JPH0954380A - Silver halide photographic sensitive material and image forming method using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material high in sensitivity and small in occurrence of black spots and fluctuation of photographic performances with time lapse and to provide the image forming method to be used therefor. SOLUTION: The silver halide photographic sensitive material contains the pyridinium salt derivative in at least one of hydrophilic colloidal layers in the photographic constituent layers and it is processed in the presence of a pyridine derivative in this image forming method. The photosensitive material contains the pyridinium salt derivative and the pyridine derivative in any of hydrophilic colloidal layers. The photosensitive material contains the pyridine derivative in at least one of the photographic constituent layers comprising a support and an emulsion protective layer and at least 2 emulsion layers, and silver halide grains having an average silver chloride content of >=60mol% and sensitized by a merocyanine or cyanine dye and a hydrazine derivative.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silver halide photographic light-sensitive material and an emulsion thereof and an image forming method, and more particularly to a method for producing a black-and-white silver halide photographic light-sensitive material and an emulsion thereof and an image forming method. More specifically, it relates to a silver halide photographic light-sensitive material for printing plate making, a method for producing an emulsion thereof and an image forming method.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials are widely used because they can form images with high sensitivity and high resolution. For printing and plate making, high image quality is required. A silver halide photographic light-sensitive material containing a pyridinium compound, for example, has been proposed as a means of obtaining a high-contrast image.However, in such a light-sensitive material, a non-developed portion called a pepper fog should be formed in the unexposed area. The generated black spots appeared, and the image quality was degraded. On the other hand, the inventor tried to solve the problem by adding a specific development inhibitor to the light-sensitive material, but the image quality was softened during raw storage of the light-sensitive material, and a sufficient effect was not obtained.

On the other hand, in recent years, the generation of halftone dots by a laser scanner has become more important, but the conventional photosensitive material has a problem that the unexposed portion is also developed and crushed when reproducing large points. As a solution, a photosensitive material coated with a photosensitive silver halide emulsion layer with different sensitivity appeared, but in the high-sensitivity layer, there was a problem that pepper fog was more likely to occur during raw storage, and the image was not reproduced yet. There was room for improvement in sex. Further, pepper fog frequently occurs with a decrease in sulfite ion used as a preservative and a rise in pH due to the fatigue of the treatment liquid over time, which significantly reduces the commercial value as a sensitizer for printing plate making. there were. Therefore, there has been a strong demand for a system that maintains high sensitivity and high contrast even after being stored fresh and improves black spots.

[0004]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide a silver halide photographic light-sensitive material having photographic characteristics of high sensitivity and γ of more than 10 by using a developing solution which is stable at a low pH and has little black spots. A material, a method for producing a silver halide emulsion used therein, and an image forming method thereof are provided. A second 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 does not change with time, a method for producing a silver halide emulsion used therein and an image forming method thereof.

[0005]

As described above, an object of the present invention is to provide a novel photographic light-sensitive material for printing. An object of the present invention is to provide a photographic light-sensitive material for printing plate making which has less pepper fog even after raw storage. Another object of the present invention is to have excellent image reproducibility even after being stored rawly,
It is to provide a photographic light-sensitive material and an image forming method.
Another object of the present invention is to provide a photographic light-sensitive material and an image forming method which have high processing stability even after being stored for a while.

The above objects have been achieved by the following methods.

[0007] 1. A silver halide photographic light-sensitive material containing a pyridinium salt derivative in at least one hydrophilic colloid layer in a photographic light-sensitive material constituting layer comprising at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer. Is processed in the presence of a pyridine derivative to form an image of a silver halide photographic light-sensitive material.

2. Containing a pyridinium salt derivative and a pyridine derivative in the same or different hydrophilic colloid layers in a photographic light-sensitive material constituent layer comprising at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer A silver halide photographic light-sensitive material characterized by being

3. Support, emulsion protective layer and at least 2
At least one layer in the photographic light-sensitive material layer comprising two emulsion layers contains a pyridine derivative, and the emulsion layer has an average silver chloride content of 60 mol% or more and is sensitized with a merocyanine or cyanine dye. 3. The silver halide photographic light-sensitive material as described in the above item 2, wherein the halogenated particles and a hydrazine derivative are contained.

4. 4. The silver halide photographic light-sensitive material as described in 2 or 3 above, wherein the emulsion layer farther from the support has higher sensitivity than the emulsion layer closer to the support.

5. Item 5. The silver halide photographic light-sensitive material as described in Item 2, 3 or 4 above, which contains a compound capable of releasing a development inhibitor by being oxidized by an oxidized product of a developing agent.

6. Item 6. The silver halide photographic light-sensitive material described in Item 2, 3, 4 or 5, containing at least one hardener which acts by activating a carboxyl group.

7. 7. The silver halide photographic light-sensitive material as described in 6 above, wherein the hardener is represented by the general formula [1].

[0014]

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(In the formula, R ₁ and R ₂ represent an alkyl group or an aryl group, and R ₁ and R ₂ may form a ring. R ₃ represents a hydrogen atom or a substituent. L represents a single bond. Or a divalent group, X ₁ represents a single bond, —O—, or —N (R ₄ ) —,
R ₄ represents a hydrogen atom, an alkyl group or an aryl group. ) 8. 8. The silver halide photographic light-sensitive material described in item 2, 3, 4, 5, 6 or 7, wherein the pyridine nucleus of the pyridine derivative is substituted with at least one carbamoyl group.

9. 8. The silver halide photographic light-sensitive material described in item 2, 3, 4, 5, 6 or 7, wherein the pyridine nucleus of the pyridine derivative is substituted with at least one hydroxy group.

10. The silver halide photographic light-sensitive material described in 2, 3, 4, 5, 6, 7, 8 or 9 is treated with a developer having a pH of 11.0 or less using dihydroxybenzenes as a developing agent. A method for forming an image on a silver halide photographic light-sensitive material.

11. The silver halide photographic light-sensitive material according to the above item 2, 3, 4, 5, 6, 7, 8 or 9 contains ascorbic acid and / or erythorbic acid, does not contain hydroquinone and has a pH of 11.0 or less. An image forming method for a silver halide photographic light-sensitive material, which comprises processing with a developing solution.

The present invention will be described in detail below.

The pyridine derivative used in the present invention is preferably a compound represented by the following general formula [2].

[0021]

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In the formula, R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, a cyano group, A hydroxy group, a mercapto group, an amino group, an alkoxy group, an aryloxy group, an acyl group, a carbamoyl group, an acylamino group, a ureido group, a sulfamoyl group and a sulfonamide group are represented by R ₅ , R ₆ and R ₇ which are simultaneously hydrogen. It does not represent an atom. R ₅ , R ₆ , and R ₇ are preferably alkyl groups having 1 to 6 carbon atoms (for example, methyl group, ethyl group, butyl group, 2-hydroxyethyl group, etc.), hydroxy group, halogen atom (for example, fluorine atom, Chlorine atom etc.), alkoxy group (eg methoxy group, ethoxy group, methylenedioxy group, 2-hydroxyethoxy group, n-butoxy group etc.), substituted amino group (eg dimethylamino group, diethylamino group, di (n -Butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-ethyl-N-
Methanesulfonamidoethylamino group, morpholino group,
Piperidino group, pyrrolidino group etc.), carbamoyl group (eg methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group etc.), carboxy group, sulfonamide group (eg methanesulfonamide group, benzenesulfonamide group etc.), sulfamoyl group (eg (Sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), and particularly preferably carbamoyl group, hydroxy group and mercapto group. The pyridine derivative used in the present invention is particularly preferably a mono-substituted product or a di-substituted product.

Specific examples of the pyridine derivative used in the present invention are shown below, but the invention is not limited thereto.

[0024]

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[0025]

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[0026]

[Chemical 6]

The pyridine derivative particularly preferably used in the present invention is a compound substituted with at least one carbamoyl group and / or at least one hydroxy group, and specific examples thereof include 2-pyridinol and picolinamide. When the pyridine derivative used in the present invention is substituted with a hydroxy group, a compound in which the pyridine nucleus is substituted is particularly preferable. The pyridine derivative preferably used in the present invention is a compound substituted with at least one carbamoyl group, and specific examples thereof include nicotinamide and the like.

The addition amount of the pyridine derivative of the present invention 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. When it is contained, it is preferably in the range of 10 ^-6 to 10 ^-1 mol per mol of silver halide, particularly 10
A range of ^-5 to 10 ^-2 mol is preferred. Further, in the present invention, two or more kinds of pyridine derivatives can be contained in any layer in any state. When the pyridine derivative of the present invention is used by adding it to a developing solution, the addition amount to the developing solution is
The range is preferably from 10 ⁻⁴ to 10 mol / l, more preferably from 10 ⁻³ to 1 mol / l. Two or more pyridine derivatives can be contained in the developer when added.

Examples of the pyridinium salt derivative used in the present invention include compounds represented by the following general formula [Pa], [Pb] or [Pc].

[0030]

[Chemical 7]

In the formula, A ₁ , A ₂ , A ₃ , A ₄ and A ₅ represent a non-metal atom group for completing the nitrogen-containing heterocycle,
It may contain an oxygen atom, a nitrogen atom, or a sulfur atom, and the benzene ring may be condensed. A ₁ , A ₂ , A ₃ , A ₄
And the heterocycle composed of A ₅ may have a substituent and may be the same or different. As the substituent, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxy group, an alkoxy group,
It represents an aryloxy group, an amide group, a sulfamoyl group, a carbamoyl group, a ureido group, an amino group, a sulfonamide group, a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group and an arylthio group. Preferred examples include A ₁ , A ₂ , A ₃ , A ₄ and A _{5 which} are 5- or 6-membered rings (for example, pyridine, imidazole, thiozole, oxazole, pyrazine, pyrimidine rings, etc.). A pyridine ring can be mentioned.

B _P represents a divalent linking group, and the divalent linking group is alkylene, arylene, alkenylene or --SO ₂
-, -SO-, -O-, -S-, -CO-, -N
(R ₁₁ )-, (R ₁₁ represents an alkyl group, an aryl group, or a hydrogen atom) are used alone or in combination.
Preferred examples of B _p include alkylene, alkenylene, and alkylene oxide.

R ₈ , R ₉ and R ₁₀ are saturated and unsaturated alkyl groups having 1 to 20 carbon atoms. R ₈ and R ₉ may be the same or different. As the substituents, A ₁ , A ₂ ,
It has the same meaning as the groups mentioned as the substituents for A ₃ , A ₄ and A ₅ .

As a preferred example, R ₈ , R ₉ and R ₁₀ each represent a substituted or unsubstituted aryl group or alkyl group. A more preferred example is a substituted alkyl group having 4 to 10 carbon atoms. X _p represents a counter ion necessary for balancing the charges of the entire molecule, and examples thereof include chloride ion, bromine ion,
It represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate and oxalate. 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 compounds are shown below.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

[Chemical 12]

The optimum amount of addition varies depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of inhibitor, etc., but generally 10 per mol of silver halide
The range is preferably from ^-6 to 10 ^-1 mol, particularly from 10 ^-5 to 10 ^-2.
A molar range is preferred. Further, in the present invention, three or more kinds of pyridinium salt derivatives can be contained in any layer in any state.

The redox compound capable of releasing the development inhibitor by being oxidized by the oxidant of the developing agent according to the present invention will be described.

The redox compound has a group in its molecular structure which can be oxidized by an oxidant of a developing agent,
Examples thereof include hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines and reductones.

Preferred redox compounds are the following general formulas [3], [4], [5], [6] and [7].
Alternatively, it is a compound represented by [8] and a compound having a -NHNH- group.

[0044]

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In the formula, R ₁₂ represents an alkyl group, an aryl group or a heterocyclic group. R ₁₃ and R ₁₄ are a hydrogen atom, an acyl group,
Carbamoyl group, cyano group, nitro group, sulfonyl group,
It represents an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group. R ₁₅
Represents a hydrogen atom. R _{16 to} R ₂₁ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. r ₁ , r ₂ and r ₃
Represents a substituent capable of substituting on the benzene ring. X ₂ and X ₃ are −
Represents O- or -NH-. Z ₁ represents an atomic group necessary for forming a 5- or 6-membered heterocycle. W is -N (R ₂₂₎ R
₂₃ or —OH, and R ₂₂ and R ₂₃ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. W ₂ represents SO ₂ or CH ₂ .

COUP represents a coupler residue capable of causing a coupling reaction with an oxidized product of an aromatic primary amine developing agent, and a star 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 represents 0 or 1.

PUG represents a group capable of becoming a development inhibitor when released.

The above general formulas [3], [4], [5],
In [6], [7] or [8], R ₁₂ and R _{16 to} R ₁₆
Preferable examples of the alkyl group, aryl group and heterocyclic group represented by ₂₃ 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 ₁₃ and R ₁₄ , preferably an acyl group and carbamoyl group. And a cyano group. The total number of carbon atoms in these groups is preferably 1 to 20. R _{12 to} R ₂₃ may further have a substituent, and examples of the substituent include a 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 groups (eg, benzyl group, 2-phenethyl group, etc.), aryl groups (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.), alkylthio group (eg Methylthio group, ethylthio group, butylthio group etc.), arylthio group (eg phenylthio group etc.), sulfonylamino group (eg methanesulfonylamino group, benzenesulfonylamino group etc.), ureido group (eg 3-methylureido group, 3,3) -Dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, etc.),
Carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.) ,
Aryloxycarbonyl group (for example, phenoxycarbonyl group, etc.), sulfonyl group (for example, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.),
Acyl group (eg acetyl group, propanoyl group, butyroyl group etc.), amino group (methylamino group, ethylamino group, dimethylamino group etc.), hydroxyl group, nitro group, imide group (eg phthalimido group etc.), heterocyclic group (For example, a pyridyl group, a benzimidazolyl group, a benzthiazolyl group, a 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.
Colorless coupler residues include open-chain or cyclic active methylene compounds (eg, indanone, cyclopentanone, malonic acid 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).

[0052]

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In the formula, R ₂₄ represents an acylamido group, anilino group or ureido group, and R ₂₅ represents a phenyl group which may be substituted with one or more halogen atoms, alkyl groups, alkoxy groups or cyano groups.

[0054]

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In the formula, R ₂₆ and R ₂₇ represent a halogen atom, an acylamido group, an alkoxycarbonylamido group, a sulfoureido group, an alkoxy group, an alkylthio group, a hydroxy group or an aliphatic group, and R ₂₈ and R ₂₉ are each a fatty acid. It represents a group group, an aromatic group or a heterocyclic group. Further, one of R ₂₈ and R ₂₉ may be a hydrogen atom. a is an integer of 1 to 4, b
Represents an integer of 0 to 5. When a and b are plural, R ₂₆ , R
₂₇ may be the same or different, and R ₂₈ and R ₂₉ may be the same or different.

[0056]

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In the formula, R ₃₀ represents a tertiary alkyl group or an aromatic group, and R ₃₁ represents a hydrogen atom, a halogen atom or an alkoxy group. R ₃₂ represents an acylamide group, an aliphatic group, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, an alkoxy group, a halogen atom or a sulfonamide group.

[0058]

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In the formula, R ₃₃ represents an aliphatic group, an alkoxy group, an acylamino group, a sulfonamide group, a sulfamoyl group, a diacylamino group, and R ₃₄ represents a hydrogen atom, a halogen atom or a nitro group.

[0060]

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R ₃₅ and R ₃₆ represent a hydrogen atom, an aliphatic group, 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.

Tm represents a timing group, preferably-
OCH ₂ — or other divalent timing groups, eg US Pat. Nos. 4,248,962 and 4,409,323.
No. or No. 3,674,478, Research D
isclosure 21228 (December 1981)
Month), or JP-A-57-56837 and JP-A-4-43.
Those described in Japanese Patent No. 8 and the like can be mentioned.

PUG is a group that can be released to become a development inhibitor, and examples of the development inhibitor include those described in US Pat.
477,563, JP-A-60-218644, 6
The development inhibitors described in 0-221750, 60-233650, 61-11743 and the like can be mentioned.

The general formula [3] to be used in the present invention will be described below.
Specific examples of the compound represented by [8] are listed, but the present invention is not limited thereto.

[0066]

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[0067]

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[0068]

[Chemical 21]

[0069]

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[0070]

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[0071]

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[0072]

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[0073]

[Chemical formula 26]

General formula [3] preferably used in the present invention
The compound represented by [8] is preferably contained in an amount of 1 × 10 ⁻⁶ to 5 × 10 ⁻² mol, and more preferably 1 × 10 ⁻⁴ to 2 × 10 ⁻² mol per mol of silver halide. Is preferred.

The compounds represented by the above general formulas [3] to [8] 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 may be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or ultrasonic waves according to a method known as a solid dispersion method.

Next, a preferable compound having a --NHNH-- group as a redox group is a compound represented by the following general formula [RE
-A] or a compound represented by [RE-b].

General formula [RE-a] T-NHNHCO- (Time) -PUG General formula [RE-b] T-NHNHCOCO- (Time) -PUG General formula [RE-a], [RE-b]: T represents an optionally substituted aryl group or an optionally substituted alkyl group. Examples of the aryl group represented by T 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 (preferably Those having 2 to 20 carbon atoms, such as methyl, ethyl, isopropyl group, dodecyl group, etc.),
An alkoxy group (preferably having a carbon number of 2 to 21, such as a methoxy group or an ethoxy group), an aliphatic acylamino group (preferably having an alkyl group having a carbon number of 2 to 21,
Examples thereof include an acetylamino group, a heptylamino group, etc.), an aromatic acylamino group, and the like. In addition to these, for example, a substituted or unsubstituted aromatic ring as described above is -CONH-,
_{-O -, - SO 2 NH -} , - NHCONH -, - CH 2 C
Also included are those linked by a linking group such as HN-.

Development inhibitors which serve as PUG include 5-nitroindazole, 4-nitroindazole, 1-phenyltetrazole, 1- (3-sulfophenyl) tetrazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 5 -Nitroimidazole, 4-nitroimidazole and the like can be mentioned. These development-inhibiting compounds are bound to the CO site of T-NHNH- (CO) ₁ or _2- via the (Time) group. Time has the same meaning as Tm shown for the redox compound.

In addition, a development inhibitor such as triazole, indazole, imidazole, thiazole or thiadiazole may be introduced into a hydroquinone compound having a ballast group. For example, 2- (dodecyloxyethylthiopropionamide) -5- (5-nitroindazol-2-yl) hydroquinone, 2- (stearylamide) -5- (1-phenyltetrazole-5
-Ilthio) hydroquinone, 2- (2,4-di-t-
Amylphenoxypropionic acid amide) -5- (5-nitrotriazol-2-yl) hydroquinone, 2-dodecylthio-5- (2-mercaptothiadiazole-5
-Ilthio) hydroquinone and the like. The redox compound can be synthesized with reference to the description in US Pat. No. 4,269,929. 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. Further, those which are difficult to dissolve in water or an organic solvent can be arbitrarily dispersed with an average particle diameter of 0.01 to 6 μm by high speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion or the like. For dispersion, a surfactant such as an anion or nonion, a thickener, a latex, or the like can be added and dispersed. The amount of redox compound added is preferably from 10 ^-6 to 10 ^-1 mol, and more preferably from 10 ^-4 to 10 ^-1 mol per mol of silver halide.
^-2 mole range.

Among the compounds represented by the general formula [RE-a] or [RE-b], particularly preferable compounds are shown below.

[0082]

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[0083]

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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.

In the present invention, the redox compound can be present in the silver halide emulsion layer, in a layer adjacent to the emulsion layer, another layer via the adjacent layer, or the like. Particularly preferably,
The emulsion layer and / or the 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 silver halide photographic light-sensitive material according to the present invention, generally known sulfur sensitization, reduction sensitization and noble metal sensitization methods are used in combination with chemical sensitization using a compound such as Se or Te. May be.

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.

The gold sensitization method is a typical one of the noble metal sensitization methods, 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 reduction sensitizers include stannous salts, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

In the silver halide photographic light-sensitive material according to the present invention, the halogen composition of silver halide in the silver halide emulsion is pure silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride or 60 mol%. The above is silver chloroiodobromide containing silver chloride.

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. What is particle size?
In the case where the particles are spherical or particles that can be approximated to spheres, this means particle diameter. If the particle is a cube, convert it to a sphere,
The diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE Mee).
s & T. H. By James: The theory o
f the photographic processes
s), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmillan")).

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrow, and in particular, the total number of particles is 9% within a particle size range of ± 40% of the average particle size.
A so-called monodisperse emulsion containing 0%, preferably 95%, is 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 in which grains are formed in the presence of excess silver ions (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 include cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt and 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).

In the present invention, it is preferable to use a nucleation accelerator in order to effectively promote the contrast enhancement. Examples of the nucleation accelerator include Japanese Patent Application No. 6-103982, pp. 28-
The compounds described on page 29 are mentioned, and specific examples thereof are described in, for example, Japanese Patent Application No. 6-103982, pages 30 to 35 (N.
a-1) to (Na-22) or (Nb-1) to (Nb)
The compounds described as -12) can be mentioned, but the invention is not limited thereto.

Preferred examples of the nucleation accelerator are mentioned here for reference, but the present invention is not limited thereto.

[0099]

[Chemical 29]

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 pyridinium salt derivative and the nucleation accelerator used in the present invention can be used in any layer on the silver halide emulsion layer side, but preferably in the silver halide emulsion layer or its adjacent layer. It is preferable to use. The black-and-white light-sensitive material according to 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 development replenishment amount and the fixing replenishment amount are 300 ml or less per 1 m ² in order to reduce the amount of waste liquid. Preferably it is 75 to 200 ml per m ² .

In order to shorten the developing time, the present invention has 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 by using the automatic developing machine. It is preferably -60 seconds. The total processing time referred to here includes the total process time required for processing the black-and-white light-sensitive material, and specifically, for the processing, such as development, fixing, bleaching, washing, stabilizing, and drying. Time including all process time, that is, Dr
It is the time of y to Dry. 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, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, silicon carbide, etc., can be directly heated and radiated by passing an electric current.
It emits infrared rays by transmitting heat to radiators such as stainless steel, nickel, and various types of ceramics) that includes a zone that dries.

The silver halide emulsion of the present invention can be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus,
A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus, and the like. A benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may be substituted on carbon atoms. In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus,
A 5- to 6-membered heterocyclic ring such as a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied. Specifically, Research Disclosure No. 176
Volume RD-17643 (December 1978 issue) No. 2 and 3
, U.S. Pat. Nos. 4,425,425 and 4,425,4
No. 26 can be used. The sensitizing dye may be dissolved by using ultrasonic vibration described in U.S. Pat. No. 3,485,634. Other methods for dissolving or dispersing the sensitizing dye of the present invention in an emulsion include those described in U.S. Pat. Nos. 3,482,981, 3,585,195, 3,469,987 and 3,469,987. 3,425,835 and 3,342,605, British Patents 1,271,329 and 1,038,029,
No. 1,121,174, U.S. Pat. No. 3,660,101
No. 3,658,546 can be used. These sensitizing dyes may be used alone,
Combinations of these may be used, and combinations of sensitizing dyes are often used particularly for supersensitization. Useful supersensitizing dye combinations and supersensitizing substances are described in Research Disclosure (Research).
h Disclosure) Volume 176 17643 (19
Issued December 1978), page 23, IV, section J.

The light-sensitive material of the present invention may contain various dyes for the purpose of improving safety of safelight. Preferred dyes include those represented by the following general formulas [I] to [VI].

[0106]

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In the formula, A and A ′, which may be the same or different, each represents an acidic nucleus, Q represents an aryl group or a heterocyclic group, B represents a basic nucleus, and Q ′ represents a heterocyclic group. And X ₄ and Y, which may be the same or different, each represents an electron-withdrawing group, and L ₁ , L ₂ and L ₃ each represent a methine group. m ₂ represents 0 or 1, t represents 0, 1 or 2, and p ₂ represents 1 or 2. However, the dyes represented by the general formulas [I] to [VI] have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule.

Examples of the aryl group represented by Q in the above general formulas [I] and [IV] include a phenyl group and a naphthyl group. Examples of the heterocyclic group represented by Q include pyridine, quinoline, isoquinoline, pyrrole, pyrazole, imidazole and indole residues.

The aryl group and the heterocyclic group include those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group,
Carboxy group, cyano group, hydroxy group, mercapto group, amino group, alkoxy group, aryloxy group, acyl group, carbamoyl group, acylamino group, ureido group,
Examples thereof include a sulfamoyl group and a sulfonamide group, and two or more of these substituents may be combined. Preferably,
Alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, butyl group, 2-hydroxyethyl group, etc.), hydroxy group, halogen atom (eg, fluorine atom, chlorine atom, etc.), alkoxy group (eg, methoxy group) , Ethoxy group, methylenedioxy group, 2-hydroxyethoxy group,
n-butoxy group, etc.), substituted amino group (eg, dimethylamino group, diethylamino group, di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-
Ethyl-N-methanesulfonamide ethylamino group, morpholino group, piperidino group, pyrrolidino group etc.), carboxy group, sulfonamide group (eg methanesulfonamide group, benzenesulfonamide group etc.), sulfamoyl group (eg sulfamoyl group, methyl (Sulfamoyl group, phenylsulfamoyl group, etc.), and these substituents may be combined.

The acidic nuclei represented by A and A'in the general formulas [I], [II] and [III] are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanin, hydantoin and thio. Hydantoin, oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone,
Pyrazolopyridone and the like.

The basic nucleus represented by B in the general formulas [III] and [V] is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole, thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole. , Indole, etc.

The electron withdrawing groups represented by X ₄ and Y in the general formulas [IV] and [V] may be the same or different,
Examples thereof include a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxy group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group and a sulfamoyl group.

The heterocycle represented by Q'in the general formula [VI] is
Examples include pyridine, pyridazine, quinoline, pyrrole, pyrazole, imidazole and indole.

L ₁ , L ₂ and L _{3 of the} general formulas [I] to [V]
The methine group represented by includes those having a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, isobutyl, etc.),
Aryl groups (eg phenyl, p-tolyl, p-chlorophenyl etc.), alkoxy groups having 1 to 4 carbon atoms (eg methoxy group, ethoxy group etc.), aryloxy groups (eg phenyl group etc.), aralkyl groups (eg benzyl) Group, phenethyl group, etc.), heterocyclic group (eg, pyridyl, furyl, thienyl, etc.), substituted amino group (eg, dimethylamino, tetramethyleneamino, anilino, etc.), alkylthio group (eg, methylthio group, etc.).

Next, specific examples of the dye used in the present invention will be given.

[0116]

[Chemical 31]

[0117]

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[0118]

[Chemical 33]

These dyes have at least one dissociative proton having a pKa of 4 to 11, preferably 4.5 to 7.0 in a mixed solvent of water-ethanol volume ratio of 1: 1. To have. Further, in the present invention, the immobilization can be achieved by the silver salt and the silver complex formed by the reaction of the dye and the silver ion. Preferred dyes capable of forming silver salts of such dyes are, for example, JP-A-5-18123.
The compounds represented by the general formulas [I] to [V], the general formulas [I '] to [V'], and the general formula [VI] described on page 4 to page 28 of the No. 0 specification are mentioned. To be More specific compounds include I-1 to 37, II-1 to 5, III-1 to 7, and IV-1 to P-6 to P-46 described in the same specification.
6, V-1 to 5, I'-1 to 12, II'-1 to 9, II
I'-1 to 9, IV'-1 to 9, V'-1 to 6, VI-1 to
52 is mentioned.

In the present invention, the above general formulas [I] to [V
The method for dispersing the dye represented by I] is not particularly limited, but a known method such as an acid precipitation method, a ball mill, a jet mill or an impeller dispersion method can be applied.

The average particle size of the finely dispersed dye fine particles of the present invention can be any value, but is preferably 0.01.
˜20 μm, more preferably 0.03 to 2 μm. Further, the coefficient of variation of the particle diameter of the solid dispersed dye fine particles of the present invention is preferably 60% or less, more preferably 40% or less.

The layer containing the fine dye particles of the present invention is provided between the emulsion layer and the support. Preferably, the first undercoat layer is provided on the support, and the hydrophilic colloid second undercoat layer containing the dye fine particles of the present invention is provided thereon. The addition amount of the fine dye particles 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.

[0123] The hydrophilic colloid layer containing a dye fine particles of the present invention, the coating amount is 0.05 g / m ² or more 0.5 g / m ²
But less than 0.18 g / m ^{2 and} more than 0.4
It is less than 2 g / m ² . Further, in order to enhance the effect of the present invention, it is preferable that the ratio of the average particle diameter of the dye fine particles to the film thickness of the dye layer is 0.2 to 2.0.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during 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 (particularly 1-
Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines and mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3,3). 3a, 7-tetrazaindenes), pentazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like can be added. it can.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention 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. Etc. alone It can be used in combination.

As the hardener, the following general formula [1] is used.
The compound represented by is particularly preferably used.

[0127]

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In the compound represented by the general formula [1],
R ₁ and R ₂ have a linear, branched or cyclic carbon number of 1 to 2
And an alkyl group of 0 (eg, methyl group, ethyl group, butyl group, cyclohexyl group, 2-ethylhexyl group, dodecyl group, etc.). R ₁ and R ₂ may have a substituent, and examples of the substituent include the above-mentioned general formula [I].
And a substituent for substituting the aryl group represented by Q of [VI], and a substituent for substituting the heterocycle represented by Q and Q ′ of the general formulas [I], [IV] and [VI]. There are some.

It is also preferable that R ₁ and R ₂ are combined to form a ring together with a nitrogen atom, and particularly preferable examples are cases where a morpholine ring and a pyrrolidine ring are formed. R ₃ 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 represents a single bond, an alkylene group having 1 to 20 carbon atoms (eg, methylene group, ethylene group, trimethylene group, propylene group, propylene group), 6 to 2 carbon atoms.
0 arylene group (for example, phenylene group) and a divalent group (for example, paraxylene group) obtained by combining them, an acylamino group (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 ₄ )-, wherein R ₄ is a hydrogen atom or has 1 to 20 carbon atoms.
Is an alkyl group (for example, a methyl group, an ethyl group, a benzyl group, etc.), an aryl group having 6 to 20 carbon atoms (for example, a phenyl group), and an alkoxy group having 1 to 20 carbon atoms (for example, a methoxy group). A hydrogen atom is particularly preferable.

Specific examples of the compound represented by the general formula [1] 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.

Specific examples of the compound represented by the general formula [1] include the following.

[0133]

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[0134]

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The photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer of the present invention may be used for various purposes such as coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. Known surfactants may be used.

Gelatin is advantageously used 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 hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-
Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

Examples of gelatin include lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The photographic emulsion of the present invention may 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 or the like alone or in combination;
Alternatively, it is possible to use a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, or the like. it can.

Various other additives are used in the light-sensitive material used in the present invention. For example, desensitizers, plasticizers, slip agents, development accelerators, oils, and the like can be used.

Regarding these additives and the above-mentioned additives, specifically, Research Disclosure 176
Nos. (Ibid.), Pages 22-31, etc. can be used.

In the light-sensitive material used in the present invention, the emulsion layer and the protective layer may be a single layer or a multilayer 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 photographic emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for light-sensitive materials. Those useful as the flexible support include films made of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, and 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, 1-aryl-3-pyrazolines (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-amino (Phenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.), transition metal complex salts (T
A complex salt of a transition metal such as i, V, Cr, Mn, Fe, Co, Ni, Cu, etc. These may have a reducing power in order to be used as a developing solution. For example, Ti ³⁺ , V ²⁺ ,
It takes the form of a complex salt such as Cr ²⁺ , Fe ^2+, etc.
Examples include aminopolycarboxylic acids and salts thereof such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA), and phosphoric acids and salts thereof such as hexametapolyphosphoric acid and tetrapolyphosphoric acid. ) Can be used alone or in combination.
A combination of pyrazolidones and dihydroxybenzenes,
Or a combination of aminophenols and dihydroxybenzenes or a combination of 3-pyrazolidones and ascorbic acid, a combination of aminophenols and ascorbic acid, a combination of 3-pyrazolidones and transition metal complex salts,
It is preferable to use a combination of aminophenols and transition metal complexes. The developing agent is usually 0.01 to
It is preferably used in an amount of 1.4 mol / l.

In the present invention, as a silver sludge-preventing agent, JP-B-62-4702, JP-A-3-51844,
4-26838, 4-362942, 1-3
Examples thereof include compounds described in No. 19031.

In particular the general formula

The compound represented by [9] is preferable.

[0146]

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In the formula, R ₄₁ , R ₄₂ and R ₄₃ are each a hydrogen atom,
-SM ₁ group, hydroxy group, lower alkoxy group, -CO
OM ₂ group, amino group, —SO ₃ M ₃ group or lower alkyl group, and at least one of R ₄₁ , R ₄₂ and R ₄₃ 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 ₄₁ , R ₄₂ and R ₄₃ are groups having 1 to 5 carbon atoms, and the amino group represented by R ₄₁ , R ₄₂ and R ₄₃ is substituted or non-substituted. It represents a substituted amino group, and a preferred substituent is a lower alkyl group. General formula

In [9], the ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

The following general formula

Specific examples of the compound represented by [9] are shown below, but the present invention is not limited thereto.

[0149]

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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, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) may be added to the developer. , Solubilizers (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg 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. In order to set the total processing time (Dryto Dry) to 60 seconds or less, the pH of the developer is preferably adjusted to 8.5 to 10.5.

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 commonly 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.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, for example, aluminum chloride, aluminum sulfate, potassium alum and the like.

The fixing solution may contain a preservative (eg, sulfite or bisulfite), a pH buffer (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 fixed 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 diluted before 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.

[0159]

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

Example 1 (Preparation of Silver Halide Emulsion A1) An average thickness of 0.05 mol% of silver chloride and the balance of silver bromide was 0.0 by a simultaneous mixing method.
A silver chlorobromide core particle having a 5 μm average diameter of 0.15 μm was prepared. At the time of mixing the core particles, K ₃ Rh (NO) ₄ (H ₂ O) ₂ was added in an amount of 8 × 10 ⁻⁸ mol per mol of silver, and K ₃ OsCl ₆ was added in an amount of 8 × 10 ⁻⁶ mol per mol of silver. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆
^Was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. Further, KI conversion was carried out using fine silver iodide grains, and the resulting emulsion had a core / shell type monodisperse (variation coefficient 10%) silver chloroiodobromide (silver chloride 90 mol%, average diameter 0.2 μm).
(A silver iodobromide 0.2 mol%, the balance being silver bromide). Then, a modified gelatin described in JP-A-2-280139 (in which an amino group in gelatin is substituted with phenylcarbamyl, for example, as disclosed in JP-A-2-28013)
No. 9, 287 (3) (exemplified compound G-8) and desalted. The EAg after desalting was 190 mv at 50 ° C. Further, a bactericide containing the compounds (A), (B) and (C) was added in an amount of 50 mg per mol of silver, and ossein gelatin was added to redisperse it. The EAg after desalting was 190 mv at 50 ° C.

To the obtained emulsion, potassium bromide and citric acid were added to adjust the pH to 5.6 and EAg123mv,
After adding 1 × 10 ⁻³ mol of sodium p-toluenethiosulfonate, the temperature was maintained at 60 ° C., and chloroauric acid: 2 × 10 ⁻⁵ mol, and sulfur (dissolved in methanol): 2 per mol of silver.
60 minutes after the addition of × 10 ^-5 mol, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added at 2 × 10 ^-3 mol per mol of silver, and 1-phenyl-5-mercaptotetrazole was 3 ×. Aging was completed by adding 10 ⁻⁴ mol. After completion, add gelatin and add potassium iodide to 300m
1 mol of g / Ag was added.

(Preparation of silver halide emulsion A2) A silver halide emulsion A2 was prepared in exactly the same manner as the silver halide emulsion A1, except that the addition amount of the Rh complex was 9 × 10 ^-8 mol / Ag. .

(Preparation of silver halide photographic light-sensitive material) A gelatin subbing layer of the following Formulation 1 was applied on a support so that the amount of gelatin was 0.5 g / m ^2, and then the halogenation of Formulation 2 was performed. The silver emulsion layer 1 had a silver amount of 1.5 g / m ² and the gelatin amount of 1.0 g / m ² , and the silver halide emulsion layer 2 of Formula 3 was further formed thereon with a silver amount of 1.5 g / m ^2. Then, a coating solution for protective layer having the following Formulation 4 was simultaneously multilayer-coated so that the amount of gelatin was 1.0 g / m ² , and the amount of gelatin was 0.6 g / m ² . On the other side of the undercoat layer, the following formulation 5
The backing layer of No. 6 above was coated with a polymer layer of the following Formulation 6 so that the gelatin amount was 0.6 g / m ^2, and the backing protective layer of the following Formulation 7 was further added thereto at a gelatin amount of 0.4.
g / m ² with the emulsion layer side and the curtain coating method.
A sample was obtained by simultaneous multilayer coating at a speed of 00 m / min.

Formulation 1 (Composition of gelatin undercoat layer) Gelatin 0.5 g / m ² Sodium polystyrene sulfonate a (Average molecular weight 500000) 10 mg / m ² Redox compound (Powder having a particle size of 0.1 μm dispersed with ZrO beads) Listed in Table 1 Dye (dissolved in alkaline solution, neutralized with citric acid to precipitate crystals) (AD-12) average particle size 0.08 μm 20 mg / m ² S-1 (sodium- Iso-amyl-n-decylsulfosuccinate) 0.4 mg / m ² Formulation 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A2 Sensitizing dye d- so that the amount of silver is 1.5 g / m ^2. 1 6 mg / m ² sensitizing dye ^d-2 3mg / m 2 redox compound (those that have been in the powder particle size 0.1μm dispersed in ZrO beads) nitrate Tl 0.5 mg / Ag1 mol pin according to table 1 Jiniumu salt derivatives (Table 1 described) 6 × 10 ^-3 mol / Ag1 mol present in pyridine derivative Table 1 of the invention wherein the compound e 100 mg / m ² Polymer latex (JP-A 4-359254 Patent Example 1 as described) 0 0.5 g / m ² hardener (K-2) 5 mg / m ² S-1 0.7 mg / m ² saponin 20 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² dye a 20 mg / m ² ascorbine Acid 20 mg / m ² EDTA 50 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Formulation 3 (silver halide emulsion layer 2 composition) Silver halide emulsion A1 Silver amount to be 1.5 g / m ² Sensitizing dye d -1 0.5 mg / m ² dye (after dissolution in an alkali solution, neutralized with citric acid, which precipitate crystals) (AD-12) mean particle size 0.08 .mu.m 20 mg / m ² pyrid Um salt derivatives (described in Table 1) 6 × 10 ^-3 mol / Ag1 described pyridine derivative Table 1 molar invention S-1 1.7mg / m ² 2- mercapto-6-hydroxy purine 1mg / m ² EDTA 50mg / M ² Styrene-maleic acid copolymer (molecular weight 70,000) 10 mg / m ² polymer latex (as described in JP-A-4-359254, Example 1) 0.5 g / m ² Gelatin is a phthalated gelatin coating solution. The pH was 4.8.

Formulation 4 (Emulsion protective layer composition) Gelatin 0.6 g / m ² Amino compound AM-1 20 mg / m ² S-1 12 mg / m ² Matting agent: Spherical polymethylmethacrylate 25 mg / average particle size 3.5 μm m ² matting agent: average particle size 8μm of amorphous silica 12.5 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² surfactant h 1 mg / m ² slip agent (silicone oil) 4 mg / m ² Colloidal silica (average particle size 0.05 μm) 20 mg / m ² Hardener (K-2) 30 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Formulation 5 (backing layer composition) Gelatin 0.6 g / m ² S -1 5 mg / m ² latex polymer f 0.3 g / m ² colloidal silica (average particle size 0.05μm) 70mg / m ² of polystyrene sulphonic acid Thorium 10 mg / m ² Compound i 100 mg / m ² formulation 6 (Polymer Layer Composition) latex j (methyl methacrylate: acrylic acid = 97: 3) 1.0g / m 2 hardener g 6 mg / ^{m 2} formulation 7 (Backing protective Layer) Gelatin 0.4 g / m ² Matting agent: Monodisperse polymethylmethacrylate having an average particle size of 5 μm 50 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant h 1 mg / m ² Dye k 20 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Zinc hydroxide 50 mg / m ²

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Embedded image

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Embedded image

The samples obtained are shown in Table 1.

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[Table 1]

The obtained sample No. 1 to No. After exposing 19 to a step wedge and exposing it at a wavelength of 633 nm as a substitute property of HeNe laser light, dry a rapid processing automatic processor GR-26SR manufactured by Konica Corporation using a developer and a fixer having the following compositions. One of the zone transport rollers
The pair was processed under the following conditions by using the developing solution shown in Table 2 and the fixing solution shown below in an automatic developing machine capable of heating.

[0171]

[Table 2]

(Fixing solution composition) Ammonium thiosulfate (70% aqueous solution) 200 ml / l Sodium sulfite 22 g / l Boric acid 9.8 g / l Sodium acetate trihydrate 70 g / l Acetic acid (90% aqueous solution) 14.5 g / l Tartaric acid 3 g / l Aluminum sulfate (27% aqueous solution) 25 ml / l Sulfuric acid was adjusted so that the pH of the used solution was 4.9.

(Processing conditions) (Process) (Temperature) (Condition A time) (Condition B time) Development 38 ° C. 12 seconds 7 seconds Fixing 35 ° C. 10 seconds 6 seconds Washing 40 ° C. 10 seconds 6 seconds Drying 50 ° C. 12 seconds 7 Seconds Total 44 seconds 26 seconds (Replenishment amount of processing agent) (Replenishment condition 1) (Replenishment condition 2) 74cc 35cc per developer large all size processing Fixer large all size processing 120cc 60cc (evaluation of sensitivity and gamma) Obtained developed sample is PDA
It was measured with -65 (Konica Digital Densitometer). The sensitivities in the table are the material numbers. It was expressed as a relative sensitivity when the sensitivity at a density of 1 was 2.5 and the sensitivity was 100. Further, gamma has a density of 0.
It is represented by a tangent of 1 and 3.0, and if the gamma value in the table is less than 7, it cannot be used, and if it is 7 or more and less than 10, it is still insufficient. Only when the gamma value is 10 or more, a very high contrast image is obtained, indicating that the material is a sufficiently practicable photosensitive material.

(Evaluation of Black Spots) The obtained developed sample was visually evaluated using a magnifying glass of 100 times, and was classified into 5 grades of 5, 4, 3, 2, 1 in the order of less black spots. It was ranked. Ranks 1 and 2 are levels that are not practically desirable. Table 3 shows the evaluation results.

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[Table 3]

It can be seen that the samples of the present invention show little deterioration in sensitivity and softening, and the generation of black spots is suppressed.

Example 2 (Evaluation of Raw Preservability) An unexposed sample was placed in a dark room at 23 ° C. and 48%.
After left at RH for 2 hours, it was sealed in an aluminum vapor deposition barrier bag and left at 55 ° C. for 2 days as a forced deterioration sample, and the same evaluation as above was performed together with an unexposed refrigerated storage sample for comparison.

(Evaluation of Processing Stability) After exposing 100 large size samples exposed to light, the same deterioration evaluation as above was carried out for the forcibly deteriorated samples.

Prior to the following evaluation, each of the above emulsions alone (except for the other emulsion layer in the above formulation) was applied and passed through an interference filter of 633 nm.
^{When the} sensitivity was evaluated by the reciprocal of the exposure amount for giving a density of 4 by sensitometry with high illuminance of ^-5 seconds, the sensitivity of emulsion 2 was -12.5% with respect to emulsion 1. Table 4 shows the evaluation results.

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[Table 4]

The samples of the present invention show little deterioration in sensitivity and softening after raw storage and in large-scale processing of light-sensitive materials.
It can be seen that the generation of black spots is suppressed.

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EFFECTS OF THE INVENTION A high-hardness silver halide photographic light-sensitive material and an image forming method therefor, in which sensitivity deterioration and softening hardly occur even after raw storage and in large-scale processing of the light-sensitive material, and black spots are suppressed. Was given.

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Claims (11)

[Claims] 1. A halogen containing a pyridinium salt derivative in at least one hydrophilic colloid layer in a photographic light-sensitive material constituting layer comprising at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer. An image forming method for a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material in the presence of a pyridine derivative. 2. A pyridinium salt derivative in a hydrophilic colloid layer which may be the same or different in a photographic light-sensitive material constituting layer comprising at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer. And a pyridine derivative, which is a silver halide photographic light-sensitive material. 3. At least one of the constituent layers of a photographic light-sensitive material comprising a support, an emulsion protective layer and at least two emulsion layers.
The emulsion layer contains a pyridine derivative, and the emulsion layer has an average silver chloride content of silver halide of 60 mol% or more and contains a merazine or cyanine dye-sensitized halogen particle and a hydrazine derivative. The silver halide photographic light-sensitive material according to claim 2. 4. The silver halide photographic light-sensitive material according to claim 2, wherein the emulsion layer farther from the support has a higher sensitivity than the emulsion layer closer to the support. 5. The silver halide photographic light-sensitive material according to claim 2, which contains a compound capable of releasing a development inhibitor by being oxidized by an oxidized product of a developing agent. 6. The silver halide photographic light-sensitive material according to claim 2, comprising at least one hardener which acts by activating a carboxyl group. 7. The silver halide photographic light-sensitive material according to claim 6, wherein the hardener is represented by the general formula [1]. Embedded image (In the formula, R ₁ and R ₂ represent an alkyl group or an aryl group,
R ₁ and R ₂ may form a ring. R ₃ represents a hydrogen atom or a substituent. L represents a single bond or a divalent group. X ₁ represents a single bond or —O—, —N (R ₄ ) —, and R ₄ represents a hydrogen atom, an alkyl group or an aryl group. ) 8. The silver halide photographic light-sensitive material according to claim 2, wherein the pyridine nucleus of the pyridine derivative is substituted with at least one carbamoyl group. 9. The silver halide photographic light-sensitive material according to claim 2, wherein the pyridine nucleus of the pyridine derivative is substituted with at least one hydroxy group. 10. A silver halide photographic light-sensitive material according to claim 2, 3, 4, 5, 6, 7, 8 or 9 is prepared by using a developing solution containing dihydroxybenzenes as a developing agent and having a pH of 11.0 or less. A method for forming an image on a silver halide photographic light-sensitive material, which comprises processing. 11. A silver halide photographic light-sensitive material according to claim 2, 3, 4, 5, 6, 7, 8 or 9, containing ascorbic acid and / or erythorbic acid, containing no hydroquinone and having a pH of An image forming method for a silver halide photographic light-sensitive material, which comprises processing with a developing solution of 11.0 or less.