueous solution 220 ml Saponin 33% (W / V) aqueous solution 7.6 ml Sodium dodecylbenzenesulfonate 20% (W / V) aqueous solution 7.6 ml 1-decyl-2- (3-isopentyl) succinate-2 -Sodium sulfonate 4% (W / V) aqueous solution 1.0 ml Polymer latex (copolymer of cyclohexyl-methacrylate, isononyl acrylate, glycidyl-acrylate and styrene-isoprene sulfonic acid having an average particle size of 0.25 μm) 20% (W / V) Emulsion solution 111 ml Citric acid 7% (W / V) aqueous solution 1.3 ml Water-soluble copolymer of styrene sulfonic acid and maleic acid 4% (W / V) aqueous solution 14 ml 2-Methyl-5-chloroisothiazole-3- ON 5% (W / V) methanol solution 0 After addition of 4ml noted additives, the total amount of the coating solution was adjusted with pure water so that the 1057ml emulsion coating solution.

<Preparation of Silver Halide Photographic Emulsion Coating Solution E3 for Image Forming Layer> Inorganic sulfur and potassium chloroaurate were added to the above silver halide emulsion E1 to carry out chemical sensitization, and the following additives were added and coated. The total amount of the liquid was adjusted to be 303 ml with pure water to prepare a silver halide photographic emulsion coating liquid E3 for the image forming layer.

Saponin 33% (W / V) aqueous solution 2.2 ml Sodium dodecylbenzenesulfonate 20% (W / V) aqueous solution 2.2 ml 1-decyl-2- (3-isopentyl) succinate-2-sodium sulfonate 4 % (W / V) aqueous solution 0.3 ml polymer latex (copolymer of cyclohexyl-methacrylate, isononyl acrylate, glycidyl-acrylate and styrene-isoprene sulfonic acid having an average particle size of 0.25 μm) 20% (W / V) emulsion liquid 31.8 ml (H) hydrazine derivative 2% (W / V) methanol solution 7.7 ml (N) amine compound 5% (W / V) aqueous solution 4 ml Citric acid 7% (W / V) aqueous solution 0.4 ml (S- 1) 2% (W / V) aqueous solution 26.5 ml 2-mercaptohypoxanthine 0.1. % (W / V) alkaline aqueous solution 4 ml Ethylenediaminetetraacetic acid sodium 5% (W / V) aqueous solution 10 ml Spirobis (3,3-dimethyl-5,6-dihydroxyindane) 5% (W / V) methanol solution 1.5 ml Hydroquinone 20% (W / V) aqueous solution 2.5 ml Water-soluble copolymer of styrene sulfonic acid and maleic acid 4% (W / V) aqueous solution 4 ml 2-methyl-5-chloroisothiazol-3-one 5% (W / V) Methanol solution 0.4 ml <Preparation of coating liquid M1 for intermediate layer> Gelatin 12% (W / V) aqueous solution 250 ml Saponin 33% (W / V) aqueous solution 11 ml Sodium dodecylbenzenesulfonate 20% (W / V) aqueous solution 10 ml Quent Acid 7% (W / V) aqueous solution 3 ml Dimezone S 2% (W / V) methanol solution 20 ml Zorcin 20% (W / V) aqueous solution 40 ml Garlic acid propyl ester 10% Methanol solution 60 ml (Dye F) 2% (W / V) aqueous solution 700 ml Styrene sulfonic acid and maleic acid water-soluble copolymer 4% (W / V) aqueous solution 22.7 ml 2-bromo-2-nitro-1,3-propanediol 0.1% (W / V) aqueous solution 6 ml After addition of the above additives, as will be described later, a fine particle dispersion of the dye compound of the present invention for comparison and for comparison. Liquid 250 ml or gelatin liquid G 250 ml was added so as to be a combination of Table 1 and Table 2, and pure water was adjusted so that the total amount was 1414 ml to prepare an intermediate layer coating liquid.

<Preparation of Coating Liquid P1 for Protective Layer> Gelatin 12% (W / V) aqueous solution 250 ml 1-decyl-2- (3-isopentyl) succinate-2-sodium sulfonate 4% (W / V) aqueous solution 50 ml NaCl 10% aqueous solution 22 ml Amorphous silica (average particle size 3.5 μm) 2 g Amorphous silica (average particle size 6 μm) 4 g (S-2) 0.08% (W / V) methanol solution 70 ml Citric acid 7% (W / V) Aqueous solution 5.1 ml Dimezone S 2% (W / V) methanol solution 20 ml (Dye F) 2% (W / V) aqueous solution 700 ml Water-soluble copolymer of styrene sulfonic acid and maleic acid 4% (W / V) aqueous solution 22.7 ml 2-bromo-2-nitro-1,3-propanediol 0.1% (W / V) aqueous solution 6 ml After addition and mixing of the above additives, dyeing The following fine particle dispersion or gelatin solution G of the object was added to a combination of Table 1 and Table 2, the total amount to prepare a protective layer coating solution was adjusted with pure water so that the 1414Ml.

<Preparation of Hardener Liquid MH1 for In-Line Addition of Intermediate Layer> 10% (W / V) aqueous solution of hardener H-1 300 ml <Preparation of Hardener liquid PH1 for in-line addition of protective layer> Hardener A 2.5% (W / V) aqueous solution of H-2 187 ml Pure water 113 ml The above additives were mixed to prepare 300 ml of a hardener solution PH1 which was mixed and added inline to the protective layer coating solution immediately before coating.

<Preparation of Dye Fine Particle Dispersion> Comparative Compound-
1, comparative compound-2, exemplary compounds D-8 and D- of the present invention
10, D-38, D-40, D-41, D-48, D-
49, D-52, D-60, D-63, D-67, D-
71, D-73, D-77, D-79, and D-81 were the coating amounts of Table 1 and Table 2, respectively, and 30 g of gelatin,
A solution of 147 mg of citric acid, 400 mg of isopropylnaphthalene sulfonic acid and 3 g of phenol dissolved in 240 ml of pure water was placed in a sand mill container, and Zr of 1 mmφ was used.
After dispersing with O ₂ beads for 10 hours and finishing with pure water to 250 ml, the mixture was cooled and set to prepare a fine dye particle dispersion having an average dye particle diameter of 0.20 μm.

<Preparation of Gelatin Solution G> The procedure is the same as the preparation of the dye fine particle dispersion described above, except that the gelatin solution G is excluded.
Was prepared.

<Preparation of Backing Layer Coating Liquid BC1> Gelatin 32.4 g Pure water 696 ml (Dye C) 6% (W / V) aqueous solution 64 ml (Dye D) 5% (W / V) aqueous solution 24 ml Saponin 33% ( W / V) Aqueous solution 6.6 ml Polymer latex (Copolymer of cyclohexyl-methacrylate, isononyl acrylate, glycidyl-acrylate and styrene-isoprene sulfonic acid having an average particle size of 0.10 μm) 20% (W / V) emulsion liquid 33.6 ml 10% (W / V) zinc oxide solid fine particles (average particle size 0.15 μm) dispersion 10 ml (K) solid fine particles (average particle size 0.1 μm) dispersion 10 ml Citric acid 7% (W / V) aqueous solution 3.8 ml sodium styrenesulfonate 4% (W / V) aqueous solution 23 ml After adding and mixing the above additives, A backing layer coating solution BC1 was prepared by adjusting with pure water so that the total amount was 895 ml.

<Preparation of Coating Solution BP1 for Backing Protective Layer> Gelatin 24.9 g Pure water 605 ml 2% (W / V) dispersion of methyl methacrylate (average particle size 7 μ) 72 ml 1-decyl-2- (3 -Isopentyl) succinate-2-sulfonate sodium 4% (W / V) aqueous solution 11 ml Glyoxal 4% (W / V) aqueous solution 4 ml After adding and mixing the above additives, adjust with pure water so that the total amount becomes 711 ml and backing A protective layer coating liquid BP1 was prepared.

<Preparation of Backing Layer Hardener Liquid BH1 for In-line Addition> Pure water 27.22 ml Methanol 1.5 ml H-3 Hardener 1.28 ml NaCl 0.005 g Coating solution for protective layer by mixing the above additives Immediately before coating, 30 ml of the hardener solution BH1 which was mixed and added inline was added.

(Preparation of Sample Nos. 1-1 to 1-60) Combination of Table 1 and Table 2 on one side of a 100 μm-thick polyethylene terephthalate transparent support which had been subjected to undercoating in advance from the side closer to the support. So that the gelatin lower layer coating solution has a gelatin dry weight of 0.5 g / m ² , and the image forming layer emulsion coating solution E3 has a gelatin dry weight of 1.0 g / m ² .
m ² and silver coating amount 3.5 g / m ² , the intermediate layer coating solution had a gelatin dry weight of 0.3 g / m ² , and the exposed visible image forming layer emulsion solution had a gelatin dry weight of 0.4 g / m ^2. Then, the coating solution for protective film layer was simultaneously multi-layered so that the dry weight of gelatin was 0.3 g / m ² so that the amount of silver deposited was 0.4 g / m ² .

In that case, the MIX ratio of the hardener liquid MH1 for in-line addition of the intermediate layer and the hardener liquid PH1 for in-line addition of the protective layer to the main liquid (P1) was adjusted to the above-mentioned finishing ratio for each main liquid. Immediately before coating, the mixture was applied. Simultaneously, the backing layer coating liquid BC1 is mixed with the backing layer in-line addition hardener liquid BH1 at the finishing ratio described above on the opposite side of the support immediately before coating so that the gelatin dry weight becomes 1.8 g / m ^2. Then, the backing protective layer coating solution BP1 was multi-layered so that the dry weight of gelatin was 0.5 g / m ² . After coating all coating liquids at a coating liquid temperature of 35 ° C, treat them with cool air at 5 ° C for 6 seconds and set them, and then control the conditions to keep the drying temperature at 35 ° C or less and the film surface temperature at 20 ° C or less in order The layer is dried for 2 minutes, and within 20 seconds after the completion of drying, the drying temperature is 50 ° C. and the dew point is −5.
The sample of Table 1 and Table 2 was created by processing at 50 ° C. for 50 seconds.

(Evaluation method) The following evaluations were performed using the samples obtained by the above method, and the obtained results are shown in Tables 1 and 2.
It was shown to.

(Evaluation of Sensitivity) A bright room UV printer P-627FA manufactured by Dainippon Screen Co., Ltd. was used, and a 100 μm-thick 50% hard dot halftone transmissive film original was used as an original to prepare an emulsion layer for the support of the sample. Sec (LogE) is the common logarithmic value of the reciprocal of the exposure time, which is 50% after processing under the following processing conditions.
And

Processing conditions Development conditions 34 ° C. 12 seconds Fixing conditions 32 ° C. 12 seconds Water washing conditions Normal temperature 10 seconds Drying conditions 40 ° C. 10 seconds Developer formulation Pure water 205.7 ml Diethylenetriamine-5-acetic acid 3.63 g Sodium sulfite 52.58 g Boric acid 8.0 g KBr 4.0 g Potassium carbonate (49% (W / V) aqueous solution) 112.24 g 2-Mercaptohypoxanthine 0.07 g Diethylene glycol 40 g Benzotriazole 0.21 g Hydroquinone 20 g Dimezone S 0.85 g 1-Phenyl-5- Mercaptotetrazole 0.03 g Potassium hydroxide (48.55% (W / V) aqueous solution) 14 ml At the time of use, water was added to finish to 1 liter, which was set in an automatic processor for use. The pH was 10.4.

Fixer formulation Ammonium thiosulfate (70% (W / V) aqueous solution) 262 g Pure water 79 ml Sodium sulfite 22 ml Boric acid 9.78 ml Sodium acetate 38.5 g Acetic acid (90% (W / V) aqueous solution) 13.28 g Tartaric acid ( 50% (W / V) aqueous solution) 7.27 g Aluminum sulphate (Al2O3 equivalent content is 8.1% (W / W) aqueous solution) 26.5 g Water is added at the time of use to finish to 1 liter and set in an automatic processor. did. The pH was 4.85.

(Evaluation of γ) Using a bright room UV printer P-627FA manufactured by Dainippon Screen Co., Ltd.
Exposure was carried out while suction-adhering the emulsion layer coating side to the sample support using a step wedge film having a thickness of 00 μm, and after processing under the above processing conditions, a density of 0.05 was obtained, which is the logarithm of the reciprocal of the exposure amount. Is E (0.05), and the logarithm of the reciprocal of the exposure amount that gives a density of 2.5 is E (2.5).
Was calculated by the following formula.

Γ = 2.45 / (E (0.05) −E (2.5)) (Evaluation of Safelight Durability) A fading prevention lamp manufactured by Toshiba Corporation was used as a safelight light source, and each test sample was tested. The emulsion side is placed in the safelight light source direction with respect to the support, and the irradiation time is changed with a safelight light amount of 300 Lux, and the fog density after processing is +0.000 according to the same processing conditions as in "Evaluation of sensitivity".
The time to rise by 35 was designated as T (min).

(Evaluation of Residual Color Contamination) Unexposed samples were subjected to the same processing conditions as in “Evaluation of Sensitivity” according to the same processing conditions, five sheets were piled up, and a sensory evaluation was visually conducted in five stages. "5" is the best "1"
Is the lowest, and "3" or more is a practical level.

The above results are shown in Tables 1 and 2.

(Photographic performance evaluation method) Trace of sticking In FIG. 1, the halftone dot image film 2 is placed on the sticking bases 3 and 5, and the periphery of the halftone dot image film is fixed with a transparent scotch tape for platemaking. If there is no tape mark (stick mark) after the exposure and development process, "5",
Marks were conspicuous, and the worst level was set to "1" and evaluated in 5 levels. In FIG. 1, reference numeral 1 represents a return photosensitive material (sample), 5 a line drawing positive image film, and 6 a gut mask film.

[0251]

Embedded image

[0252]

Embedded image

[0253]

Embedded image

[0254]

[Table 1]

[0255]

[Table 2]

As is clear from Tables 1 and 2, the present invention has improved handleability in a bright room, has no residual color contamination even in rapid processing, and has no deterioration in gamma (γ). It can be seen that a photosensitive material can be obtained.

Example 2 The sample obtained in Example 1 was treated by the method described in Example 1 to evaluate halftone dots and storability, and the results are shown in Tables 3 and 4.
Summarized in The evaluation items and evaluation criteria are as follows.

(Halftone Quality) After halftone exposure was carried out so that the halftone dot area would be 90%, the halftone quality was divided into 10 levels, and each sample was visually evaluated with a magnifying glass (× 100). The best halftone dot quality is 10 and 1 is an extremely bad level, and 5
The above is the practical level.

(Storage stability) The obtained sample was stored at a temperature of 23.
After adjusting the humidity at 50 ° C. and RH of 50%, the emulsion layer surface side and the backing layer surface side were brought into contact with each other and stacked and sealed. This sample was heated at
The sample was stored under conditions of 0 ° C. and RH of 20% for 5 days, and the sensitivity of the sample after storage was determined with the sensitivity of the sample before storage being 100.
Here, the reciprocal of the exposure amount necessary to obtain a density of 2.5 was used as the sensitivity.

[0260]

[Table 3]

[0261]

[Table 4]

As is clear from Tables 3 and 4, Samples 2-1 to 2-60 of the present invention have good halftone dot quality and excellent storage stability.

Further, ascorbic acid 40 g and erythorbic acid 40 g were used in place of the hydroquinone 20 g in the developer of Example 1, and the same treatment as in Example 2 was carried out using the sample obtained in Example 1, When the same evaluation was performed, the same effect as in Example 2 was obtained.

[0264]

EFFECTS OF THE INVENTION According to the present invention, as demonstrated in the examples, excellent safe light resistance, improved handleability in a bright room, no residual color contamination even during rapid processing, and no deterioration in contrast. Further, a silver halide photographic light-sensitive material excellent in storage stability and a processing method thereof were obtained.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an outline of an exposure method for evaluation of a sticking mark.

[Explanation of symbols]

 1 Photosensitive material for return (sample) 2 Halftone image film 3 Base for sticking 4 Base for sticking 5 Line drawing positive image film 6 Gut mask film

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 5/29 501 G03C 5/29 501 5/30 5/30

Claims (11)

[Claims] 1. A silver halide photographic light-sensitive material having a silver halide photographic emulsion layer on a support and a non-photosensitive hydrophilic colloid layer, wherein at least one hydrophilic colloid layer has the following general formula (1): ) A silver halide photographic light-sensitive material comprising a solid fine particle dispersion of a dye represented by Embedded image [In formula, Za, Zb, and Zc are -N = or -C, respectively.
(R ² ) =, R ¹ and R ² represent a hydrogen atom or a monovalent substituent, L ¹ , L ² and L ³ each represent a methine group, and B ¹
Represents an oxygen-containing 6-membered ring, and n represents 0 or 1. ] 2. A silver halide photographic light-sensitive material having a light-sensitive silver halide photographic emulsion layer on a support and a non-light-sensitive hydrophilic colloid layer, wherein at least one hydrophilic colloid layer has the following general formula: A silver halide photographic light-sensitive material comprising a solid fine particle dispersion of the dye represented by (2) or the general formula (3). Embedded image [In the formula, G ₁ and G ₂ are cyano groups, —COR ³ , and —CONR ^{3
_{R 4, -OCOR 3, -SO 2}} R 3, represents _{^{-SO 2 NR 3 R 4, R}} 3, R 4 represents an alkyl group, an aryl group, a heterocyclic group or an alkenyl group, G _1, G ₂ is They may be the same or different, and R ³ and R ⁴ may combine with each other to form a 5- or 6-membered ring. L ¹ , L ² and L ³ each represent a methine group,
B ¹ represents an oxygen-containing 6-membered ring, and n represents 0 or 1. ] [Chemical 3] [In formula, A represents the following structures. R ^{12 of} the following structure,
R ¹³ and R ¹⁴ represent a hydrogen atom or a substituent. R ¹² , R ¹³
May be linked to each other to form a 5- or 6-membered ring.
L ¹ , L ² and L ³ each represent a methine group, B ₁ represents an oxygen-containing 6-membered ring, and n represents 0 or 1. [Formula 4] 3. The silver chloride content is 70 mol% or more,
At least one silver halide photographic emulsion layer containing 1 × 10 ^-9 to 1 × 10 ^-2 mol of a salt of a transition metal selected from rhodium, ruthenium, iridium, rhenium, chromium, osnium and copper per mol of silver halide is used. Have layers,
A solid fine particle dispersion of a dye represented by the following general formula (4) in at least one hydrophilic colloid layer in a silver halide photographic light-sensitive material which has a non-photosensitive hydrophilic colloid layer and can be used in a bright room environment. A silver halide photographic light-sensitive material comprising: Embedded image [In the formula, A ¹ represents a pyrazolotriazole or an acidic nucleus. L ¹ , L ² and L ³ each represent a methine group, B ¹ represents an oxygen-containing 6-membered ring, and n represents 0 or 1. ] 4. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, which contains a hydrazine derivative. 5. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, which contains a pyridinium salt derivative. 6. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, which contains a tetrazolium salt derivative. 7. A hardener which acts by activating a carboxyl group, as claimed in claim 3.
The silver halide photographic light-sensitive material as described in 4, 5, or 6. 8. The silver halide photographic light-sensitive material according to claim 7, wherein the hardener is represented by the following general formula (5). [Chemical 6] [In the formula, R ⁶ and R ₇ represent an alkyl group or an aryl group, and R ⁶ and R ⁷ may form a ring. R ⁸ represents a hydrogen atom or a substituent. L ⁴ represents a single bond or a divalent group. X ¹ represents a single bond or —O—, —N (R ⁹ ) —, R
⁹ represents a hydrogen atom, an alkyl group or an aryl group. ] 9. The silver halide according to claim 3, wherein B ¹ in the general formula (4) has a structure represented by the following general formula (6) or general formula (6 ′). Photographic material. Embedded image [In the formula, R ₁₂ , R ₁₃ and R ₁₄ represent a hydrogen atom or a non-metal substituent. ] 10. The method of claim 1, 2, 3, 4, 5, 6, 7,
The silver halide photographic light-sensitive material described in 8 or 9 has dihydroxybenzenes as a developing agent and has a pH of 9.5 or more and a pH of 1 or more.
A method of processing a silver halide photographic light-sensitive material, which comprises processing with a developing solution of 1.0 or less. 11. The method of claim 1, 2, 3, 4, 5, 6, 7,
The silver halide photographic light-sensitive material described in 8 or 9 contains at least one compound selected from ascorbic acid (salt) and / or erythorbic acid (salt), and does not contain hydroquinone and has a pH of pH 9.5 or more 11 A method of processing a silver halide photographic light-sensitive material, which comprises processing with a developing solution of 0.0 or less.