JPH09101584A - Silver halide photographic sensitive material and its image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive material small in black spots in an image and fluctuation of the photographic performance of the photosensitive material and the manufacture method of a silver halide emulsion to be used for it and its image forming method. SOLUTION: This silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer and at least one nonphotosensitive hydrophilic colloidal layer and it contains a nucleator and it is processed in the presence of a pyrazine derivative in this image forming method, and at least one of the hydrophilic colloidal layers contains the nucleator and at least one of them including this contains 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 nucleating agent such as a hydrazine derivative or a pyridinium compound has been proposed as a means for obtaining a high-contrast image. Black spots appearing in what should be called non-developed areas called "pots" appear, which deteriorates the image quality. 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 crushed when reproducing the large dots. As a solution, a photosensitive material coated with a photosensitive silver halide emulsion layer with different sensitivity appeared, but in the high-sensitivity layer, the problem that black spots are more likely to occur after raw storage is improved and image reproducibility is improved. There was room for Further, black spots frequently occur due to a decrease in sulfite ion, which is generally used as a preservative, and an increase in pH due to the fatigue of the treatment liquid over time, and the commercial value as a photosensitive material for printing plate making is remarkably reduced. Therefore, there has been a strong demand for a system for improving the black spots while maintaining the high sensitive tone even after raw storage.

[0003]

SUMMARY OF THE INVENTION 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 few black spots even after being stored raw. Another object of the present invention is to provide a photographic light-sensitive material and an image forming method which are excellent in image reproducibility even after being stored raw. 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.

That is, a silver halide photographic light-sensitive material having a high sensitivity and a photographic characteristic with less black spots, in which γ exceeds 10 by using a stable developer at a low pH, a method for producing a silver halide emulsion used therefor and an image thereof. An object of the present invention is to provide a method for forming a silver halide photographic light-sensitive material, a method for producing a silver halide emulsion used therefor and a method for forming an image thereof, in which the photographic performance of the light-sensitive material is little changed with time.

[0005]

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

1) A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer and containing a nucleating agent in the presence of a pyrazine derivative. A method for forming an image on a silver halide photographic light-sensitive material, characterized in that

2) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer, any one of the hydrophilic colloid layers forming a photographic light-sensitive material constituting layer. A silver halide photographic light-sensitive material characterized by containing a nucleating agent in one layer and a pyrazine derivative in any one of the hydrophilic colloid layer and other hydrophilic colloid layers.

3) A pyrazine derivative in any one of hydrophilic colloid layers having a support, a silver halide emulsion protective layer and at least two silver halide emulsion layers and forming a photographic light-sensitive material constituting layer. At least one of the silver halide emulsion layers contains merocyanine or cyanine dye-sensitized silver halide grains having an average silver chloride content of 60 mol% or more and a nucleating agent. And a silver halide photographic light-sensitive material.

4) The silver halide photographic light-sensitive material as described in 3 above, wherein the silver halide emulsion layer on the side far from the support has higher sensitivity than the silver halide emulsion layer on the side near the support.

5) The silver halide photographic light-sensitive material described in 2, 3, or 4 above, which contains a compound which releases a development inhibitor when oxidized by an oxidized product of a developing agent.

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

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

[0013]

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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.
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 ), R ₄
Represents a hydrogen atom, an alkyl group or an aryl group. 8) The silver halide photographic light-sensitive material as described in any one of 2 to 7 above, wherein the pyrazine derivative is substituted with at least one carbamoyl group.

9) The silver halide photographic light-sensitive material as described in any one of 2 to 8 above, wherein the pyrazine derivative is pyrazine amide.

10) The silver halide photographic light-sensitive material described in any one of 2 to 9 above, wherein the nucleating agent is a hydrazine derivative.

11) The silver halide photographic light-sensitive material described in any one of 2 to 9 above, wherein the nucleating agent is a pyridinium salt derivative.

12) A silver halide characterized in that the silver halide photographic light-sensitive material described in any one of 2 to 11 above is treated with a developer having a pH of 11.0 or less using dihydroxybenzenes as a developing agent. Image forming method for photographic light-sensitive material.

13) The silver halide photographic light-sensitive material described in any one of 2 to 11 is treated with a developing solution containing ascorbic acid and / or erythorbic acid and containing no hydroquinone and having a pH of 10.8 or less. An image forming method for a silver halide photographic light-sensitive material, comprising:

The present invention will be described in more detail. The pyrazine derivative used in the present invention is preferably a compound represented by the following general formula (2).

[0021]

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In the general formula (2), R ₅ , R ₆ , R ₇ and R ₈
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 , R ₇ and R. ₈ is 3
They do not represent a hydrogen atom at the same time. R ₅ , R ₆ , R ₇ ,
R ₈ is preferably an 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 (for example, methoxy group, ethoxy group, methylenedioxy group, 2-hydroxyethoxy group, n-butoxy group, etc.), substituted amino group (for example, 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 (for example, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group) Etc.), carboxy group, sulfonamide group (for example, methanesulfonamide group, Emissions Zen sulfonamido group),
It is a sulfamoyl group (for example, a sulfamoyl group, a methylsulfamoyl group, a phenylsulfamoyl group, etc.), and a carbamoyl group is particularly preferable. The pyrazine derivative used in the present invention is particularly preferably a mono-substituted product or a di-substituted product. Specific examples of the pyrazine derivative used in the present invention are shown below, but the present invention is not limited thereto.

[0023]

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The pyrazine derivative particularly preferably used in the present invention is a compound substituted with at least one carbamoyl group, and the pyrazine derivative more preferably used is a carbamoyl group substituted with a substituent having 6 or less carbon atoms. It is a substituted compound, and specific examples thereof include (10) of the above specific examples, more preferably a compound substituted with an unsubstituted carbamoyl group, and specific examples thereof include pyrazine amide. The addition amount of the pyrazine 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. The range of 10 ^-6 to 10 ^-1 mol is preferable, and the range of 10 ^-5 to 10 ^-2 mol is particularly preferable, per 1 mol of silver halide. Further, in the present invention, two or more kinds of pyrazine derivatives can be contained in any layer in any state. When the pyrazine derivative of the present invention is used by adding it to a developing solution, the addition amount to the developing solution is preferably in the range of 10 ⁻⁴ to 10 mol / l, more preferably 10 ⁻³ to 1 mol / l. Is. Two or more pyrazine derivatives can be contained in the developer when added.

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

The redox compound has hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, reductones and the like as redox groups. A preferred redox compound is a compound having a -NHNH- group as a redox group and the following general formulas (3), (4), (5), (6),
It is a compound represented by (7) or (8).

[0027]

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The compound having a --NHNH-- group as a redox group is represented by the following general formula [RE-a] or [RE-a]
-B].

General formula [RE-a] T-NHNHCOV- (Time) -PUG General formula [RE-b] T-NHNHCOCOV- (Time) -PUG General formula [RE-a], [RE-b]: T and V each represent an optionally substituted aryl group or an optionally substituted alkyl group. PUG represents a photographically useful group, Ti
me represents a timing 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. Preferred substituents are linear or branched. An alkyl group (preferably having 2 to 20 carbon atoms such as methyl, ethyl, isopropyl group, dodecyl group, etc.), an alkoxy group (preferably having 2 to 21 carbon atoms, such as methoxy group, ethoxy group),
Aliphatic acylamino groups (preferably having an alkyl group having 2 to 21 carbon atoms, such as acetylamino group, heptylamino group, etc.), aromatic acylamino groups, and the like,
These other, for example, a substituted or unsubstituted aromatic rings, such as described above -CONH -, - O -, - SO 2 NH -, - N
HCONH -, - including those attached with a linking group such as CH ₂ CHN-.

As photographically useful groups, 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 inhibitor compounds are T-
It can be connected to the CO site of NHNH-CO- directly via a heteroatom such as N or S or via an alkylene, phenylene, aralkylene, or aryl group and further via a heteroatom such as N or S. 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-
(Dodecylethylene oxide thiopropionamide) -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, etc. Can be mentioned. As the timing group, a group having the same meaning as Tm described later can be mentioned.

Redox compounds are described in US Pat.
The compound can be synthesized with reference to the description in JP-A-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 compounds are added by adding alcohols such as methanol and ethanol, glycols such as ethylene glycol, triethylene glycol and propylene glycol, ethers, 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 addition amount of the redox compound is preferably from 10 ^-6 to 10 ^-1 mol, and more preferably from 10 ^-4 to 1 per mol of silver halide.
It is in the range of 0 ^-2 mol.

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

[0035]

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[0036]

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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.

Next, the general formulas (3), (4),
The redox compound represented by (5), (6), (7) or (8) will be described.

General formulas (3), (4), (5), (6),
In (7) or (8), R ₉ represents an alkyl group, an aryl group or a heterocyclic group. R ₁₀ and R ₁₁ are a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group,
Sulfonyl group, aryl group, oxalyl group, heterocyclic group,
It represents an alkoxycarbonyl group or an aryloxycarbonyl group. R ₁₂ represents a hydrogen atom. R _{13 to} R ₁₈ 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 ₂ and X ₃ represent O or NH. Z ₁ represents an atomic group necessary for forming a 5- or 6-membered heterocycle. W ₂ is N
(R ₁₉ ) R ₂₀ or O, and R ₁₉ and R _{20 each} represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. C
OUP 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 represents 0 or 1. PUG represents a development inhibitor.

In the general formulas (3) to (8), R ₉
And an alkyl group represented by R _{13 to} R ₂₀ , an aryl group,
Preferred examples of the heterocyclic group include a methyl group, a p-methoxyphenyl group, and a pyridyl group. R ₁₀ and R ₁₁
Embedded image acyl group, carbamoyl group, cyano group, nitro group, sulfonyl group, aryl group, oxalyl group, heterocyclic group, alkoxycarbonyl group, aryloxycarbonyl group, preferably an acyl group, carbamoyl group,
It is a cyano group. The total carbon number of these groups is 1 to 20.
It is preferred that R _{9 to} R ₂₀ may further have a substituent, and examples of the substituent include a halogen atom (chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, isopropyl group, hydroxyethyl group). ,
Methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl group (for example, cyclopentyl group,
Cyclohexyl group), 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.), alkylthio group (eg methylthio group, ethylthio group, butylthio group etc.) ), An arylthio group (eg, a phenylthio group, etc.), a sulfonylamino group (eg, a methanesulfonylamino group, a benzenesulfonylamino group, etc.),
Ureido group (for example, 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.) An alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), a sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), an 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 (for example, phthalimido group, etc.),
Heterocyclic groups (for example, a pyridyl group, a benzimidazolyl group, a benzothiazolyl group, a benzoxazolyl group, etc.) are exemplified.

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 are those represented by the general formula (Coup-1) to the general formula (Coup-8).
Can be represented by

[0042]

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In the formula, R ₂₁ represents an acylamido group, anilino group or ureido group, and R ₂₂ represents a phenyl group which may be substituted with one or more halogen atoms, an alkyl group, an alkoxy group or a cyano group.

[0044]

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In the formula, R ₂₃ and R ₂₄ 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 ₂₅ and R ₂₆ are each a fatty acid. Represents a group, an aromatic group or a heterocyclic group. Further, one of R ₂₅ and R ₂₆ 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 integers of 2 or more, R ₂₃ and R ₂₄ may be the same or different.

[0046]

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In the formula, R ₂₇ represents a tertiary alkyl group or an aromatic group, and R ₂₈ represents a hydrogen atom, a halogen atom or an alkoxy group. R ₂₉ 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.

[0048]

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In the formula, R ₃₀ represents an aliphatic group, an alkoxy group, an acylamino group, a sulfonamide group, a sulfamoyl group, a diacylamino group, and R ₃₁ represents a hydrogen atom, a halogen atom or a nitro group.

[0050]

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R ₃₂ and R ₃₃ 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.

The timing group represented by Tm is preferably --OCH ₂ --or another divalent timing group, for example, US Pat. Nos. 4,248,962 and 4,409,3.
No. 23, or No. 3,674,478, Research
Disclosure 21228 (December 1981)
Month), or JP-A-57-56837 and JP-A-4-43.
Examples thereof include those described in JP-A-8.

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.

General formulas (3) to (3) used in the present invention are described below.
Specific examples of the compound represented by (8) are listed, but the present invention is not limited thereto.

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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General formula (3) preferably used in the present invention
The compounds represented by (8) to (8) are preferably contained in an amount of 1 × 10 ^-6 mol to 5 × 10 ^-2 mol, and particularly 1 × 10 ^-4 mol 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 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.

In the present invention, these redox compounds can be present in the silver halide emulsion layer, in a layer adjacent to the emulsion layer, in another layer via the adjacent layer, or the like. 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, the hydrazine derivative is preferably a compound represented by the following general formula (H).

[0068]

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[0069] In the formula, E represents represents a heterocycle containing at least one aryl group, or a sulfur atom or an oxygen atom, G is - (CO) _nh - group, a sulfonyl group, a sulfoxy group, -P
(= O) R ₃₅ - represents a group or an iminomethylene group,, n
h represents an integer of 1 or 2, E ₁ and E ₂ both 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 ₃₄ represents Each 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 ₃₅ 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.

[0071]

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In the formula, R ₃₆ is an aliphatic group (eg, octyl group, decyl group), aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or heterocyclic group (eg, pyridyl group, thienyl group, Represents a furyl group),
As these groups, those further substituted with a suitable substituent are preferably used. Furthermore, the R ₃₆ preferably contains at least one ballast group or a silver halide adsorption accelerating group.

The anti-diffusion group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group is an alkyl group having 8 or more carbon atoms and relatively inert to photographic properties. , Alkenyl 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 ₃₇ 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. Most preferred R ₃₇ includes —COOR ₃₈ group and —CON
(R ₃₉ ) (R ₄₀ ) group can be mentioned (R ₃₈ represents an alkynyl group or a saturated heterocyclic group, R ₃₉ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ₄₀ 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.

[0080]

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[0081]

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[0082]

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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 according to the present invention can be synthesized by a known method. For example, US Pat.
It can be synthesized by a method as described in columns 59 to 80 of No. 29,248.

The amount of addition may be any amount as long as it causes 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 preferably used in the present invention is added to the silver halide emulsion layer and / or its adjacent layer.

The hydrazine compound used in the present invention can be used in any layer on the silver halide emulsion layer side, but is preferably used in the silver halide emulsion layer or its adjacent layer. In the present invention, 3
More than one kind of hydrazine compound can be contained in any layer in any state.

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

[0089]

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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 ₄₄ )-, (R ₄₄ 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 ₄₁ , R ₄₂ and R ₄₃ have 1 or more carbon atoms and 20
The following saturated and unsaturated alkyl groups are represented. R ₄₁ , R
₄₂ may be the same or different. The substituent has the same meaning as the group mentioned as the substituent of A ₁ , A ₂ , A ₃ , A ₄ and A ₅ .

Preferred examples are R ₄₁ , R ₄₂ and R ₄₃
Each represents a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group. A more preferred example is a substituted alkyl group having 4 to 10 carbon atoms. Xp represents a counter ion required to balance the charge of the whole molecule, and represents, for example, chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate. np represents the number of counterions required to balance the charge of the entire molecule, and np is 0 in the case of an inner salt. Specific examples of the compounds are shown below.

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[0095]

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[0096]

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[0097]

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[0098]

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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 it is 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.

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

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

The gold sensitization method is a typical one of the noble metal sensitization methods, and uses a gold compound, mainly a gold complex salt. 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 salts, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

In 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 chloroiodo containing 60 mol% or more of silver chloride. It is 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. 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. 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.

It is also possible to use a method of forming grains in the presence of excess silver ions (so-called reverse mixing method). 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 compounds described in Japanese Patent Application No. 6-103982, pages 28 to 29, and specific examples thereof are described in Japanese Patent Application No. 6-103982, pages 30 to 35 (Na -1) to (Na-22) or (Nb-1) to
The compound described as (Nb-12) can be mentioned. Specific examples of other preferable nucleation promoting compounds are:
The example described in JP-A-6-258751 (2-
1) to (2-20) and the compounds of (3-1) to (3-6) described in JP-A-6-258751. Here, as a reference, preferred examples of the nucleation accelerator are given,
It is not limited to this.

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The nucleation accelerator used in the present invention can be used in any layer on the silver halide emulsion layer side, but is preferably used in the silver halide emulsion layer or its adjacent layer. . The amount of the nucleation accelerator used in the light-sensitive material is 5 × 10 ^{−7 to} 5 × 10 5 per mol of silver halide.
^-1 mol is preferable, and particularly 5 × 10 ^{-6 to} 5 × 1
It is preferably in the range of 0 ^-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 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 the 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, 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).

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In the formula, A and A ′, which may be the same or different, each represents an acidic nucleus, B represents a basic nucleus, Q represents an aryl group or a heterocyclic group, 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 represents a methine group. m ₂ represents 0 or 1,
t represents 0, 1 or 2, and p ₂ represents 0 or 1.
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.

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.

A of the general formulas (I), (II) and (III)
The acidic nucleus represented by A and A ′ is preferably 5-
Examples thereof include pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, and pyrazolopyridone.

The basic nucleus represented by B in the general formulas (III) and (V) is preferably pyridine, quinoline,
Oxazole, benzoxazole, naphthoxazole, thiazole, benzothiazole, naphthothiazole, indolenine, pyrrole, indole.

X ₄ and Y of the general formulas (IV) and (V)
The electron withdrawing groups represented by may be the same or different, and 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. Is mentioned.

Examples of the heterocyclic group represented by Q'in the general formula (VI) include pyridine, pyridazine, quinoline, pyrrole, pyrazole, imidazole and indole.

L ₁ , L ₂ and L of the general formulas (I) to (V)
_The methine group represented by ₃ includes those having a substituent,
Examples of the substituent include an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a hexyl group, etc.), an aryl group (for example, a phenyl group, a tolyl group, a 4-hydroxyphenyl group, etc.), and a carbon number of 1 to 1. 4 alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group (eg, phenoxy group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), heterocyclic group (eg, pyridyl group,
A furyl group, a thienyl group, etc.), a substituted amino group (eg, a dimethylamino group, a diethylamino group, an anilino group, etc.), and an alkylthio group (eg, a methylthio group, etc.) can be mentioned.

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

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These dyes have at least one dissociative proton having a pKa in the range of 4 to 11, preferably 4.5 to 7.0 in a mixed solvent of water-ethanol in a volume ratio of 1: 1. To have.

Further, in the present invention, the immobilization can be carried out by the silver salt and the silver complex formed by the reaction between the dye and the silver ion. A preferable dye capable of forming a silver salt of such a dye is, for example, JP-A-5-181230.
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 specification. . More specific compounds include I-1 to 37, II-1 to 5, III-1 to 7, IV-1 to 1 described in pages 6 to 46 of 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 diameter of the finely dispersed dye fine particles of the present invention can take any value, but it 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. Hydrophilic colloid layer containing a dye fine particles of the present invention, coating amounts is less than 0.05 g / m ² or more 0.5 g / m ^2, preferably 0.18 g / m ² or more 0.42 g /
less than m ² . Further, in order to further enhance the effect of the present invention, the ratio of the average particle size of the dye fine particles to the film thickness of the dye layer is 0.
It is preferably set to 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 production 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 (especially 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 , 3a, 7-tetrazaindenes), pentazaindenes and the like; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like. Can be.

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 above-mentioned general formula (1) is used.
The compound represented by is particularly preferably used. (As a precaution, the structure is shown below as general formula (9).)

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In the compound represented by the general formula (9),
R ¹ and R ² have a linear, branched or cyclic carbon number of 1 to 2
Examples thereof include an alkyl group of 0 (for example, a methyl group, an ethyl group, a butyl group, a cyclohexyl group, a 2-ethylhexyl group, a dodecyl group, etc.) and an aryl group having 6 to 20 carbon atoms (for example, a phenyl group, a naphthyl group, etc.). R ¹ and R ² may have a substituent, and examples of the substituent include a substituent which substitutes the aryl group represented by Q in the general formulas (I) and (IV) described above. Q in formulas (I), (IV) and (VI)
And those mentioned as the substituents for substituting the heterocycle represented by Q ′.

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 the case of forming a morpholine ring or a pyrrolidine ring. 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 ¹ represents a single bond, an alkylene group having 1 to 20 carbon atoms (eg, methylene group, ethylene group, trimethylene group, propylene group), an arylene group having 6 to 20 carbon atoms (eg, phenylene group), and those Represents a divalent group (for example, a baraxylene group), an acylamino group (for example, —NHCOCH ₂ — group), a sulfonamide group (for example, —NHSO ₂ CH ₂ — group) and the like. Among them, preferred are a single bond, an alkylene group such as a methylene group and an ethylene group, and an acylamino group. X ³ represents a single bond or —O—, —N (R ⁴ ) —, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, benzyl group, etc.), carbon number. It is an aryl group having 6 to 20 (for example, a phenyl group or the like) or an alkoxy group having 1 to 20 carbon atoms (for example, a methoxy group or the like), and a hydrogen atom is particularly preferable.

Specific examples of the compound represented by the general formula (9) 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 (9) include the following.

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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 aid, antistatic property, 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 polymer substances such as a single or copolymer such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole 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 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 multi-layer 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 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 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 the present invention, when processing is performed by using an automatic developing machine in order to shorten the developing time, the total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone is 10 times. 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.

Further, in the automatic processor, a heat transfer material having a temperature of 90 ° C. or higher (for example, a heat roller of 90 ° C. to 130 ° C.) or a radiation object having a temperature of 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 developing agents that can be used in the present invention include dihydroxybenzenes (eg, 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. ), Etc., can be used alone or in combination, a combination of 3-pyrazolidones and dihydroxybenzenes, or a combination of aminophenols and dihydroxybenzenes or a combination of 3-pyrazolidones and ascorbic acid, It is preferable to use a combination of aminophenols and ascorbic acid, a combination of 3-pyrazolidones and transition metal complex salts, and a combination of aminophenols and transition metal complex salts. Further, the developing agent is preferably used usually in an amount of 0.01 to 1.4 mol / liter.

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

Particularly preferred are the compounds represented by formula (as).

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In the formula, R ₅₁ , R ₅₂ and R ₅₃ 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 ₅₁ , R ₅₂ and R ₅₃ 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 the lower alkoxy group represented by R ₅₁ , R ₅₂ , and R ₅₃ are groups having 1 to 5 carbon atoms, respectively, and the amino group represented by R ₅₁ , R ₅₂ , and R ₅₃ is substituted or expensive. It represents a substituted amino group, and a preferred substituent is a lower alkyl group. In formula (as), the ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.
Specific examples of the compound represented by formula (as) are shown below, but the invention is not limited thereto.

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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. Sulfite used as a preservative in the present invention,
Examples of metabisulfite 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.

In the developer, 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.) , 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. Total processing time (Dry to Dry) is 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 liquid, 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 acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, etc. can be added to the fixing solution. The fixing solution optionally contains compounds such as a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), and a chelating agent capable of softening water. be able to.

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

[0169]

【Example】

Example 1 (Preparation of silver halide emulsion A1) An average diameter of 0.0 mol% of silver chloride was 70 mol% and the rest was silver bromide by using the double-sided mixing method.
9 μm silver chlorobromide core particles were prepared. When mixing the core particles, K ₃ Rh (NO) ₄ (H ₂ O) ₂ was added in an amount of 7 × 10 ⁻⁸ mol per mol of silver per mol of silver, and K ₃ Os was used.
PH ₆ at 40 ° C. in the presence of 8 × 10 ^-6 mol of Cl ₆ .
An aqueous silver nitrate solution and a water-soluble halide solution were simultaneously mixed while maintaining the silver potential (EAg) at 165 mV. The core particles were shelled using the double-mix method with EAg lowered to 125 mV with saline. At that time, K ₂ IrC was added to the halide solution.
1 ₆ was added in an amount of 3 × 10 ^-7 mol, and K ₃ RhCl ₆ was added in an amount of 9 × 10 ^-8 mol. Further, KI conversion was performed using silver iodide fine particles, and the obtained emulsion was a core / shell type monodispersion having an average diameter of 0.15 μm (coefficient of variation: 10
% Of silver chloroiodobromide (70 mol% of silver chloride, 0.2% of silver iodobromide)
(Mol%, the remainder being silver bromide). Then, a modified gelatin described in JP-A-2-280139 (in which the amino group in the gelatin is substituted with phenylcarbamyl, for example, JP-A-2-280139, 287)
Desalting was performed using the exemplified compound G-8) on page (3). The EAg after desalting was 190 mv at 50 ° C.

In the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1.5 × 10 ^-3 mol per mol of silver, and potassium bromide in an amount of 8.5 × 10 5.
PH 5.6, EAg12 with addition of ^-4 mol and citric acid
After adjusting to 3 mv and adding 1 × 10 ⁻³ mol of sodium p-toluenesulfonylchloramide trihydrate (chloramine T) to cause a reaction, the inorganic sulfur (S
₈ ) Compound (Seisin Enterprise Co., Ltd .; saponin added using PM-1200 and dispersed to an average of 0.5 μm)
After adding 1.5 × 10 ⁻⁵ mol of chloroauric acid and performing chemical ripening at a temperature of 55 ° C. until the maximum sensitivity is obtained, 50
At 100 ° C., 100 mg of sensitizing dye d-1 and 5 mg of trihexylamine were added, and the temperature was further lowered to 40 ° C., and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per mole of silver. 2 × 10 ^-3 mol, 1-phenyl-
After adding 3 × 10 ⁻⁴ mol of 5-mercaptotetrazole and 5 × 10 ⁻³ mol of potassium iodide, the pH was adjusted to 5.1 with citric acid.

(Preparation of Silver Halide Emulsion A2) With respect to silver halide emulsion A1, the reaction temperature was raised to 50 ° C. to make the grain size 0.19 μm, and K ₃ RhCl ₆ in the shell portion was adjusted to 6 × 10 6.
Except that the ^-8 mol exactly the same silver halide emulsion A
2 was prepared. With the same chemical sensitization, the emulsion of A2 is 40% faster than the emulsion of A1.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner containing hydrazine derivative) A gelatin subbing layer of the following Formulation 1 was prepared on a support with a gelatin content of 0.
45 g / m so that the ^2, amount of silver 1.5 g / m ² of silver halide emulsion layers 1 formulation 2 thereon, the amount of gelatin 0.
The silver halide emulsion layer 2 of Formula 3 was further added thereon so as to have a silver amount of 1.5 g / m ² and a gelatin amount of 0.65 g / m ² so as to have a silver content of 65 g / m ^2.
Was applied simultaneously so that the amount of gelatin became 0.7 g / m ² . On the other side of the undercoating layer, a backing layer of the following formulation 5 was provided with a gelatin amount of 1.5 g / m ^2, and a backing protective layer of the following formulation 6 was provided thereon with a gelatin amount of 0.8 g / m 2. ^The emulsion layer side and the emulsion layer side were simultaneously multilayer-coated at a speed of 200 m / min by a curtain coating method so as to obtain a layer 2 and then cooled and set. Then, the backing layer side was simultaneously multilayer-coated and cooled and set at -1 ° C. A sample was obtained by simultaneously drying both sides.

Formulation 1 (gelatin undercoat layer composition) Gelatin 0.45 g / m ² saponin 56.5 mg / m ² redox compound (19) (dissolved in ethyl acetate and dispersed in gelatin solution, and then removed ethyl acetate under reduced pressure) 25 mg / m ² solid disperse dye (AD-12) 50 mg / m ² sodium polystyrene sulfonate (average molecular weight 500000) 15 mg / m ² bactericide (z) 0.5 mg / m ² .

Formulation 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A1 Silver amount 1.5 g / m ² equivalent amount Sensitizing dye (d-1) 150 mg / Ag 1 mol Hydrazine compound (H-9) 2 × 10 ^-3 mol / Ag 1 mol Amino compound (N-6) 7 mg / m ² Pyrazine derivative of the present invention (described in Table 1) Sodium-di- (3-ethyl-n-butyl) sulfosuccinate 100 mg / m ² Polymer latex (L1) (particle size 0.25 μm) 0.25 g / m ² Hardener (K-2) 5 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 0.7 mg / m ² naphthalene sulfone sodium 8 mg / m ² saponin 20 mg / m ² hydroquinone 20 mg / m ² 2-mercapto-6-hydroxy-purine 2 mg / m ² colloidal silica (average particle size 0.0 μm) 150mg / m ² of ascorbic acid ^{20mg / m 2 EDTA2Na 25mg / m} 2 Sodium polystyrenesulfonate 15 mg / m ² coating solution pH was 5.2.

Formulation 3 (composition of silver halide emulsion layer 2) Silver halide emulsion A2 Silver amount 1.5 g / m ² equivalent amount Sensitizing dye (d-2) 100 mg / Ag 1 mol Hydrazine compound (H-2) 4 × 10 ^-3 mol / Ag 1 mol Amino compound (N-6) 7 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 1.7 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² Pyrazine derivative of the invention (described in Table 1) Gallic acid n-propyl ester 50 mg / m ² mercaptopyrimidine 1 mg / m ² EDTA 2Na 50 mg / m ² Styrene-maleic acid copolymer (molecular weight 70,000 mg / m ² polymer latex ( L2) (JP-A-5-66512, Example 3 Type Lx-3 composition (9)) 0.25 g / m ² colloidal silica (average particle size of 0. (05 μm) 150 mg / m ² Gelatin was phthalated gelatin and the coating solution pH was 4.8.

Formulation 4 (Emulsion protective layer composition) Gelatin 0.6 g / m ² Amino compound (N-6) 14 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² Matting agent: Average particle Spherical polymethylmethacrylate having a diameter of 3.5 μm 25 mg / m ² Average particle diameter 8 μm Indeterminate silica 12.5 mg / m ² Surfactant (S1) 26.5 mg / m ² Lubricant (silicone oil) 4 mg / m ² Polymer latex (L3) (particle size 0.10 μm) 0.25 g / m ² colloidal silica (average particle size 0.05 μm) 150 mg / m ² dye (f1) 20 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Hardener (K-2) 30 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Bactericide (z) 0.5 mg / m ² .

Formulation 5 (Backing layer composition) Gelatin 0.6 g / m ² Sodium-iso-amyl-n-decylsulfosuccinate 5 mg / m ² Polymer latex (L3) 0.3 g / m ² Colloidal silica (average particle size) 0.05 μm) 100 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Dye (f1) 65 mg / m ² Dye (f2) 15 mg / m ² Dye (f3) 100 mg / m ² 1-Phenyl-5-mercaptotetrazole 10 mg / m ² Hardener (h2) 100 mg / m ² Zinc hydroxide 50 mg / m ² EDTA2Na 50 mg / m ² .

Formulation 6 (Backing protective layer) Gelatin 0.4 g / m ² Matting agent: Monodispersed polymethylmethacrylate having an average particle size of 5 μm 50 mg / m ² Average particle size 3 μm Indeterminate silica 12.5 mg / m ² Sodium-di -(2-Ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant (S1) 1 mg / m ² Dye (f1) 65 mg / m ² Dye (f2) 15 mg / m ² Dye (f3) 100 mg / m ² Dye ( AD-13) (solid dispersion) 20 mg / m ² Sodium-di- (3-ethyl-n-butyl) sulfosuccinate 50 mg / m ² Hardener (K-2) 20 mg / m ² Sodium polystyrene sulfonate 10 mg / When adding m ² solid disperse dye, dye exemplification (AD-13)
After dissolving in alkali, 1.2 times equivalent amount of citric acid with respect to the acid group was added for acid precipitation. Other dyes (including those after Example 2) were dispersed with ZrO beads to obtain a powder dispersion having a particle size of 0.1 μm.

[0179]

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[0180]

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[0181]

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The obtained samples are shown in Table 1.

(1 composition of developer) Per 1 l of used solution diethyltriamine pentaacetic acid / 5 sodium salt 1 g sodium sulfite 42.5 g potassium sulfite 17.5 g potassium carbonate 55 g hydroquinone 20 g 1-phenyl-4-methyl-4-hydroxymethyl- 3-Pyrazolidone 0.85 g Potassium bromide 4 g 5-Methylbenzotriazole 0.2 g Boric acid 8 g Diethylene glycol 40 g Compound (as-3) 0.078 g KOH was added in an amount to bring the pH to 10.4.

(Developer 2 composition) Diethyltriamine pentaacetic acid / 5 sodium salt 1 g / l Sodium sulfite 40 g / l Sodium ascorbate 20 g / l 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.85 g / L Potassium carbonate 45 g / l Benzotriazole 0.2 g / l Potassium bromide 4 g / l Boric acid 8 g / l Diethylene glycol 40 g / l 1-Phenyl-6-mercaptotetrazole 0.03 g / l Potassium hydroxide 17. 5 g / l Compound (as-3) 0.078 g / l Water and potassium hydroxide are added to make 1 liter / pH 9.4.

(Fixing solution composition) Ammonium thiosulfate (70% aqueous solution) per 1 liter of working solution 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Aluminum sulfate (27% aqueous solution) 25 ml sulfuric acid was used to adjust the pH of the working solution to 4.9.

(Processing Conditions) (Process) (Temperature) (Condition A) (Condition B) 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) (Condition A) (Condition B) Developing solution Large size processing per sheet processing 74cc 35cc Fixing solution Large size processing per sheet processing 120cc 60cc (Evaluation of sensitivity and gamma) Obtained sample 633n as an alternative to a He-Ne laser light source using an optical wedge
High-intensity exposure was performed for 10 ⁻⁵ seconds with a light source equipped with an interference filter of m, and development processing was performed under the above conditions. The obtained developed sample was measured for sensitivity, fog and gamma using a digital densitometer PDA-65 (manufactured by Konica [Co.]).
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 is represented by tangents of densities of 0.1 and 3.0. 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 five 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.

(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.

Table 2 shows the evaluation results.

[0190]

[Table 1]

[0191]

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[0192]

[Table 2]

From Table 2, it can be seen that the silver halide photographic light-sensitive material for a printing plate-making scanner of the present invention has little sensitivity variation and softening, and black spots are suppressed.

Example 2 Example 1 was repeated except that 15 mg / m ² of compound P-1 was used in each of silver halide emulsion layer 1 and silver halide emulsion layer 2 in place of hydrazine derivatives H-9 and H-10. Similarly, the samples shown in Table 3 were prepared and evaluated in the same manner as in Example 1, and the results in Table 4 were obtained.

[0195]

[Table 3]

[0196]

[Table 4]

From Table 4, it can be seen that the silver halide photographic light-sensitive material for a printing plate-making scanner of the present invention has little sensitivity variation and softening, and black spots are suppressed.

Example 3 In Example 1, the following sensitizing dyes were used instead of d-1 and d-2, and the following d-3, d-4 and d-5 were used, and an addition layer of solid disperse dye (AD-12) was used. A gelatin subbing layer and an emulsion layer 1
Sample No. shown in Table 5 was the same as in Example 1 except that 20 mg / m ^{2 was} used for each (lower layer). 3-1 to 3-7 are created, and the exposure machine is an infrared semiconductor laser light source recorder MT-
The same evaluation as in Example 1 was performed except that R1120 (manufactured by Dainippon Screen Mfg. Co., Ltd.) was used, and the results in Table 6 were obtained.

[0199]

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[0200]

[Table 5]

[0201]

[Table 6]

From Table 6, it can be seen that the silver halide photographic light-sensitive material for a printing plate-making scanner of the present invention has little sensitivity variation and softening, and the generation of black spots is suppressed.

[0203]

INDUSTRIAL APPLICABILITY According to the present invention, a silver halide photographic light-sensitive material having a high sensitivity of γ of more than 10 and photographic characteristics with less black spots and a silver halide emulsion used therefor are produced by using a developing solution stable at low pH. It was possible to provide a method and an image forming method thereof, and to provide a silver halide photographic light-sensitive material in which the photographic performance of the light-sensitive material does not fluctuate with time, a method of producing a silver halide emulsion used therein and an image forming method thereof.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical indication location G03C 1/33 G03C 1/33 1/43 1/43 5/29 501 501/29 501 501 5/30 5/30

Claims (13)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer and containing a nucleating agent in the presence of a pyrazine derivative. A method for forming an image on a silver halide photographic light-sensitive material, characterized in that 2. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer, any of the hydrophilic colloid layers forming a photographic light-sensitive material constituting layer. A silver halide photographic light-sensitive material characterized by containing a nucleating agent in one layer and a pyrazine derivative in any one of the hydrophilic colloid layer and other hydrophilic colloid layers. 3. A pyrazine derivative in any one of hydrophilic colloid layers having a support, a silver halide emulsion protective layer and at least two silver halide emulsion layers, and forming a photographic light-sensitive material constituting layer. At least one of the silver halide emulsion layers contains merocyanine or cyanine dye-sensitized silver halide grains having an average silver chloride content of 60 mol% or more and a nucleating agent. And a silver halide photographic light-sensitive material. 4. The silver halide photographic light-sensitive material according to claim 3, wherein the silver halide emulsion layer farther from the support has a higher sensitivity than the silver halide emulsion layer closer to the support. 5. The silver halide photographic light-sensitive material according to claim 2, 3 or 4, further comprising a compound which releases 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, which contains 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 following general formula (1). Embedded image (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. Represents the group of.
X ₁ represents a single bond or O or N (R ₄ ), and R ₄ represents a hydrogen atom, an alkyl group or an aryl group. ) 8. The pyrazine derivative is substituted with at least one carbamoyl group.
7. A silver halide photographic light-sensitive material according to any one of items 1 to 7. 9. The silver halide photographic light-sensitive material according to claim 2, wherein the pyrazine derivative is pyrazine amide. 10. The silver halide photographic light-sensitive material according to claim 2, wherein the nucleating agent is a hydrazine derivative. 11. The silver halide photographic light-sensitive material according to any one of claims 2 to 9, wherein the nucleating agent is a pyridinium salt derivative. 12. A silver halide photographic light-sensitive material according to any one of claims 2 to 11, which is treated with a developer having a pH of 11.0 or less using dihydroxybenzenes as a developing agent. Image forming method of silver photographic light-sensitive material. 13. The silver halide photographic light-sensitive material according to claim 2, which is treated with a developing solution containing ascorbic acid and / or erythorbic acid, containing no hydroquinone, and having a pH of 10.8 or less. An image forming method for a silver halide photographic light-sensitive material, comprising: