JP3448722B2 - Silver halide photographic material and image forming method thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, 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, screening methods such as high definition and FM screening for forming images with halftone dots smaller than before have begun to spread. For such a screening method, a super-hard tone type photosensitive material, which is easy to obtain small dot density, is suitable. Various photographic techniques are known as photographic techniques capable of reproducing super-high contrast images in a photosensitive material for printing plate making. Among them, for example, a silver halide photographic light-sensitive material containing a hydrazine derivative as shown in US Pat. No. 4,269,929 and a silver halide photographic light-sensitive material containing a nucleation accelerator as shown in JP-A-4-98239. The material is known. Further, in such a screening method using fine halftone dots, when the small dots are reproduced at the halftone dot% according to the theoretical value, the large dots are likely to be crushed. That is, there is a problem that the image reproducibility (linearity) is deteriorated, and this problem cannot be solved only by increasing the tone of the silver halide photographic light-sensitive material. Further, there 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. However, the addition of such a redox compound has a drawback that it is easily affected by the level of the developing solution, and particularly, the processing at pH 11.0 or higher tends to hinder the contrast.

[0003]

To solve the above problems, a first object of the present invention is to provide a silver halide photographic light-sensitive material excellent in image reproducibility (linearity). An object is to provide an image forming method having excellent contrast.

[0004]

The above objects of the present invention can be achieved by the following constitutions.

In a silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, a solid-dispersed fine particle dye is contained between the silver halide emulsion layer and the support , and the emulsion layer and the And / or its adjacent hydrophilic roller
Hydrazine derivative in at least one layer selected from the id layer
Of the emulsion layer and / or the emulsion layer closest to the support.
At least 1 selected from adjacent hydrophilic colloid layers of
Redox compound that releases a development inhibitor upon oxidation to the layer
A silver halide photographic light-sensitive material having a silver halide emulsion layer containing a.

[0006]

[0007]

[0008]

[0009]   Processing with a developer with a pH less than 11.0
Is characterized by forming a high-contrast image with γ of 10 or more.
Do,RecordOf the silver halide photographic light-sensitive material,Image formation
Method.

The present invention will be described in detail below.

In the present invention, a photosensitive silver halide emulsion layer containing a solid-dispersed fine particle dye (hereinafter referred to as solid fine particle dispersion) is provided between the silver halide emulsion layer and the support. As the dye used in the solid fine particle dispersion,
It is preferable to use the compounds of the general formulas [1] to [6].

[0012]

[Chemical 1]

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, 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, rhodanine, 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. The heterocyclic groups represented by Q and Q'in the general formulas [1], [4] and [6] include, for example, pyridyl group, quinolyl group, isoquinolyl group, pyrrolyl group, pyrazolyl group, imidazolyl group and indolyl group. Base,
A furyl group, a thienyl group and the like can be mentioned. 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. As a preferable substituent, an alkyl group having 1 to 8 carbon atoms (for example, 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.), C1-C6 alkoxy group (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, sulfagroup) Yl group, methylsulfamoyl group, and phenyl sulfamoyl groups)
Therefore, 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 or different, and the substituent constant Hammett's σ _p value (edited by Toshio Fujita, “Chemical Region Special Issue No. 122, Structure-Activity Relationship of Drugs”, 96-103 ( 197
9) Listed in Nanko-do and other places. ) Is 0.3 or more, for example, a cyano group, an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl group, 4-hydroxy group). Phenoxycarbonyl 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 -Ethylsulfonamidocarbonyl group, etc., alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, octylsulfonyl group, etc.), arylsulfonyl group (eg If phenylsulfonyl group, 4-chlorosulfonyl group, etc.).

L ₁ , L ₂ and L of 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.), aryl group (eg, phenyl group, tolyl group, 4-hydroxyphenyl group, etc.), 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,
Examples thereof include a diethylamino group, an anilino group, etc.) and an alkylthio group (eg, methylthio group, etc.).

In the present invention, among the dyes represented by the general formulas [1] to [6], 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.

[0021]

[Chemical 2]

[0022]

[Chemical 3]

[0023]

[Chemical 4]

Other preferred specific examples of the compounds represented by the general formulas [1] to [6] include Japanese Patent Application No. 5-277011.
No. I-1 to No. I-30, II-1 to II on pages 19 to 30
-12, III-1 to III-8, IV-1 to IV-9, V-1 to
Examples thereof include V-8 and VI-1 to VI-5, but are not limited thereto.

A method for producing a solid fine particle dispersion of a dye according to the present invention is described in JP-A-52-92716 and JP-A-55-155350.
Issue 55-155351, Issue 63-197943, Issue 3-182743,
The method described in WO88 / 04794 or the like 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. 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,
A method of precipitating fine particle solids by lowering H to weakly acidic or a method of simultaneously mixing a weak alkaline solution of the compound and an acidic aqueous solution while adjusting pH to prepare fine particle solids 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 present invention is produced in the presence of an aqueous dispersion medium, it is preferable that a surfactant coexists 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 or an alkylbenzene sulfonate. , Alkylnaphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, N-acyl-N-alkyl taurines and other anionic surfactants and saponins, alkylene oxide derivatives, etc. , Nonionic surfactants such as alkyl esters of sugars. The above-mentioned anionic surfactants are particularly preferable. Specific examples of the surfactant include, for example, compounds 1 to 32 described in Japanese Patent Application No. 5-277011, pp. 46 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 the dye 1 is used.
0.1 mg to 2000 mg per g is preferable, more preferably 0.5 m
It may be g to 1000 mg, particularly preferably 1 mg to 500 mg.

The concentration of the dye in the dispersion is 0.01 to 5
It is preferably used so as to be 0% by weight, more preferably 0.1 to 30% 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 types, and both activators may be combined.

The solid fine particle dispersion of the present invention is preferably dispersed so that the average particle diameter is 0.01 μm to 5 μm, more preferably 0.01 μm to 1 μm, and particularly preferably 0.01 μm to 0.5 μm. . The coefficient of variation of the particle size distribution is preferably 50% or less,
More preferably 40% or less, particularly preferably 30%
It is the following solid fine particle dispersion. Here, the variation coefficient of the particle size distribution is a value represented by the following formula.

(Standard deviation of particle size) / (Average value of particle size) × 100 In 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, N-
Dimethylacrylamide, poly-N-vinylpyrrolidone,
Synthetic hydrophilic polymers such as polymethacrylic acid, agar, gum arabic, alginic acid, albumin and casein can be used. You may use these in combination of 2 or more types. The addition amount of the hydrophilic colloid added to the solid fine particle dispersion of the present invention is 0.1% to 1 by weight.
It is preferable to add 2%, and more preferably 0.5% to 8%.

The solid fine particle dispersion of the present invention is required to be contained in at least one silver halide emulsion layer between the silver halide emulsion layer and the support. A layer constituting a silver halide emulsion layer,
It can also be used in layers such as an emulsion layer upper layer, an emulsion layer lower layer, a protective layer, a support undercoat layer and a backing layer. 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 preferable 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. 5 mg to 800 mg,
Particularly preferred is 10 mg to 500 mg.

In the present invention, the hydrazine derivative is preferably a compound represented by the following general formula [H].

[0034]

[Chemical 5]

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, sulfonyl group, 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 is 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.

[0037]

[Chemical 6]

In the formula, R ¹ is an aliphatic group (eg octyl group, decyl group), an aromatic group (eg phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (eg pyridyl group, thienyl group, Represents a furyl group),
Those groups which are further substituted with an appropriate 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 having 8 or more carbon atoms is relatively inert to photographic properties, such as an alkyl group. , 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 adsorbing group described in JP-A No. 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
When is 2 or more, 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.

In the general formula [Ha], R ² represents 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, a carbamoyl group or an oxycarbonyl group. Most preferred R ² includes a —COOR ₃ group and a —CON (R ₄ ) (R ₅ ) group (R ₃ represents an alkynyl group or a saturated heterocyclic group,
R ₄ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or 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.

[0046]

[Chemical 7]

[0047]

[Chemical 8]

[0048]

[Chemical 9]

[0049]

[Chemical 10]

[0050]

[Chemical 11]

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 the method as described in No. 248, columns 59 to 80.

The amount of addition may be any amount that makes the toner to have a high contrast (a high contrast amount), and the optimum amount 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. Generally, it is in the range of 10 ^-6 to 10 ^-1 mol, and preferably in the range of 10 ^-5 to 10 ^-2 mol, per mol of silver halide.

The hydrazine derivative preferably used in the present invention is added to the silver halide emulsion layer and / 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].

[0056]

[Chemical 12]

In the general formula [Na], R ₁₁ , R ₁₂ , R
₁₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group. A ring can be formed by R ₁₁ , R ₁₂ , and R ₁₃ . 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 to have diffusion resistance,
More preferably, the molecular weight is 300 or more. Further, preferable adsorption groups include heterocycle, mercapto group, thioether group, thione group, thiourea group and the like. 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.

[0059]

[Chemical 13]

[0060]

[Chemical 14]

[0061]

[Chemical 15]

[0062]

[Chemical 16]

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 300.
That is all. Further, as a preferable silver halide adsorbing group, a group having the same meaning as the silver halide adsorbing group of the compound represented by the general formula [H] can be mentioned.

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

[0065]

[Chemical 17]

[0066]

[Chemical 18]

Specific examples of other preferable nucleation promoting compounds are exemplified in JP-A-6-258751 (2-1).
To (2-20) and (3-1) described in 6-258751
To (3-6).

The hydrazine compound and nucleation accelerator used in the present invention can be used in any layer on the silver halide emulsion layer side, but are preferably used in the silver halide emulsion layer or its adjacent layer. It is preferable. The addition amount varies depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is generally 10 ^-6 to 10 ^-1 per mol of silver halide. A molar range is preferable, and a range of 10 ⁻⁵ to 10 ⁻² mol is particularly preferable.

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.

Preferred redox compounds are compounds having a --NHNH-- group as a redox group and the following general formulas [7], [8],

It is a compound represented by [9], [10], [11] or [12].

[0072]

[Chemical 19]

[0073]

[Chemical 20]

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

General Formula [RE-a] T-NHNHC0V- (Time) -PUG General Formula [RE-b] T-NHNHCOCOV- (Time) -PUG In General Formulas [RE-a] and [RE-b], T and V each represent an optionally substituted aryl group or an optionally substituted alkyl group. Examples of the aryl group represented by T and V include a benzene ring and a naphthalene ring,
These rings may be substituted with various substituents, and preferred substituents are linear or branched alkyl groups (preferably having 2 to 20 carbon atoms 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, such as acetylamino group, heptylamino group, etc. ), an aromatic acylamino group, and the like, these other, for example, a substituted or unsubstituted aromatic rings, such as described above -CONH -, - O -, - sO 2 NH -, - NHCONH -, - CH 2 Also included are those linked by a linking group such as CHN-. Photographic useful groups include 5-nitroindazole, 4-nitroindazole, 1-phenyltetrazole, 1- (3-sulfophenyl) tetrazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 5-nitroimidazole, 4 -Nitroimidazole and the like can be mentioned. These development-inhibiting compounds are 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-
(Dodecyl ethylene oxide thiopropionic acid amide)
-5- (5-nitroindazol-2-yl) hydroquinone, 2-
(Stearylamide) -5- (1-phenyltetrazole-5-thio) hydroquinone, 2- (2,4-di-t-amylphenoxypropionic acid amide) -5- (5-nitrotriazol-2-yl)
Examples thereof include hydroquinone and 2-dodecylthio-5- (2-mercaptothiothiadiazole-5-thio) hydroquinone. The redox compound can be synthesized with reference to the description in US Pat. No. 4,269,929. The redox compound can be contained in the emulsion layer, in the hydrophilic colloid layer adjacent to the emulsion layer, or in the hydrophilic colloid layer via the intermediate layer.

The above redox compound is added by adding alcohols such as methanol and ethanol, glycols such as ethylene glycol, triethylene glycol and propylene glycol, ether, dimethylformamide,
It can be added after being dissolved in esters such as dimethyl sulfoxide, tetrahydrofuran and ethyl acetate, and ketones such as acetone and methyl ethyl ketone. Further, those which are difficult to dissolve in water or an organic solvent can be arbitrarily dispersed with an average particle size of 0.01 to 6 μm by high speed impeller dispersion, 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 amount of redox compound added is preferably in the range of 10 ^-6 to 10 ^-1 mol, and more preferably 10 ^-4 to 10 ^-2 mol, per mol of silver halide.

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

[0078]

[Chemical 21]

[0079]

[Chemical formula 22]

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

Further, the above general formulas [7], [8],

[9],
The redox compound represented by [10], [11] or [12] will be described.

General formulas [7], [8],

[9], [1
0], [11] or [12], R ₁ represents an alkyl group, an aryl group or a heterocyclic group. R ₂ and R ₃
Represents 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 ~ R ₉
Represents 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 and X ₂ represent O or NH. Z ₁ is 5-6
Represents a group of atoms necessary to form a member heterocycle. W is N
It represents (R ₁₀₎ R ₁₁ or OH,, R ₁₀ and R ₁₁ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. CO
UP 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.

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

[9], [1
0], [11] or [12] (hereinafter, in the formula), the alkyl group, aryl group and heterocyclic group represented by R ₁ and R _{5 to} R ₁₁ are preferably a methyl group and p-methoxyphenyl. Group, pyridyl group and the like. 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 carbon number of these groups is preferably 1-20. 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.), cyano group, acylamino Groups (eg acetylamino group, propionylamino group etc.), alkylthio groups (eg methylthio group, ethyl O group, butylthio group, etc.), an arylthio group (e.g., phenylthio group), a sulfonylamino group (e.g., methanesulfonylamino group, etc. benzenesulfonylamino group),
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.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.) ,
Aryloxycarbonyl group (eg, phenoxycarbonyl group), sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.),
Acyl group (eg acetyl group, propanoyl group, butyroyl group etc.), amino group (methylamino group, ethylamino group, dimethylamino group etc.), hydroxyl group, nitro group, imide group (eg phthalimido group etc.), heterocyclic group (For example, a pyridyl group, a benzimidazolyl group, a benzthiazolyl group, a benzoxazolyl group and the like). Examples of the coupler residue represented by COUP include the following. Examples of cyan coupler residues include phenol couplers and naphthol couplers. Examples of magenta couplers include 5-pyrazolone couplers, pyrazolone couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and indazolone couplers. Examples of the yellow coupler residue include a benzoylacetanilide coupler, a pivaloylacetanilide coupler, and a malondianilide coupler. Colorless coupler residues include open-chain or cyclic active methylene compounds (eg, indanone, cyclopentanone, malonic acid diester, imidazolinone, oxazolinone, thiazolinone, etc.). Further, among the coupler residues represented by Coup, those which are preferably used in the present invention are represented by the general formula (Co
It can be represented by up-1) to general formula (Coup-8).

[0084]

[Chemical formula 23]

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.

[0086]

[Chemical formula 24]

In the formula, R ₁₈ and R _{19 each} represent a halogen atom, an acylamido group, an alkoxycarbonylamido group, a sulfouride 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 and 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.

[0088]

[Chemical 25]

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.

[0090]

[Chemical formula 26]

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.

[0092]

[Chemical 27]

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 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, 4,409,323, or 3,674,478.
No. 4, Research Disclosure 21228 (December 1981), or JP-A-57-56837 and JP-A-4-438.

Preferred development inhibitors for PUG are, for example, US Pat. No. 4,477,563, JP-A-60-218644, and JP-A-60-22175.
No. 0, No. 60-233650, or No. 61-11743.

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

[0098]

[Chemical 28]

[0099]

[Chemical 29]

[0100]

[Chemical 30]

[0101]

[Chemical 31]

[0102]

[Chemical 32]

[0103]

[Chemical 33]

[0104]

[Chemical 34]

[0105]

[Chemical 35]

General formula [7] preferably used in the present invention
The compound represented by [12] is preferably contained in an amount of 1 × 10 ⁻⁶ to 5 × 10 ⁻² mol, and more preferably 1 × 10 ⁻⁴ to 2 × 10 ⁻² mol per mol of silver halide. Is preferred.

The compounds represented by the above general formulas [7] to [12] are suitable water-miscible organic solvents such as alcohols,
It can be used by dissolving it in ketones, dimethyl sulfoxide, dimethylformamide, methyl cellosolve and the like. It is also possible to add it as an emulsified dispersion using a known oil. Further, the compound powder may be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or ultrasonic waves according to a method known as a solid dispersion method.

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

The gelatin used in these layers can be swollen with a known cross-linking agent, but in order to cross-link each layer, it is preferable to adjust the molecular weight or use a cross-linking accelerator. Usually, the amount of gelatin in each layer is 0.1g-2.0g /
It is preferably m ² . The cross-linking agent is preferably used at 0.01 mmol to 1 mmol per gram gelatin.

In the present invention, generally known sulfur sensitization, Se, Te sensitization, reduction sensitization and noble metal sensitization methods may be appropriately selected and used in combination, and chemical sensitization is not performed. May be.

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

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

Examples of the reduction sensitizer include stannous salt, amines,
Formamidine sulfinic acid, a silane compound, etc. can be used.

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

The average grain size of silver halide is preferably 0.7 μm or less, and particularly preferably 0.5 to 0.1 μm. The average particle size is a term that is commonly used and easily understood by experts in the field of photographic science. The particle size means a particle diameter when the particles are spherical or particles which can be approximated to a sphere. When the particle is a cube, it is converted into a sphere, and the diameter of the sphere is taken as the particle size. For more information on determining the average particle size, see Mies, James: The Theory of the
Photographic process (CEMees & T.H.James
Author: The theory of the photographic process), No. 3
Edition, pp. 36-43 (1966 (published by McMillan "Mcmillan")).

The shape of the silver halide grains is not limited,
Any shape such as a flat plate shape, a spherical shape, a cubic shape, a 14-sided shape, a regular octahedron shape or the like may be used. Also, it is preferable that the particle size distribution is narrow, especially 90% of the total number of particles within the particle size range of ± 40% of the average particle size.
%, Preferably 95%, so-called monodisperse emulsions are preferred.

As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a forward mixing method, a 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 a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. A silver halide emulsion having a uniform grain size can be obtained.

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

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Resear
ch Disclosure) No. 176, 17643, pages 22-23 (December 1978)
It is described in the literature described or cited.

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

In 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 referred to here includes all process times required for processing the black-and-white light-sensitive material, and specifically, for processing, for example, developing, fixing, bleaching, washing, stabilizing, drying, etc. It is the time that includes all the process time, that is, the time to Dry to Dry. 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 at 90 ° C. to 130 ° C.) or 150
Radiant objects above ℃ (for example, tungsten, carbon, nichrome, mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc. to generate heat and radiate heat directly, or heat energy from resistance heating element to copper, stainless steel, nickel, various Those that emit infrared radiation by transmitting heat to a radiator such as ceramic) and those that have a drying zone are included.

The silver halide emulsion used in 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 normally used for cyanine dyes as a basic heterocyclic nucleus 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, that is, an indolenine nucleus,
Benzindolenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, 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. As a nucleus having a ketomethylene structure in a merocyanine dye or a complex merocyanine dye, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5-6 membered heterocyclic ring such as a thiobarbituric acid nucleus can be applied.
Specifically, Research Disclosure Vol. 176 RD-17
643 (December 1978 issue) page 2-3, US Pat. No. 4,425,425
Nos. 4,425,426 can be used. The sensitizing dye may be dissolved using ultrasonic vibration described in US Pat. No. 3,485,634. In addition, as a method of dissolving or dispersing the sensitizing dye of the present invention in an emulsion, U.S. Patent Nos. 3,482,981 and 3,585,1 are cited.
No. 95, No. 3,469,987, No. 3,425,835, No. 3,342,605
, British Patents 1,271,329, 1,038,029, 1,121,17
The methods described in US Pat. No. 4, U.S. Pat. Nos. 3,660,101 and 3,658,546 can be used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure 176, 17643 (published in December 1978), page 23.

The silver halide photographic light-sensitive material of the present invention comprises
For the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance,
Various compounds can be included. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, for example triazain Denes, tetrazaindenes (particularly 4-hydroxy-substituted-1,3,3a, 7-tetrazaindenes), pentazaindenes, etc .; benzenethiosulfonic acid, benzene Luffin acid, can be added to many compounds known as antifoggants or stabilizers such as benzenesulfonic acid amide.

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,
Methyloldimethylhydantoin etc.), dioxane derivative (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.), mucohalogen acids (mucochloric acid, phenoxymucochloric acid etc.) isoxazole , 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.

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 hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid,
A wide variety of synthetic hydrophilic polymeric substances such as polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers can be used.

As the gelatin, other than lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Gelatin enzymatic degradation products 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 (eg vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination,
Alternatively, it is possible to use a polymer having a monomer component of a combination of these and acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, or the like. it can.

The silver halide photographic light-sensitive material of the present invention comprises
Various other additives are used. For example, desensitizer,
Examples include plasticizers, slip agents, development accelerators, oils, and the like.

Regarding these additives and the above-mentioned additives, specifically, those described in Research Disclosure No. 176 (supra), pages 22 to 31 can be used.

In the silver halide photographic light-sensitive material of 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 multiple layers, an intermediate layer or the like may be provided between them.

In the silver halide photographic 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 silver halide photographic light-sensitive materials. Useful as the flexible support are films made of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene and polyethylene terephthalate.

Examples of the developing agent that can be used in the present invention include dihydroxybenzenes (eg, hydroquinone, chlorohydroquinone, bromhydroquinone, 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-aryl-3-pyrazolines (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline , 1- (p-aminophenyl)
-3-aminopyrazoline, 1- (p-amino-N-methylphenyl)
-3-aminopyrazoline, etc.), transition metal complex salts (Ti, V,
It is a complex salt of a transition metal such as Cr, Mn, Fe, Co, Ni, Cu, etc., 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. in the form of complex salts, and as ligands, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA)
Examples thereof include aminopolycarboxylic acids and salts thereof, and phosphoric acids such as hexametapolyphosphoric acid and tetrapolyphosphoric acid and salts thereof. ), 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 usually preferably used in an amount of 0.01 to 1.4 mol / liter.

In the present invention, as a silver sludge-preventing agent, JP-B-62-4702, JP-A-3-51844, and JP-A-4-26838,
The compounds described in JP-A 4-362942, JP-A 1-319031 and the like can be mentioned. Further, the developing waste liquid can be regenerated by energizing it. Specifically, put a negative electrode (for example, an electric conductor or semiconductor such as stainless steel wool) in the developing waste solution and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) in the electrolyte solution, and perform anion exchange. The waste developer tank and the electrolyte solution tank are in contact with each other through the film, and both electrodes are energized for regeneration. It is also possible to process the light-sensitive material according to the present invention 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. Further, there is a method of processing the light-sensitive material while energizing the developing solution, and at that time, an additive which can be added to the developing solution as described above can be additionally added. When the developer waste liquid is regenerated and used, transition metal complex salts are preferable as the developing agent of the developer used.

Examples of sulfites and metabisulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably 0.25 mol / liter or more. It is particularly preferably 0.4 mol / liter or more.

If necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, citric 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, antifoaming agents, antifoggants (for example, 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.), development accelerator (for example, US Pat. No. 2,304,025)
Nos. 5,047,456 and Japanese Patent Publication No. 47-45541), a hardener (eg glutaraldehyde or its bisulfite adduct), an antifoaming agent and the like can be added. By adjusting the pH of the developing solution to 8.5 to 10.9, a high contrast image with a gamma (γ) of 10 or more can be obtained.

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 a developing treatment is often used as one of the rapid processing methods for a light-sensitive material in combination with a silver salt stabilizing treatment with a thiocyanate, and can be applied to such a processing solution.
In the case of such rapid processing, the effect of the present invention is particularly great.

As the fixing liquid, those having a generally 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.
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.

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

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

In the development processing of the present invention, the development temperature is
The temperature can be set within a normal temperature range of 20 to 35 ° C, or can be set within the range of high temperature treatment of 35 to 40 ° C.

[0145]

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

Example 1 (Preparation of Silver Halide Emulsion A1) An average thickness of 0.05 μm comprising 95 mol% of silver chloride and the balance of silver bromide by using the simultaneous mixing method.
A silver chlorobromide core particle having 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 added in an amount of 8 × 10 ^-8 mol per mol of silver, and K ₃ OsCl ₆ was added in an amount of 8 × 10 ^-6 per mol of silver.
Mol added. The core particles were shelled using the double jet method. At that time, K ₂ IrCl ₆ was added 3 × per mol of silver.
10 ^-7 mol was added. Further, using silver iodide fine particles, KI
After conversion, the resulting emulsion has an average diameter of 0.2 μm.
Was a cubic crystal emulsion of core / shell type monodisperse (variation coefficient 10%) silver chloroiodobromide (90 mol% silver chloride, 0.2 mol% silver iodobromide, the rest being silver bromide). Then, JP-A-2-2801
Modified gelatin described in Japanese Patent No. 39 (a gelatin in which an amino group is substituted with phenylcarbamyl, for example, JP-A-2-2801).
No. 39, page 287 (3), Exemplified Compound G-8) was used for desalting. The EAg after desalting was 190 mv at 50 ° C.

4-hydroxy-6-methyl-1, was added to the resulting emulsion.
3,3a, 7-tetrazaindene was added at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH.
Adjust to 5.6, EAg123mv, add 1 × 10 ^-3 mol of sodium p-toluenethiosulfonate, and then add the compounds of the present invention and sulfur compounds as shown in Table 1 until the maximum sensitivity is obtained at a temperature of 60 ° C. Chemically aged. 4-hydroxy after aging
-6-Methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol, silver 1-phenyl-5-mercaptotetrazole in an amount of 3 × 10 ^-4 mol and silver, and iodine was added. 300 mg of potassium iodide / 1 mol of Ag was added.

(Preparation of silver halide emulsions A2 and 3) The amount of the Rh complex added to silver halide emulsion A1 was 9 × 10 ^-8.
A silver halide emulsion A2 was prepared in exactly the same manner except that the mole ratio was Ag / Ag mole.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner containing hydrazine derivative) A gelatin subbing layer having the following formulation 1 was coated on a support to give a gelatin amount of 0.5 g.
/ M ² on top of which silver halide emulsion layer 1 of Formula ² has a silver content of 1.5 g / m ² , and the amount of gelatin is 1.0 g / m ^2, and a halogen of Formula 3 on the upper layer. The silver halide emulsion layer 2 was made to have a silver amount of 1.5 g / m ² and a gelatin amount of 1.0 g / m ^2, and a protective layer coating solution of the following prescription 4 was further added to give a gelatin amount of 0.6 g / m ^2.
Simultaneous multilayer coating. On the opposite subbing layer, a backing layer of the following formulation 5 was prepared so that the amount of gelatin was 0.6 g / m ^2, and a polymer layer of the following formulation 6 was further formed on the backing layer of the formulation 7 below. The protective layer is curtain coated with the emulsion layer side so that the amount of gelatin is 0.4 g / m ^2.
A sample was obtained by simultaneous multilayer coating 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 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 ² equivalent amount Sensitizing dye d-1 6 mg / m ² Sensitizing dye d-2 3 mg / m ² Thallium nitrate 0.5 mg / Ag 1 mol hydrazine compound exemplified H-7 2 × 10 ^-3 mol / Ag1 mole amino compound AM-1 40mg / m ² compound e 100 mg / m ² polymer latex f 0.5 g / m ² hardener g 5 mg / m ² Sodium - iso -Amyl-n-decyl sulfosuccinate 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 Formulation 3 (composition of silver halide emulsion layer 2) Silver halide emulsion A1 Silver equivalent to 1.5 g / m ² Sensitizing dye d-1 0.5 mg / m ² Hydrazine derivative Exemplified H-7 2 × 10 ^-3 mol / Ag 1 mol Amino compound AM-1 20 mg / m ² Sodium -Iso-amyl-n-decylsulfosuccinate 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 f 0.5 g / 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 AM-1 20 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² Matting agent: Average particle size 3.5 μm Spherical polymethylmethacrylate 25 mg / m ² Average particle size 8 μm Indeterminate silica 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 size 0.05 μm) 20 mg / m ² Hardener j 30 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Formulation 5 (Backing layer composition) Gelatin 0.6 g / m ² Sodium-iso-amyl -n-decyl sulfosuccinate 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) LATEC j (methyl methacrylate: acrylic acid = 97: 3) 1.0g / m 2 hardener g 6 mg / ^{m 2} formulation 7 (backing protective layer) Gelatin
0.4 g / m ² matting agent: monodisperse polymethylmethacrylate having an average particle size of 5 μm 50 mg / m ² sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² surfactant h 1 mg / m ² dye k 20 mg / M ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² Hardener g 20 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Zinc hydroxide 50 mg / m ² When a disperse dye is added, AD-8 (Dye Exemplified by ball milling into powder having a particle size of 0.1 μm) is added to emulsion layer 1 (lower layer) at 20 mg / m ² , and redox compound RE-1 (ZrO beads). Dispersed with
In the case of adding 0.1 μm powder), 50 mg / m ^{2 was} added to a layer as shown in Table 1 to prepare samples 1 to 8. However, Sample 8 was processed with the developing solution having a pH of 11.6.

[0152]

[Chemical 36]

[0153]

[Chemical 37]

(Developer Composition) Per 1 L of Working Solution Diethyltriamine pentaacetic acid / 5 sodium salt 1 g Sodium sulfite 42.5 g Potassium sulfite
17.5g Potassium carbonate 55g Hydroquinone 20g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.85g Potassium bromide 4g 5-Methylbenzotriazole 0.2g Boric acid 8g Diethylene glycol 40g 8-Mercaptoadenine 0.3g KOH solution To give a pH of 10.4.

[0155] (Fixer composition) Per 1 liter of solution used   200 ml ammonium thiosulfate (70% aqueous solution)   Sodium sulfite 22g   Boric acid 9.8g   Sodium acetate trihydrate 34g   Acetic acid (90% aqueous solution) 14.5g   Tartaric acid 3.0g   Aluminum sulfate (27% aqueous solution) 25 ml   The pH of the working solution was adjusted to 4.9 with sulfuric acid.

[0156] (Evaluation of sensitivity, gamma, and point quality [DQ]) An optical wedge was used for the obtained sample, and a light source equipped with an interference filter of 633 nm was used as a substitute for the He-Ne laser light source.
Perform high intensity exposure of 0 ^-5 seconds, development processing was carried out under the conditions described above.

A digital densitometer P was used to obtain the developed sample.
The sensitivity, fog, and gamma were measured using DA-65 (manufactured by Konica Corporation). The sensitivities in the table are expressed as relative sensitivities when the sensitivity at 2.5 in Document No. 1 is 100. Also,
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. It is shown that a gamma value of 10 or more gives a super-high contrast image for the first time, and it is a sufficiently practical photosensitive material.

[0158] The spot quality was visually evaluated on a 5-point scale. Less fringes are preferable, and the practical lower limit is 3.

(Evaluation method of large dot missing, practical density) The large dot missing is theoretically obtained when the exposure amount is changed by halftone dots (FM screening) of 8 μm random pattern with SG-747RU and the treatment is performed under the above conditions. At the exposure amount at which 2% is actually reproduced to 2%, what percentage theoretically should be 95% is measured by the dot% measurement mode of the X-Rite 361T densitometer. The measured value is preferably close to 95%.

The practical density was determined by measuring the density of the solid area (100% area) using a digital densitometer PDA-65.

The evaluation results are shown in Table 1.

[0162]

[Table 1]

From Table 1, the sample of the present invention is excellent in linearity. Further, it can be seen that the sample treated at a pH of less than 11.0 is particularly excellent in linearity and contrast.

Example 2 In Example 1, the following sensitizing dyes d-1 and d-2 were replaced by the following d-3 and d-4, and the solid disperse dye was replaced by AD-8 by AD-6, Addition layer is gelatin subbing layer and emulsion layer 1
The same results as in Example 1 were obtained except that 20 mg / m ^{2 was} used in each (lower layer) and the exposure machine was an infrared semiconductor laser light source recorder MT-R1120 (manufactured by Dainippon Screen Mfg. Co., Ltd.). Got

[0165]

[Chemical 38]

[0166]

According to the present invention, a silver halide photographic light-sensitive material excellent in linearity and high contrast can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 1/40 G03C 1/06 501 G03C 1/43

Claims (2)

(57) [Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, comprising a solid-dispersed fine-grained dye between the silver halide emulsion layer and the support.
And the hydrophilic colloid adjacent to the emulsion layer and / or
A hydrazine derivative in at least one layer selected from the
And the emulsion layer closest to the support and / or its
At least one layer selected from adjacent hydrophilic colloid layers
Redox compounds that release development inhibitors when oxidized to
A silver halide photographic light-sensitive material having a silver halide emulsion layer contained therein. 2. Processing with a developer having a pH of less than 11.0.
Characterized by forming a high-contrast image with γ of 10 or more
An image of the silver halide photographic light-sensitive material according to claim 1,
Forming method.