JPH0926640A - Silver halide photographic sensitive material and image forming method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material for printing plate making in which high contrast with high density is obtd., good dot imaging property is obtd. without producing continuous large dots, and production of black spots is suppressed, and to provide its image forming method. SOLUTION: This silver halide photographic sensitive material has at least two silver halide emulsion layers on one surface of a supporting body and a nonphotosensitive intermediate layer between the emulsion layers. The emulsion layer and/or a hydrophilic colloid layer adjacent to the emulsion layer contain a hydrazine deriv. The nonphotosensitive intermediate layer contains a dye dispersed in a solid state. Further, the emulsion layer nearest to the supporting body and/or the hydrophilic colloid layer adjacent to this layer contain a redox compd. which releases a development inhibitor by oxidation. An image of high contrast with θ=10 to 30 is obtd. by processing the photosensitive material with a developer of pH 9.5 to 11.2.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In recent years, in the printing plate making scanner market, a screening method for forming an image with halftone dots smaller than the conventional one, such as high definition and FM screening, has begun to spread. For these screening methods,
Ultra-high contrast type light-sensitive material that is easy to get a small density of density is suitable.

Various techniques are known as photographic techniques for obtaining super-high contrast image reproduction in photosensitive materials for printing plate making. Among them, for example, a silver halide photographic light-sensitive material containing a hydrazine derivative disclosed in U.S. Pat. No. 4,269,929 or a halogen containing a nucleation accelerator as disclosed in JP-A-4-98239. A silver halide photographic light-sensitive material is known.

A technique for improving photographic performance by incorporating a compound releasing a photographically useful group by a redox reaction into a light-sensitive material containing a hydrazine compound is disclosed in JP-A-4-438.

However, the addition of such redox compounds is susceptible to developer levels, and as a result,
It had a problem of destabilizing the sensitivity.

Such a problem is caused by the influence of the liquid level and the sensitivity of the developing solution as compared with the conventional method, and the reproducibility (linearity, point quality) of the halftone dots is likely to vary. However, the improvement has been strongly desired.

[0007]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is not to deteriorate the performance even under rapid processing conditions, to have a high contrast and a high density, to improve the halftone property and the deviation of large dots, and to improve the black spots. It is an object of the present invention to provide a silver halide photographic light-sensitive material for printing plate making which suppresses generation and has excellent linearity, and an image forming method thereof.

[0008]

The above objects of the present invention have been achieved by the following.

(1) In a silver halide photographic light-sensitive material having at least two silver halide emulsion layers on one surface of a support and a non-photosensitive intermediate layer between the emulsion layers, said emulsion layers And / or a hydrophilic colloid layer adjacent thereto containing a hydrazine derivative and a dye dispersed in a solid state in the non-photosensitive intermediate layer.

(2) The emulsion layer closest to the support and / or the hydrophilic colloid layer adjacent to the emulsion layer contains a redox compound which is oxidized to release a development inhibitor (1). Silver halide photographic light-sensitive material.

(3) A hard image having a gamma of 10 to 30 or more is formed by processing with a developing solution having a pH of 9.5 to 11.2. Image forming method for silver halide photographic light-sensitive material.

The present invention will be described in detail below.

In the present invention, at least two light-sensitive silver halide emulsion layers are provided on one surface of the support. Here, the two silver halide emulsion layers may have the same or different silver halide composition, sensitivity, color sensitivity, etc.,
Different sensitivities are preferred.

A non-photosensitive intermediate layer is provided between both emulsion layers.
Here, non-photosensitive means having no substantial photosensitivity, and includes a layer containing silver halide grains. A preferable non-photosensitive intermediate layer is a layer containing no silver halide grains.

The silver halide photographic light-sensitive material of the present invention contains a hydrazine derivative in the light-sensitive silver halide emulsion layer and / or the hydrophilic colloid layer adjacent thereto. The hydrophilic colloid layer here means, for example, a hydrophilic photographic constituent layer adjacent to an intermediate layer, a protective layer, an undercoat layer, an antistatic layer, a filter layer, a dye layer and other emulsion layers. The preferred hydrophilic colloid layer is an intermediate layer or a protective layer.

In the present invention, these emulsion layers and / or hydrophilic colloid layers adjacent thereto contain a hydrazine derivative. As the hydrazine derivative, a compound represented by the following general formula [H] is preferable.

[0017]

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

Of the compounds represented by the general formula [H], the compounds represented by the following general formula [Ha] are more preferred.

[0020]

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In the formula, R ¹ 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. Further, R ¹ preferably contains at least one ballast group or silver halide adsorption promoting group.

The diffusion resistant 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], X represents a group capable of substituting for a phenyl group, m represents an integer of 0 to 4, and m represents 2
In the above cases, X may be the same or different.

In the general formula [Ha], A ₃ and A ₄ have the same meanings as A ₁ and A 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.

R in the general formula [Ha]^TwoAs a hydrogen source
Child, alkyl group, alkenyl group, alkynyl group, allyl
Group, heterocyclic group, alkoxy group, hydroxyl group, amino group, cal
It represents a vamoyl group or an oxycarbonyl group. Most preferred
R^TwoAs −COOR_ThreeGroup and -CON (R_Four) (R_Five) Groups
You. R_ThreeRepresents an alkynyl group or a saturated heterocyclic group, R _Four
Is a hydrogen atom, alkyl group, alkenyl group, alkynyl
Group, an aryl group or a heterocyclic group,_FiveIs alkeni
Group, alkynyl group, saturated heterocyclic group, hydroxy group or
Represents an alkoxy group.

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0029]

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[0030]

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[0031]

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[0032]

[Chemical 6]

[0033]

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Specific examples of other preferable hydrazine derivatives include US Pat. No. 5,229,248, fourth column-
(1) to (252) described in the 60th column.

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 gives a high contrast (amount of high contrast), and the optimum amount is generally different depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor and the like. Further, it is in the range of 10 ^-6 to 10 ^-1 mol, preferably 10 ^-5 to 10 ^-2 mol, per mol of silver halide.

The hydrazine derivative according to the present invention is added to the silver halide emulsion layer or its adjacent layer. In order to effectively promote the contrast increase by the hydrazine derivative, it is preferable to use a nucleation accelerator represented by the following general formula [Na] or [Nb].

[0038]

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In the general formula [Na], R ₁₁ , R ₁₂ , and R ₁₃
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, or a substituted aryl group. R ₁₁ , R ₁₂ and R ₁₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. A compound having a molecular weight of 100 or more is preferable in order to have diffusion resistance,
More preferably, the molecular weight is 300 or more. Preferred examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group. A compound having at least one thioether group as a silver halide adsorbing group in the molecule is particularly preferable as the general formula [Na].

Specific examples of these nucleation accelerators [Na] will be given below.

[0041]

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[0042]

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[0043]

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[0044]

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In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic group or heterocyclic group. R ₁₄ represents a hydrogen atom, an alkyl group, an alkynyl group or an aryl group, and Ar and R ₁₄
May be linked by a linking group to form a ring. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, particularly preferably 30.
0 or more. Preferred examples of the silver halide adsorption group include groups having the same meaning as the silver halide adsorption group of the compound represented by the formula [H].

Specific examples of the compound of the general formula [Nb] include those shown below.

[0047]

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[0048]

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Specific examples of other preferable nucleation promoting compounds are described in JP-A-6-258751, page (13), “006”.
2) to (15), “0065” (2-
Compounds 1) to (2-20) and 3-1 to 3-6 described in JP-A-6-2587551, page (15), "0067" to page (16), "0068".

The hydrazine compound and nucleation accelerator according to 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. preferable. The addition amount is the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization,
The optimum amount varies depending on the kind of the inhibitor, etc., but in general, 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.

The non-photosensitive intermediate layer of the silver halide photographic light-sensitive material of the present invention contains a dye dispersed in a solid state.

The finely divided dye dispersed in a solid state is not particularly limited, and a photographic dye can be usually used, but the following general formula [1] to
The dye of [6] can be mentioned.

[0053]

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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 ₁ may be the same or different and 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, and t
Represents 0, 1 or 2, and p ₂ represents 0 or 1. However, the dyes represented by the general formulas [1] to [6] have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule.

The acidic nuclei represented by A and A'in the general formulas [1], [2] and [3] are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanin, hydantoin and thio. Hydantoin, oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone,
Examples include pyrazolopyridone.

The basic nucleus represented by B in the general formulas [3] and [5] is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole, thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole. , Indole.

Examples of the aryl group represented by Q in the general formulas [1] and [4] include a phenyl group and a naphthyl group. In addition, general formulas [1], [4] and [6]
Examples of the heterocyclic group represented by Q and Q ′ include a pyridyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group,
Examples thereof include a pyrazolyl group, an imidazolyl group, an indolyl group, a furyl group and a thienyl group. The aryl group and the heterocyclic group include those having a substituent, and examples of the substituent include substituents such as the amino group and the heterocyclic group of the compounds of the above general formulas [1] to [5]. And the like. These substituents may be used in combination of two or more kinds. Preferred substituents are alkyl groups having 1 to 8 carbon atoms (eg, methyl group, ethyl group, t-butyl group, octyl group, 2-hydroxyethyl group, 2-methoxyethyl group, etc.), hydroxy group, cyano group, Halogen atom (eg fluorine atom, chlorine atom etc.), alkoxy group having 1 to 6 carbon atoms (eg methoxy group, ethoxy group, 2-hydroxyethoxy group, methylenedioxy group, 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.), carboxy group, sulfonamide group (eg methanesulfonamide group, benzenesulfonamide group etc.), sulfamoyl group (eg sulfamoyl group,
(Methylsulfamoyl group, phenylsulfamoyl group, etc.), and these substituents may be combined.

X ₄ and Y _{1 of the} general formulas [4] and [5]
The electron-withdrawing groups represented by may be the same as or different from each other, and the substituent constant Hammett's σp value (edited by Toshio Fujita, “Chemical Region Special Issue No. 122, Structure-Activity Relationship of Drugs”, 96 to 10).
See page 3 (1979) Nankodo. ) Is 0.3 or more, for example, a cyano group, an alkoxycarbonyl group (eg, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, a phenoxycarbonyl group, 4 -Hydroxyphenoxycarbonyl group), carbamoyl group (eg, carbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group, etc.), acyl group (eg, methylcarbonyl group, ethylcarbonyl group, butylcarbonyl group, phenylcarbonyl group) 4-
Ethylsulfonamide carbonyl group etc.), alkylsulfonyl group (eg methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, octylsulfonyl group etc.), arylsulfonyl group (eg phenylsulfonyl group, 4-chlorosulfonyl group etc.) .

L ₁ , L ₂ and L in the general formulas [1] to [5]
_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 (eg, methyl group, ethyl group, hexyl group, etc.), an aryl group (eg, phenyl group, tolyl group, 4-hydroxyphenyl group, etc.), an aralkyl group (eg, benzyl group) Group, phenethyl group, etc.), heterocyclic group (eg, pyridyl group, furyl group, thienyl group, etc.), substituted amino group (eg, dimethylamino group, diethylamino group, anilino group, etc.), and alkylthio group (eg, methylthio group, etc.). Can be

In the present invention, among the dyes represented by the general formulas [1] to [5], a dye having at least one carboxyl group in the molecule is preferably used, and more preferably the general formula [1]. A dye represented by the formula, and particularly preferably a dye in which Q is a furyl group in the general formula [1].

Specific examples of dyes preferably used are shown below, but the dyes are not limited to these.

[0062]

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[0063]

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[0064]

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Other preferable specific examples of the compounds represented by the general formulas [1] to [5] include Japanese Patent Application No. 5-27.
No. I-1 to No. I-3 described on pages 19 to 30 of No. 7011.
0, II-1 to II-12, III-1 to III-8, IV-1 to IV
-9, V-1 to V-8, and VI-1 to VI-5 are included, but the invention is not limited thereto.

The method for producing a solid fine particle dispersion of the dye according to the present invention is described in JP-A-52-92716, JP-A-55-155350, JP-A-55-155351 and JP-A-5-155351.
The methods described in, for example, 3-197943, 3-182743, and WO88 / 04794 can be used. Specifically, it can be produced using a fine disperser such as a ball mill, a planetary mill, a vibration mill, a sand mill, a roller mill, a jet mill, and a disc impeller mill. Further, when the compound in which the solid fine particles are dispersed is water-insoluble at a relatively low pH and water-soluble at a relatively high pH, after dissolving the compound in a weak alkaline aqueous solution, p
The method of precipitating a fine particulate solid by lowering H to make it weakly acidic or the method of preparing a fine particulate solid by simultaneously mixing a weak alkaline solution of the compound and an acidic aqueous solution while adjusting the pH of the compound A dispersion can be obtained. The solid fine particle dispersion of the present invention may be used alone, or two or more kinds may be mixed and used, or may be used by mixing with a solid fine particle dispersion other than the present invention. When two or more kinds are mixed and used, they may be dispersed individually and then mixed, or may be simultaneously dispersed.

When the solid fine particle dispersion of the dye according to the present invention is produced in the presence of an aqueous dispersion medium, it is preferred that a surfactant be present during or after the dispersion. As such a surfactant, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant can be used, but preferably, for example, an alkyl sulfonate, an alkylbenzene sulfonate,
Anionic surfactants such as alkylnaphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, N-acyl-N-alkyl taurines and saponins, alkylene oxide derivatives,
Nonionic surfactants such as alkyl esters of sugars. The above-mentioned anionic surfactants are particularly preferable. Specific examples of the surfactant include Japanese Patent Application No. 5-27.
Nos. 7011 to 46-32 include the compounds 1 to 32, but are not limited thereto.

The amount of the anionic activator and / or the nonionic activator used is not uniform depending on the type of the activator or the conditions of the dispersion liquid of the dye, but usually 1 g of the dye is used.
The amount is preferably 0.1 mg to 2000 mg, more preferably 1 mg to 500 mg. The dye is used in a concentration of 0.01 to 10% by weight in a dispersion liquid, preferably 0.1 to 5% by weight.

The surfactant may be added at a position before the dispersion of the dye is started, and if necessary, it may be further added to the dye dispersion after the dispersion is completed. These anionic activators and / or nonionic activators may be used alone or in combination of two or more.

The solid fine particle dispersion of the dye according to the present invention is preferably dispersed so that the average particle size is 0.01 μm to 5 μm, more preferably 0.01 μm to
1 μm, particularly preferably 0.01 μm to 0.5 μm
It is. The coefficient of variation of the particle size distribution is 5
It is preferably 0% or less, more preferably 40%.
% Or less, and particularly preferably 30% or less. Here, the variation coefficient of the particle size distribution is a value represented by the following equation.

(Standard deviation of particle size) / (Average value of particle size) × 100 To the solid fine particle dispersion of the present invention, a hydrophilic colloid used as a binder of a photographic constituent layer is added before the start of dispersion or after the end of dispersion. can do. As the hydrophilic colloid, it is advantageous to use gelatin, but other than that, for example, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, phthalated gelatin, etc., and gelatin and a monomer having a polymerizable ethylene group are used. Graft polymers, carboxymethyl cellulose, hydroxymethyl cellulose, cellulose derivatives such as cellulose sulfate, polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-N,
Synthetic hydrophilic polymers such as N-dimethylacrylamide, poly-N-vinylpyrrolidone and polymethacrylic acid, agar, gum arabic, alginic acid, albumin and casein can be used. These may be used in combination of two or more. The amount of the hydrophilic colloid added to the solid fine particle dispersion of the present invention is preferably 0.1% to 12% by weight,
More preferably, it is 0.5% to 8%.

The solid fine particle dispersion of the present invention is used in layers constituting a photographic material such as a photosensitive silver halide emulsion layer, an emulsion layer upper layer, an emulsion layer lower layer, a protective layer, a support undercoat layer and a backing layer. It is preferable to use. In particular, in order to enhance the antihalation effect, it is preferably added to a layer between the support and the emulsion layer or a constituent layer on the side opposite to the emulsion layer.
Further, in particular, in order to enhance the effect of improving the safelight property, it is preferably added to the layer above the emulsion layer.

The preferred amount of the solid fine particle dispersion of the dye is not uniform depending on the type of the dye and the characteristics of the photographic light-sensitive material, but it is preferably 1 mg to 1 g per 1 m ^{2 of} the photographic light-sensitive material, and more preferably. It is 5 mg to 800 mg, particularly preferably 10 mg to 500 mg.

In the silver halide photographic light-sensitive material of the present invention, at least one redox compound which releases a development inhibitor upon being oxidized in the emulsion layer closest to the support and / or the hydrophilic colloid layer adjacent thereto. Contains.

The redox compound capable of releasing the development inhibitor by being oxidized will be described below.

The redox compound has hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, reductones and the like as redox groups.

Preferred redox compounds are compounds having a --NHNH-- group as a redox group and the following general formula [1],
It is a compound represented by [2], [3], [4], [5] or [6]. The compound having a -NHNH- group as a redox group is represented by the following general formula [RE-a] or [RE-b]
It is.

Formula [RE-a] T-NHNHC0V- (Time) -PUG Formula [RE-b] T-NHNHCOCOV- (Time) -PUG In the formula, T and V are each an aryl group which may be substituted. Alternatively, it represents an optionally substituted alkyl group. The aryl group represented by T and V includes a benzene ring or a naphthalene ring, and this ring may be substituted with various kinds of substituents, and a preferable substituent is a linear or branched alkyl group (preferably carbon atom). Numbers from 2 to 20, such as methyl, ethyl,
Isopropyl group, dodecyl group, etc.), alkoxy group (preferably having 2 to 21 carbon atoms, for example, methoxy group, ethoxy group, etc.), aliphatic acylamino group (preferably having alkyl group having 2 to 21 carbon atoms, for example, Acetylamino group, heptylamino group, etc.), aromatic acylamino group and the like. In addition to these, for example, the substituted or unsubstituted aromatic ring as described above is -CONH-, -O-, -SO ₂ NH-. , -NHCONH
Including those linked by a linking group such as-, --CH ₂ CHN--. As a photographically useful group, 5-nitroindazole,
4-nitroindazole, 1-phenyltetrazole, 1
-(3-Sulfophenyl) tetrazole, 5-nitrobenztriazole, 4-nitrobenzotriazole, 5-nitroimidazole, 4-nitroimidazole and the like can be mentioned. These development-inhibiting compounds are directly bonded to the CO site of T-NHNH-CO- 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. Can be connected.
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- (stearylamido) -5- (1-phenyltetrazole-5-thio) hydroquinone, 2- (2,4-di-t-amylphenopropionic acid amide-5- (5-nitrotriazol-2-yl) hydroquinone, 2-dodecylthio-5- (2-mercaptothiothiadiazole-5-thio) hydroquinone and the like can be mentioned. The redox compound can be synthesized with reference to the description in US Pat. No. 4,269,929.

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

[0080]

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[0081]

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

The above general formulas [7], [8],

[9], [1
The redox compound represented by 0], [11] or [12] will be described.

In the formula, R ₁ represents an alkyl group, an aryl group or a heterocyclic group. R ₂ and R ₃ represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group. R ₄ represents a hydrogen atom. R _{5 to} R ₉ 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 ₁ , X
₂ represents O or NH. Z ₁ represents an atomic group necessary for forming a 5- or 6-membered heterocycle. W is N (R ₁₀ ) R ₁₁ or OH
And R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

Coup represents a coupler residue capable of causing a coupling reaction with an oxidized product of an aromatic primary amine developing agent, and 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 development inhibitor.

The above general formulas [7], [8],

[9], [1
0], [11] or [12], R ₁ and R ₅ ~
Preferable examples of the alkyl group, aryl group and heterocyclic group represented by R ₁₁ include methyl group, p-methoxyphenyl group and 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 ₂ and R ₃ , 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 _{1 to} R ₁₁ 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 (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), aryl Group (eg phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group etc.), alkoxy group (eg methoxy group, ethoxy group, isopropoxy group, butoxy group etc.), aryloxy group (eg phenoxy group etc.) , A cyano group, an acylamino group (eg, acetylamino group, propionylamino group, etc.), an alkylthio group (eg, methylthio group, ethylthio group, butylthio group, etc.), an arylthio group (eg, phenylthio group, etc.),
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 ( For example, 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 (for example, acetyl group, phenyl group, etc.). Panoiru group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), a hydroxyl group, a nitro group, an imido group (e.g. phthalimido group), a Hajime Tamaki (e.g.,
Pyridyl group, benzimidazolyl group, benzthiazolyl group, benzoxazolyl group and the like).

Examples of the coupler residue represented by Coup include the following. Examples of cyan coupler residues include phenol couplers and naphthol couplers. Examples of magenta couplers include 5-pyrazolone couplers, pyrazolone couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and indazolone couplers. Examples of the yellow coupler residue include a benzoylacetanilide coupler, a pivaloylacetanilide coupler, and a malondianilide coupler.
Examples of non-colored coupler residues include open-chain or cyclic active methylene compounds (eg, indanone, cyclopentanone, malonic diester, imidazolinone, oxazolinone, thiazolinone, etc.). Further, among the coupler residues represented by Coup, those which are preferably used in the present invention can be represented by the general formula (Coup-1) to the general formula (Coup-8).

[0088]

[Chemical 21]

In the formula, R ₁₆ represents an acylamido group, anilino group or ureido group, and R ₁₇ represents a phenyl group which may be substituted with one or more halogen atoms, alkyl groups, alkoxy groups or cyano groups.

[0090]

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In the formula, R ₁₈ and R _{19 each} represent a halogen atom, an acylamido group, an alkoxycarbonylamido group, a sulfoulide group, an alkoxy group, an alkylthio group, a hydroxy group or an aliphatic group, and R ₂₀ and R ₂₁ each represent a fatty acid. Represents a group, an aromatic group or a heterocyclic group. Further, one of R ₂₀ and R ₂₁ may be a hydrogen atom. a represents an integer of 1 to 4; b represents an integer of 0 to 5; When a and b are plural, R
₁₈ may be the same or different, and R ₁₉ may be the same or different.

[0092]

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In the formula, R ₂₂ represents a tertiary alkyl group or an aromatic group, and R ₂₃ represents a hydrogen atom, a halogen atom or an alkoxy group. R ₂₄ 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.

[0094]

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In the formula, R ₂₅ represents an aliphatic group, an alkoxy group, an acylamino group, a sulfonamide group, a sulfamoyl group, a diacylamino group, and R ₂₆ represents a hydrogen atom, a halogen atom or a nitro group.

[0096]

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R ₂₇ and R ₂₈ 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 includes 5- or 6-membered heterocycle having one of O, S, and N atoms in the ring. 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 4,409,323,
Or No. 3,674,478, Research Disclosure 21
228 (December 1981), or JP-A-57-568.
No. 37, JP-A-4-438 and the like are mentioned.

Preferred development inhibitors for PUG are, for example, US Pat. No. 4,477,563 and JP-A-60-21864.
No. 4, No. 60-221750, No. 60-233650.
Or the development inhibitors described in JP-A No. 61-11743.

The general formula [7] used in the present invention will be described below.
Specific examples of the compound represented by the general formula [12] are listed, but the present invention is not limited thereto.

[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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The redox compound is added by alcohols such as methanol and ethanol, glycols such as ethylene glycol, triethylene glycol and propylene glycol, ethers, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate and other esters, acetone and the like. It can be added after being dissolved in ketones such as methyl ethyl ketone. For those that are difficult to dissolve in water or organic solvents, high-speed impeller dispersion,
The average particle size can be arbitrarily dispersed from 0.01 to 6 μm by sand mill dispersion, ultrasonic dispersion, ball mill dispersion, or the like. For the dispersion, a surface active agent such as anion or nonion, a thickener, a latex and the like can be added and dispersed. The addition amount is preferably from 10 ^-6 to 10 ^-1 mol, and more preferably from 10 ^-4 to 10 ^-2 mol, per mol of silver halide.

The redox compound of the present invention 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. In order to enhance the effect of the development inhibitor released from the redox compound, it is preferable that the layer in which the redox compound is present is adjacent to the emulsion layer via the intermediate layer. The specific layer structure is as follows: from the support / adhesive layer / transverse light blocking layer or antihalation layer / emulsion layer / intermediate layer / redox-containing layer / protective layer. Also from support / adhesive layer / transverse light blocking layer or antihalation layer /
It can be used in the order of redox-containing layer / intermediate layer / emulsion layer / protective layer. The gelatin used in these layers can be swelled with a known crosslinking agent, but in order to perform crosslinking in each layer, it is preferable to adjust the molecular weight or use a crosslinking accelerator. Usually, the amount of gelatin in each layer is 0.1 g to 2.
It is preferably 0 g / m ² . The crosslinking agent is preferably used in an amount of 0.01 to 1 mmol per gram gelatin.

In the silver halide photographic light-sensitive material of the present invention, the halogen composition of the emulsion is pure silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride or chloroiodo odor containing 60 mol% or more of silver chloride. It is preferably silver halide.

The average grain size of silver halide is preferably 0.7 μm or less, and particularly preferably 0.5 to 0.1 μm. There is no limitation on the shape of the silver halide grains, and a tabular shape,
It may be spherical, cubic, tetradecahedral, regular octahedral or any other shape. Further, it is preferable that the particle size distribution is narrow, particularly 90% of the total number of particles within a particle size range of ± 40% of the average particle size,
A so-called monodisperse emulsion containing 95% is preferable.

As the method for reacting the soluble silver salt and the soluble halogen salt in the silver halide emulsion, any one-side mixing method, simultaneous mixing method, a combination thereof and the like may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of simultaneous mixing method, a method of keeping pAg constant in the liquid phase where silver halide is formed, so-called controlled double jet method, can be used. A silver halide emulsion having an almost uniform diameter 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.

In the silver halide photographic light-sensitive material of the present invention, generally known sulfur sensitization, selenium sensitization, tellurium sensitization and reduction sensitization, and noble metal sensitization are appropriately selected and used alone or in combination. Can be sensitized. Further, chemical sensitization may not be performed.

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. Triphenylselenophosphine and the like are preferably used as the selenium sensitizer. 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 or rhodium may be contained. As reduction sensitizers, stannous salts, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

The silver halide photographic light-sensitive material of the present invention can be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used include cyanines, merocyanines, complex cyanines, complex merocyanines, holopolar cyanines, hemicyanines, 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 tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, A quinoline nucleus or the like can be applied. These nuclei may be substituted on carbon atoms. Pyrazoline as a nucleus having a ketomethylene structure in merocyanine or complex merocyanine
A 5- to 6-membered heterocyclic ring such as -5-one nucleus, thiohydantoin nucleus, rhodanine nucleus, and thiobarbituric acid nucleus can be applied.

The silver halide photographic light-sensitive material 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 the photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1
-Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3) , 3a, 7-Tetrazaindenes), pentazaindenes, etc .; Add many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. You 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 compound (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.) ),
Mucohalogenated acids (mucochloric acid, phenoxymucochloric acid, etc.) isoxazoles, dialdehyde starch, 2-
Chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination.

The light-sensitive emulsion layer and / or the non-light-sensitive 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.

It is advantageous to use gelatin as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as 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.

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, desensitizer, plasticizer,
Examples include slip agents, development accelerators, oils, and the like.

Regarding these additives and the above-mentioned additives, Research Disclosure No. 17643 (19)
(December 1978) 22-31 pages etc. can be used.

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

According to the present invention, 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 when the processing is performed by using the automatic developing machine in order to shorten the developing time. It is preferably -60 seconds.
The total processing time as used herein includes all process times required for processing the black-and-white light-sensitive material, and specifically, for example, steps such as development, fixing, bleaching, washing with water, stabilizing treatment, and drying necessary for processing. It is a time that includes all the 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-
50 seconds.

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

The 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, etc.), 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 (eg o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2) , 4-diaminophenol, etc.), pyrogallol, ascorbic acid, 1-ant Le-3-pyrazolines (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3- Aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.), transition metal complex salts {Ti, V, Cr, Mn, Fe, C
It is a complex salt of a transition metal such as o, Ni and Cu, and these may be in a form having a reducing power for use as a developing solution. For example, Ti ³⁺ , V ²⁺ , Cr ²⁺ , Fe ^2+, etc. It takes the form of complex salts, and as ligands, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and their salts, phosphoric acids such as hexametapolyphosphoric acid and tetrapolyphosphoric acid and their salts, etc. Is mentioned. } Or the like can be used alone or in combination, but 3
-Pyrazolidones and dihydroxybenzenes, or aminophenols and dihydroxybenzenes or 3-pyrazolidones and ascorbic acid, aminophenols and ascorbic acid, 3-pyrazolidones and transitions It is preferable to use it in combination with a metal complex salt or in combination with an aminophenol and a transition metal complex salt.

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

In the present invention, as a silver sludge preventive agent, JP-B-62-4702, JP-A-3-51844, JP-A-4-26838, JP-A-4-362942, and JP-A-1-31.
Examples thereof include compounds described in No. 9031.

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 placed in an electrolyte solution. The developer waste liquid tank and the electrolyte solution tank are brought into contact with each other through the electrodes, 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, preservatives, alkaline agents, pH buffers, sensitizers, antifoggants, silver sludge inhibitors, etc., which can be added to the developing solution, can be additionally added. 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 developing waste solution is recycled and used, a transition metal complex salt is preferable as the developing agent of the developing solution 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. Dissolution aids (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 the image forming method of the present invention, pH1
Γ is 10 to 3 by processing with a developing solution of less than 1.0.
It is characterized in that a high contrast image of 0 is formed.

The pH of the developing solution in the present invention is 9.5 to 1.
It is preferably adjusted to 1.2, more preferably 9.5 to 10.5. The pH of the developing solution may be adjusted by any method, but it is preferably carried out with a pH adjuster such as sulfuric acid.

As the fixing solution, those having a commonly used composition can be used. The fixing solution is generally an aqueous solution containing a fixing agent and others, and the pH is usually 3.8 to 5.8.
As a fixing agent, thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate; and organic sulfur compounds capable of forming soluble stable silver complex salts And those known as fixing agents can be used.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum and the like can be added to the fixing solution. If desired, the fixer may contain preservatives (eg sulfite, bisulfite), p
H buffer (eg acetic acid), pH regulator (eg sulfuric acid),
A compound such as a chelating agent having the ability to soften water can be included.

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

In the development processing of the present invention, the development temperature is set to 2
The temperature can be set to a normal temperature range of 0 to 30 ° C, or can be set to a high temperature treatment range of 30 to 40 ° C.

[0143]

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 the simultaneous mixing method.
A silver chlorobromide core particle having a diameter of 5 μm and an average diameter of 0.15 μm was prepared. When the core particles were mixed, K ₃ Rh (N0) ₄ (H ₂ O) ₂ was 8 × 10 ^-8 mol per 1 mol of silver, and K ₃ OsCl ₆ was 8 × 1 per 1 mol of silver.
0 ^-6 mol was added. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ is added 3 × per mol of silver.
10 ⁻⁷ mol was added. Furthermore, using silver iodide fine particles, KI
Conversion was performed and the resulting emulsion had an average diameter of 0.2.
μm Core / shell type monodisperse (variation coefficient 10%) silver chloroiodobromide (90 mol% silver chloride, 0.2 mol% silver iodobromide, the rest silver bromide) cubic emulsion there were.

Next, a modified gelatin described in JP-A-2-280139 (a compound in which the amino group in gelatin is substituted with phenylcarbamyl, for example, Exemplified compound G-8 on page 287 (3) of JP-A-2-280139) is used. Used and desalted.
The EAg after desalting was 190 mV at 50 ° C.

The resulting emulsion was treated with 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene 1 x per mole of silver
After adding 10 ^-3 mol, further adding potassium bromide and citric acid to adjust the pH to 5.6 and EAg123mv, and adding 1 × 10 ^-3 mol of sodium p-toluenethiosulfonate, and then adding gold chloride per 1 mol of silver. Acid: 2 × 10 ^-5 mol, Sulfur: 2 × 1
0 ^-5 mol was added and chemical ripening was carried out at a temperature of 60 ° C until maximum sensitivity was obtained.

After aging, 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene 3 × per mol silver
10 ⁻⁴ mol and gelatin were added, and potassium iodide was added at 300 mg / Ag 1 mol.

(Preparation of Silver Halide Emulsion A2) The addition amount of the Rh complex was 11 × with respect to the silver halide emulsion A1.
A silver halide emulsion A2 was prepared in exactly the same manner except that it was 10 ^-8 mol / mol Ag.

Preparation of silver halide photographic light-sensitive material for printing plate-making scanner containing hydrazine derivative Comparative 1 A gelatin subbing layer of the following Formulation 1 was prepared on a support so that the amount of gelatin was 0.5 g / m ² . On top of this, the silver halide emulsion layer 1 of Formulation 3 had a silver content of 3.0 g / m ² and a gelatin content of 2.0 g / m ^2, and a protective layer coating solution of the following Formulation 4 had a gelatin content of 0 g / m ^2. Simultaneous multi-layer coating was applied so that the amount would be 0.6 g / m ² . On the other side of the undercoat layer, a backing layer of the following formulation 5 was formed so that the amount of gelatin was 0.6 g / m ^2, and a polymer layer of the following formulation 6 was further formed thereon, and a polymer layer of the following formulation 7 was formed thereon. The backing protective layer has a gelatin content 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.

Comparative 2 On a support, a gelatin subbing layer of the following formulation 1 was prepared so that the amount of gelatin was 0.5 g / m ² , and a silver halide emulsion layer 1 of the formulation 2 was prepared with a silver amount of 1: 1. .5g / m ^2, so that the amount of gelatin is 1.0 g / m ^2, further amount of silver 1.5 g / m ² of silver halide emulsion layers 2 of Formula 3 thereon, the amount of gelatin 1.0 g / such that m ^2, and more below the amount of gelatin protective layer coating solution of the formulation 4 was simultaneous multilayer coating so as to be 0.6 g / m ^2. On the other side of the undercoat layer, a backing layer of the following formulation 5 was formed so that the amount of gelatin was 0.6 g / m ^2, and a polymer layer of the following formulation 6 was further formed thereon, and a polymer layer of the following formulation 7 was formed thereon. A sample was obtained by simultaneous multilayer coating of the backing protective layer with the emulsion layer side at a speed of 200 m / min by the curtain coating method so that the amount of gelatin was 0.4 g / m ² .

According to the present invention, a gelatin subbing layer having the following formulation 1 is provided on a support so that the amount of gelatin is 0.5 g / m ² , and a silver halide emulsion layer 1 having the formulation 2 is provided with a silver amount of 1. 5 g / m ² , the amount of gelatin was 1.0 g / m ² , and the following Formulation 8 was further added thereon so that the amount of gelatin was 0.6 g / m ^2, and the halogenation of Formulation 3 was further applied to the upper layer. Silver emulsion layer 2 has a silver content of 1.5
g / m ^2, so that the amount of gelatin is 1.0 g / m ^2, further below the amount of gelatin protective layer coating solution of the formulation 4 0.6g
Simultaneous multi-layer coating was applied so as to be / m ² . On the other side of the undercoat layer, a backing layer having the following Formulation 5 was used with a gelatin content of 0.
6 g / m ² of a polymer layer of the following formulation 6 and further a backing protective layer of the following formulation 7 on the emulsion layer side and the curtain so that the amount of gelatin is 0.4 g / m ^2. A sample was obtained by simultaneous multi-layer coating with a coating method at a speed of 200 m / min.

Formulation 1 (Gelatin subbing layer composition) Gelatin 0.5 g / m ² Sodium polystyrene sulfonate (average molecular weight 500000) 10 mg / m ² Redox compound (dispersed with ZrO beads into powder with a particle size of 0.1 μm) Compound shown in the table 50 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 Silver amount 1.5 g / m sensitized at ² dye d-1 6mg / m ² sensitizing dye d-2 3 mg / m ² redox compound (those that have been in the powder particle size 0.1μm dispersed in ZrO beads) table Compound shown in 50 mg / m ² Thallium nitrate 0.5 mg / Ag 1 mol Hydrazine compound H-6 2 × 10 ⁻³ mol / Ag 1 mol Hydrazine compound H-7 2 × 10 ⁻³ mol / Ag 1 mol Compound AM-1 40 mg / m ² Compound e 100 mg / m ² polymer latex (described in JP-A-4-359254, Example 1) 0.5 g / m ² Hardener g 5 mg / m ² S-1 0.7 mg / m ² saponin 20 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² ascorbic acid 20 mg / m ² EDTA 50 mg / m ² sodium polystyrene sulfonate 10 mg / m ² Recipe 3 (silver halide Emulsion layer 2 composition) Silver halide emulsion A1 Sensitizing dye d-1 0.5 mg / m ² so that the amount of silver was 1.5 g / m ^{2 The} exemplary dyes shown in the table (after being dissolved in an alkaline solution, neutralized with citric acid , Crystal precipitated) (Average particle size 0.08 μm) 20 mg / m ² Hydrazine derivative H-6 2 × 10 ^-3 mol / Ag 1 mol Hydrazine derivative H-7 2 × 10 ^-3 mol / Ag 1 mol Compound AM -1 20 mg / m ² S-1 1.7 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² EDTA 50 mg / m ² Styrene-maleic acid copolymer (molecular weight 70,000) 10 mg / m ² polymer latex ( JP-A-4-359254 (described in Example 1) 0.5 g / m ² Gelatin is phthalated gelatin and the coating solution pH is 4.8.
Met.

Formulation 4 (Emulsion protective layer composition) Gelatin 0.6 g / m ² compound AM-1 20 mg / m ² S-1 12 mg / m ² Matting agent: Spherical polymethylmethacrylate 25 mg / m ^{2 with an} average particle size of 3.5 μm Indeterminate silica with an average particle size of 8 μm 12.5 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Surfactant h 1 mg / m ² Lubricant (silicone oil) 4 mg / m ² Colloidal silica (average particle Diameter 0.05 μm) 20 mg / m ² Hardener j 30 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Recipe 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 0.05 μm) 70 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Compound i 100 mg / m ² Formulation 6 (polymer layer composition) Latex j (methyl methacrylate: acrylic acid = 97: 3) ) 1.0 g / m ² hardener g 6 mg / m ² formulation 7 (backing protective ) Gelatin 0.4 g / m ² Matting agent: monodispersed polymethylmethacrylate 50 mg / m ² Sodium an average particle diameter of 5 [mu] m - 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 Hardener g 20 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Zinc oxide 50 mg / m ² Formulation 8 (interlayer composition) Gelatin 0.5 g / m ² Sodium polystyrene sulfonate (average molecular weight: 500000) 10 mg / m ² Example dyes shown in the table (dissolved in alkaline solution, neutralized with citric acid to precipitate crystals) (average particle size 0.08 μm) 20 mg / m m ² S-1 (sodium-iso-amyl-n-decylsulfosuccinate) 0.4m
g / m ²

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The obtained sample was adhered to a step wedge, and a wavelength of 633 was used as a substitute characteristic of He-Ne laser light.
After performing exposure of nm, an automatic processor GR-26SR for rapid processing (Konica [Co.]
Manufactured) under the following conditions.

In addition, in order to evaluate the fine dot quality, SG
The same treatment was carried out after exposure with a dot pattern (FM screen) of 8 μm in a random pattern of -747 RU (manufactured by Dainippon Screen Co., Ltd.).

Developer composition (1 liter formulation) Diethylenetriamine pentaacetic acid / 5 sodium salt 1g Sodium sulfite 42.5g Hydroquinone 20g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 0.85g Potassium carbonate 55g Benzotriazole 0.2g Potassium bromide 4g Boric acid 8g Diethylene glycol 40g 1-Phenyl-6-mercaptotetrazole 0.03g Potassium 17.5g 8-Mercaptoadenine 0.078g Water and potassium hydroxide are added to adjust to 1 liter / pH 10.4.

Fixer composition (1 liter formulation) Ammonium thiosulfate (70% aqueous solution) 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 70 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3 g Aluminum sulfate (27% aqueous solution) 25 ml Water and sulfuric acid are added to adjust to 1 liter / pH 4.9.

(Processing conditions) (Process) (Temperature) (Time) Development 38 ° C. 12 seconds Fixing 35 ° C. 10 seconds Washing 40 ° C. 10 seconds Drying 50 ° C. 12 seconds Total 44 seconds (Evaluation of sensitivity and gamma) Obtained development Completed sample is PDA-6
5 (Konica Digital Densitometer). The sensitivities in the table are expressed as relative sensitivities when the sensitivity of Sample No. 1 at a concentration of 2.5 is 100. Further, (γ) gamma is represented by a tangent of densities of 0.1 and 3.0, and it cannot be used when the gamma value in the table is less than 7, and it is still insufficient if it is 7 or more and less than 10. When the gamma value is 10 or more, an ultra-high contrast image can be obtained only when the gamma value is sufficiently practicable.

(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.

(Evaluation method of linearity) SG-747RU
By changing the exposure amount with a 8 μm random pattern halftone dot (FM screen), what should theoretically be 2% is actually reproduced at 2% What is the theoretical point that should be 95%? % Was measured. It means that it is preferable that the value of the large dot omission in the table is close to 95%. (Measurement is X-Rite 361T) (Evaluation of halftone dot quality) Good order is 5, 4, 3, 2, 1, 5
Ranked into stages. Ranks 1 and 2 are practically unfavorable levels.

Prior to the above evaluation, each emulsion was coated alone (except for the other emulsion layer in the above formulation), passed through an interference filter of 633 nm, and subjected to sensitometry under high illuminance for 10 ^-5 seconds. When the sensitivity was evaluated by the reciprocal of the exposure amount that gives a density of 4, the emulsion 1 was compared to the emulsion 1 by-.
The sensitivity was 12.5%.

The obtained results are shown in Tables 1 and 2. In addition, in the table *, sample No. 11 is sample No. 7 processed at pH = 11.2, and sample No. 12 is sample No. 8 at pH = 11.
It was processed in 2.

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[Table 1]

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[Table 2]

As is apparent from the table, the sample of the present invention had a high concentration and a high gamma, and was excellent in halftone dot quality and large dot dropout. It can also be seen that the occurrence of black spots is small.

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As demonstrated in the examples, according to the present invention, it has a high contrast and high density, improves the halftone property and the deviation of large points, suppresses the generation of black spots, and has excellent linearity. A silver halide photographic light-sensitive material for printing plate making and an image forming method thereof were obtained.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least two silver halide emulsion layers on one side of a support, and a non-light-sensitive intermediate layer between the emulsion layers. / Or a silver halide photographic light-sensitive material comprising a hydrazine derivative in a hydrophilic colloid layer adjacent thereto and a dye dispersed in a solid state in the non-photosensitive intermediate layer. 2. The halogen according to claim 1, wherein the emulsion layer closest to the support and / or the hydrophilic colloid layer adjacent thereto contains a redox compound which is oxidized to release a development inhibitor. Silver halide photographic light-sensitive material. 3. A silver halide photograph according to claim 1 or 2, wherein a high tone image having a gamma of 10 to 30 is formed by processing with a developing solution having a pH of 9.5 to 11.2. Image forming method of photosensitive material.