JPH0980670A - Silver halide photographic sensitive material and its image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive material which has high density and is excellent in linearity and gradation variability. SOLUTION: This photosensitive material has at least two silver halide emulsion layers on one side of a base, contains a hydrazine derivative in at least one of the emulsion layers and/or the adjacent hydrophilic colloid layer, a redox compound which is oxidized to release a development controlling agent in the emulsion layer closest to the base and/or the adjacent hydrophilic colloid layer, and also has a layer containing a dye dispersed in solid between the emulsion layer closest to the base and the base. It preferably has a gamma (γ) of 10 or more when processed with a developer having a pH less than 11.0.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a 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 field of printing plate making, a screening method such as FM screening for forming an image with a halftone dot smaller than the conventional one has begun to spread in order to obtain a high-definition image. In this screening method,
There is a problem that small dots are hard to be formed and large dots are easily crushed, and a silver halide photographic light-sensitive material (hereinafter also referred to as a light-sensitive material) having excellent linearity is required. Higher dot quality and higher density are required.

To meet these demands, a super-high contrast type photosensitive material, which is easy to form small-dot density, is suitable.

As a photographic technique capable of reproducing an ultrahigh contrast image in a light-sensitive material for printing plate making, a light-sensitive material containing a hydrazine derivative as disclosed in, for example, US Pat. A photosensitive material containing a nucleation accelerator such as that disclosed in Japanese Patent No. 98239 has a pH of 1
It is known that even when treated with a stable developing solution of less than 1.0, excellent contrast can be obtained.

However, when a hydrazine derivative is used, high density and high halftone dot quality can be obtained, but large dots are easily crushed, black spots are likely to be generated, and photographic performance is greatly increased due to slight fluctuations in exposure conditions. There is a problem that it will fluctuate.

On the other hand, there is known a technique for improving photographic performance by using a compound releasing a photographically useful group by a redox reaction in a light-sensitive material containing a hydrazine compound. However, when the redox compound is used, the linearity is improved, but the present situation is that the sensitivity and the density are lowered, and the halftone dot quality is largely deteriorated, so that a satisfactory result cannot be obtained.

[0007]

In order to solve the above problems, the object of the present invention is to obtain high halftone dot quality and high density.
Another object of the present invention is to provide a light-sensitive material that is excellent in linearity and exposure stability and that does not cause black spots.

[0008]

The above objects of the present invention are as follows: 1. At least two silver halide emulsion layers are provided on one side of a support, and at least one of the emulsion layers and / or its adjacent hydrophilic layer. Closest to the support, containing a hydrazine derivative in the hydrophilic colloid layer, and containing a redox compound that is oxidized to the emulsion layer closest to the support and / or its adjacent hydrophilic colloid layer to release the development controlling agent. A silver halide photographic light-sensitive material characterized by having a layer containing a dye dispersed in a solid state between an emulsion layer and a support 2, gamma (γ) when processed with a developer having a pH of less than 11.0. Is 10 or more, which is achieved by the silver halide photographic light-sensitive material described in 1.

That is, the present inventors balance the promotion of nucleation and control with a hydrazine derivative and a redox compound that releases a development control agent, and further provide a solid disperse dye layer as a lower layer to obtain superhigh contrast and linearity. Together with
The inventors of the present invention have found that exposure stability can be obtained even when hydrazine is used and black spots are not generated, and the present invention has been completed.

Hereinafter, the present invention will be described specifically.

The hydrazine derivative according to the present invention includes
It is a compound represented by the following general formula [H].

[0012]

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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 a-(CO) n- group, a sulfonyl group, a sulfoxy group, or --P.
(＝ O) represents an R ₂ — group or an iminomethylene group;
Represents an integer of 1 or 2, A1, A ₂ both represent a hydrogen atom or one other is a substituted or unsubstituted alkylsulfonyl group a hydrogen atom or a substituted or unsubstituted acyl group,, R represents a hydrogen atom, Each represents a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group, carbamoyl group, or oxycarbonyl group. R ₂ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, amino group and the like.

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

[0015]

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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, cenyl 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, for example, 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 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 when m 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 is a hydrogen atom,
Alkyl group, alkenyl group, alkynyl group, allyl group,
It represents a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group, a carbamoyl group, or an oxycarbonyl group. Most preferred R ²
Is a —COOR ₃ group and —CON (R ₄ ) (R ₅ ).
And a 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,
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.

[0023]

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[0024]

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[0025]

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[0026]

[Chemical 6]

[0027]

[Chemical 7]

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

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

The hydrazine derivative used in the present invention is
It is added to the silver halide emulsion layer or an 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].

[0033]

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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,
It represents a substituted aryl group, and 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. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable. Preferred examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group. Particularly preferred as the general formula [Na] is a compound having at least one thioether group as a silver halide adsorptive group in the molecule. Specific examples of these nucleation accelerators [Na] will be given below.

[0035]

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[0036]

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[0037]

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[0038]

[Chemical 12]

In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic group or heterocyclic group. R ₁₄ is a hydrogen atom,
Represents an alkyl group, an alkynyl group, or an aryl group;
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, and particularly preferably 300 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.

[0041]

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[0042]

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Specific examples of other preferable nucleation promoting compounds include compounds (2-1) to (2-20) described in JP-A-6-258751 and 6-2587.
3-1 to 3-6 described in No. 51.

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 optimum amount to be added depends on the particle 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. It is preferably in the range of mol, particularly preferably 10 ^-5 to 10 ^-2 mol.

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

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 formulas [1], [2], [3], [4], [5] or [6].
Is a compound represented by.

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

General Formula [RE-a] T-NHNHCOV- (Time) -PUG General Formula [RE-b] T-NHNHCOCOV- (Time) -PUG 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 contains a benzene ring or a naphthalene ring, and this ring may be substituted with various substituents. As a preferable substituent, a linear or branched alkyl group (preferably having a carbon number 2-20, for example, methyl, ethyl, isopropyl group, dodecyl group, etc., alkoxy group (preferably having 2-21 carbon atoms, for example, methoxy group, ethoxy group, etc.), aliphatic acylamino group (preferably carbon number) 2 to 21 alkyl groups such as acetylamino group, heptylamino group, etc.), aromatic acylamino groups and the like. In addition to these, the substituted or unsubstituted aromatic ring as described above is -CONH. -, -O-,
It also includes those linked by a linking group such as —SO ₂ NH—, —NHCONH—, and —CH ₂ CHN—. Examples of photographically useful groups include 5-nitroindazole, 4-nitroindazole, 1-phenyltetrazole, 1- (3-sulfophenyl) tetrazole, 5-nitrobenztriazole, 4-nitrobenzotriazole, 5-nitroimidazole, 4 -Nitroimidazole and the like.

These development inhibitor compounds are T-NHNH
It can be directly connected to the CO site of —CO— via a hetero atom such as N or S, or via an alkylene, phenylene, aralkylene, or aryl group and further via a hetero atom such as N or S. In addition, a development inhibitor such as triazole, indazole, imidazole, thiazole or thiadiazole may be introduced into a hydroquinone compound having a ballast group. For example, 2- (dodecylethylene oxide thiopropionic acid amide-5-
(5-nitroindazol-2-yl) hydroquinone, 2- (stearylamido) -5- (1-phenyltetrazol-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 preferable general formulas are shown below.

[0053]

[Chemical 15]

[0054]

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

The above general formulas [1], [2], [3],
The redox compound represented by [4], [5] or [6] will be described.

General formulas [1], [2], [3], [4],
In [5] or [6], R ₁ represents an alkyl group, an aryl group or a heterocyclic group. R ₂ and R ₃ are a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group,
Sulfonyl group, aryl group, oxalyl group, heterocyclic group,
It represents an alkoxycarbonyl group or an aryloxycarbonyl group. R 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 each represent a substituent capable of substituting on the benzene ring. X ₁ and X ₂ represent O or NH. Z ₁ represents an atomic group necessary for forming a 5- or 6-membered heterocycle. W is N (R
₁₀ ) represents 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 [1], [2], [3],
In [4], [5] or [6], R ₁ and R ₅
To alkyl groups, aryl groups and heterocyclic groups represented by R ₁₁ are preferably methyl group, p-methoxyphenyl group,
Examples thereof include a pyridyl group. Among the acyl group, carbamoyl group, cyano group, nitro group, sulfonyl group, aryl group, oxalyl group, heterocyclic group, alkoxycarbonyl group and aryloxycarbonyl group represented by R 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.), cyano group, acylamino group (eg acetylamino group, propionylamino group etc.), alkylthio group (eg Methylthio group, ethylthio group, butylthio group etc.), arylthio group (eg phenylthio group etc.), sulfonylamino group (eg methanesulfonylamino group, benzenesulfonylamino group etc.), ureido group (eg 3-methylureido group, 3,3) -Dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (dimethylsulfamoylamino group, etc.),
Carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg, ethylsulfamoyl group, dimethylsulfamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.) ,
Aryloxycarbonyl group (for example, phenoxycarbonyl group, etc.), sulfonyl group (for example, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.),
Acyl group (eg acetyl group, propanoyl group, butyroyl group etc.), amino group (methylamino group, ethylamino group, dimethylamino group etc.), hydroxyl group, nitro group, imide group (eg phthalimido group etc.), heterocyclic group (For example, a pyridyl group, a benzimidazolyl group, a benzthiazolyl group, a benzoxazolyl group and the like). Examples of the coupler residue represented by COUP include the following. Examples of cyan coupler residues include phenol couplers and naphthol couplers. Examples of magenta couplers include 5-pyrazolone couplers, pyrazolone couplers, cyanoacetylcoumarone couplers, open chain acylacetonitrile couplers, and indazolone couplers. Examples of the yellow coupler residue include a benzoylacetanilide coupler, a pivaloylacetanilide coupler, and a malondianilide coupler. 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).

[0060]

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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.

[0062]

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In the formula, R ₁₈ and R _{19 each} represent a halogen atom, an acylamido group, an alkoxycarbonylamido group, a sulfoureido group, an alkoxy group, an alkylthio group, a hydroxy group or an aliphatic group, and R 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.

[0064]

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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.

[0066]

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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.

[0068]

[Chemical 21]

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 3,674,478, Reserc
h Disclosure 21228 (December 1981)
Month), or JP-A-57-56837 and JP-A-4-43.
Examples thereof include those described in JP-A-8.

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

The general formula [1] to be used in the present invention will be described below.
Specific examples of the compound represented by [6] are listed, but the present invention is not limited thereto.

[0073]

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[0074]

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[0075]

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[0076]

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[0077]

[Chemical formula 26]

[0078]

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[0079]

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[0080]

[Chemical 29]

The hydrazine derivative and the redox compound are added by adding alcohols such as methanol and ethanol, glycols such as ethylene glycol, triethylene glycol and propylene glycol, ethers, esters such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran and ethyl acetate. It can be added after being dissolved in a ketone, such as acetone or methyl ethyl ketone. Further, those which are difficult to dissolve in water or an organic solvent can be arbitrarily dispersed with an average particle diameter of 0.01 to 6 μm by high speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion or the like. For distribution,
Surface active agents such as anions and nonions, thickeners, latexes and the like can be added and dispersed. The addition amount is 10 ⁻⁶ to 10 ⁻¹ mol, and preferably 10 ⁻⁴ to 10 ⁻² mol per mol of silver halide.

In the present invention, the redox compound can be present in the silver halide emulsion layer, in a layer adjacent to the emulsion layer, in another layer via the adjacent layer, etc., but at least the emulsion layer closest to the support and / or Alternatively, it must be added to the adjacent hydrophilic colloid layer.

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. The amount of gelatin used in each layer is usually 0.1 to 2.0.
g / m ² . Crosslinking agent is 0.0 per gram gelatin
It is preferable to use 1 to 1 mmol.

In the present invention, a solid dispersion fine particle of a dye is contained between at least one silver halide emulsion layer and a support. As the dye that is solidified into fine particles,
It is preferable to use the compounds of the general formulas [7] to [12].

[0085]

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In the above general formulas [7] to [12], 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, Q ′ represents a heterocyclic group, 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 is 0, 1 or 2
And p ₂ represents 0 or 1. However, the general formula [7]
~ The dye represented by [12] is a carboxy group in the molecule,
It has at least one group selected from a sulfonamide group and a sulfamoyl group.

General formulas [7], [8] and

The acidic nuclei represented by A and A ′ in [9] are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolone, isoxazolone, indandione, pyrazolidine. Dione, oxazolidinedione, hydroxypyridone,
Examples include pyrazolopyridone.

General formula

The basic nucleus represented by B in [9] and [11] is preferably pyridine, quinoline,
Oxazole, benzoxazole, naphthoxazole, thiazole, benzothiazole, naphthothiazole, indolenine, pyrrole, indole.

Examples of the aryl group represented by Q in the general formulas [7] and [10] include a phenyl group and a naphthyl group. Further, as the heterocyclic group represented by Q and Q'in the general formulas [7], [10] and [12],
Examples thereof include pyridyl group, quinolyl group, isoquinolyl group, pyrrolyl group, pyrazolyl group, imidazolyl group, indolyl group, furyl group and 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 [7] to [12]. And the like. These substituents may be used in combination of two or more kinds. Preferred substituents have 1 to 1 carbon atoms.
8 alkyl group (for example, methyl group, ethyl group, t-butyl group, octyl group, 2-hydroxyethyl group, 2-methoxyethyl group, etc.), hydroxy group, cyano group, halogen atom, (for example, fluorine atom, chlorine atom) Etc.), an alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group,
2-hydroxyethoxy group, methylenedioxy group, butoxy group, etc.), substituted amino group (for example, dimethylamino group,
Diethylamino group, di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-ethyl-N
-Methanesulfonamidoethylamino group, morpholino group, piperidino group, pyrrolidino group, etc.), carboxy group,
A sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.) and a sulfamoyl group (eg, sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), and these substituents may be combined.

The electron withdrawing groups represented by X ₄ and Y ₁ in the general formulas [10] and [11] may be the same or different, and the σ _p value of the substituent constant Hammett (edited by Toshio Fujita, " Chemical Chemistry Special Issue No. 122, Structure-activity relationship of drug "described in pages 96 to 103 (1979) Nankodo etc.) is preferably 0.3 or more, for example, cyano group, alkoxycarbonyl group (eg, methoxycarbonyl group). , Ethoxycarbonyl group, butoxycarbonyl group,
Octyloxycarbonyl group etc.), aryloxycarbonyl group (eg 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-ethylsulfonamidocarbonyl group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, octylsulfonyl group, etc. ) And an arylsulfonyl group (for example, a phenylsulfonyl group, a 4-chlorosulfonyl group, etc.).

The methine groups represented by L ₁ , L ₂ and L ₃ in the general formulas [7] to [12] include those having a substituent, and the substituent includes, for example, an alkyl group having 1 to 6 carbon atoms. Group (eg, methyl group, ethyl group, hexyl group, etc.), aryl group (eg, phenyl group, tolyl group, 4-hydroxyphenyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), heterocyclic group (eg, pyridyl group) Group, furyl group, thienyl group etc.), substituted amino group (eg dimethylamino group, diethylamino group, anilino group etc.), alkylthio group (eg methylthio group etc.).

In the present invention, the general formulas [7] to [12]
Among the dyes represented by, a dye having at least one carboxyl group in the molecule is preferably used, more preferably a dye represented by the general formula [7], and particularly preferably in the general formula [7]. A dye in which Q is a furyl group.

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

[0094]

[Chemical 31]

[0095]

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[0096]

[Chemical 33]

Other preferable specific examples of the compounds represented by the general formulas [7] to [12] include, for example, Japanese Patent Application No.
No. 277011, pages 19-30. I-1 to N
o. I-30, II-1 to II-12, III-1 to III-8,
Examples thereof include IV-1 to IV-9, V-1 to 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-5-92716.
5-155350, 55-155351, 63
The methods described in, for example, No. 197943, No. 3-182743, and WO88 / 04794 can be used. Specifically, it can be manufactured using a fine dispersing machine such as a ball mill, a planetary mill, a vibration mill, a sand mill, a roller mill, a jet mill, and a disk impeller mill. When the compound in which 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 particulate solids by adding 1 to 2 equivalents of acid with respect to dissociation to lower the pH to make it weakly acidic, or a weak alkaline solution of the compound and an acidic aqueous solution at the same time while adjusting the pH. A dispersion of the compound can be obtained by a method of mixing to produce a fine particle solid.

The solid fine particle dispersion of the present invention may be used alone, or two or more kinds thereof 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 used as a mixture, they may be dispersed individually and then mixed, or they may be dispersed simultaneously.

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 preferable that a surfactant is allowed to coexist during or after the dispersion. Such surfactants include anionic surfactants,
Any of nonionic surfactants, cationic surfactants and amphoteric surfactants can be used, but preferably, for example, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, sulfosuccinates. , Sulfoalkyl polyoxyethylene alkyl phenyl ethers, N
Anionic surfactants such as -acyl-N-alkyl taurines and nonionic surfactants such as saponins, alkylene oxide derivatives, alkyl esters of sugars. The above-mentioned anionic surfactants are particularly preferable. Specific examples of the surfactant include Japanese Patent Application No.
The compounds 1 to 32 described on pages 46 to 32 of No. 277011 are mentioned, but not limited thereto.

The amount of the anionic activator and / or the nonionic activator used is not uniform depending on the kind of the activator or the conditions of the dispersion liquid of the dye, but usually the dye 1 is used.
The amount per g may be 0.1 mg to 2000 mg, preferably 0.5 mg to 1000 mg, and more preferably 1 mg to 500 mg.

The concentration of the dye in the dispersion is 0.01
It is used in an amount of about 50% by weight, preferably 0.1.
~ 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 and / or nonionic activators
Each of them may be used alone, or two or more of them may be combined together, and the activators of both may be combined.

The solid fine particle dispersion of the dye according to 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, particularly preferably 0.01 to 0.5 μm.
μm. The dispersion coefficient of the particle size distribution is preferably 50% 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 must be contained in at least one hydrophilic colloid layer between at least the support and the emulsion layer closest to the support. 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,
It can also be used as a base subbing 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 order to maximize the effect of improving linearity, the silver halide emulsion layer closest to the support and at least one hydrophilic layer between the silver halide emulsion layer and the support are hydrophilic. It is preferably contained in the colloid layer.

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 is 1 mg to 1 g, and more preferably ⁵ mg to 800 mg per 1 m ^{2 of} the photographic light-sensitive material. And particularly preferably 10 mg to 500 mg.

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, or 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. As the Se sensitizer, triphenylselenophosphine or the like is preferably used.

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

The reduction sensitizers include stannous salts, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

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

The average grain size of silver halide is preferably 0.7 μm or less, and more preferably 0.5 to 0.1 μm. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. What is particle size?
In the case where the particles are spherical or particles that can be approximated to spheres, this means particle diameter. If the particle is a cube, convert it to a sphere,
The diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE Mee).
s & T. H. By James: The theory o
f the photographic processes
s), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmillan")).

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

As the method 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.

It is also possible to use a method of forming grains in the presence of excess silver ions (so-called reverse mixing method). As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Thus, a silver halide emulsion having a nearly uniform grain size can be obtained.

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

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

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

In order to shorten the developing time, the present invention provides a total processing time (Dry to Dry) of 10 days from the time when the leading edge of the film is inserted into the automatic developing machine to the time when the film comes out of the drying zone when processing is performed using the automatic developing machine. It is preferably -60 seconds. The total processing time referred to here includes the total process time required for processing the black-and-white light-sensitive material, and specifically, for the processing, such as development, fixing, bleaching, washing, stabilizing, and drying. Time including all process time, that is, Dr
It is the time of y to Dry. More preferably, the total processing time (Dry to Dry) is 15 to 50 seconds.

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

The developing agents that can be used in the present invention include dihydroxybenzenes (eg, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone). 3-pyrazolidones (eg 1
-Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-
3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), pyrogallol,
Ascorbic acid, 1-aryl-3-pyrazolines (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-amino (Phenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.), transition metal complex salts (T
It is a complex salt of a transition metal such as i, V, Cr, Mn, Fe, Co, 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⁺ ,
It takes the form of complex salts such as Cr ²⁺ , Fe ²⁺ , and the ligands are:
Examples include aminopolycarboxylic acids and salts thereof such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA), and phosphoric acids and salts thereof such as hexametapolyphosphoric acid and tetrapolyphosphoric acid. ), Etc., can be used alone or in combination, a combination of 3-pyrazolidones and dihydroxybenzenes, or a combination of aminophenols and dihydroxybenzenes or a combination of 3-pyrazolidones and ascorbic acid, It is preferable to use a combination of aminophenols and ascorbic acid, a combination of 3-pyrazolidones and transition metal complex salts, and a combination of aminophenols and transition metal complex salts. Further, the developing agent is preferably used usually in an amount of 0.01 to 1.4 mol / liter.

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

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

Examples of sulfites and metabisulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l. Particularly preferably, it is at least 0.4 mol / liter.

If necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, 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, 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. By adjusting the pH of the developer to 8.5 to 10.9, a high-contrast image with 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 development processing is often used as one of the rapid processing methods for photosensitive materials in combination with silver salt stabilization processing using thiocyanate, and can be applied to such processing solutions.
In the case of such rapid processing, the effect of the present invention is particularly large.

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

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, etc. can be added to the fixing solution.

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

The developing solution may be a mixture of fixed 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 used after being diluted at the time of use, or may be used as it is.

In the development processing of the present invention, the development temperature can be set in the usual temperature range of 20 to 35 ° C. or in the high temperature processing range of 35 to 40 ° C.

[0134]

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

Example 1 (Preparation of silver halide emulsion A1) An average thickness of 0.05 mol% of silver chloride and the balance of silver bromide was 0.0 by a simultaneous mixing method.
A silver chlorobromide core particle having a 5 μm average diameter of 0.15 μm was prepared. At the time of mixing the core particles, K ₃ Rh (NO) ₄ (H ₂ O) was added in an amount of 8 × 10 ⁻⁸ mol per mol of silver, and K ₃ OsCl ₆ was added in an amount of 8 × 10 ⁻⁶ mol per mol of silver. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆
^Was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver.

Further, KI conversion was carried out using fine silver iodide grains, and the resulting emulsion had a core / shell type monodisperse (variation coefficient of 10%) silver chloroiodobromide (90 mol of silver chloride having an average diameter of 0.2 μm). %, 0.2 mol% silver iodobromide, and the balance silver bromide).

Then, the modified gelatin described in JP-A-2-280139 (a gelatin in which an amino group is substituted with phenylcarbamyl, for example, JP-A-2-280139)
No. 287 (3) page, exemplary compound G-8) was used for desalting. The EAg after desalting was 190 mV at 50 ° C.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the obtained emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added. To pH 5.6 and EAg123 mV, and sodium p-toluenethiosulfonate 1 × 10 ⁻³
Chloramine T 350m per mol silver after adding mol
g, 0.6 mg of inorganic sulfur (S ₈ ) and 6 mg of trichloroaurate were added, and chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained.

After the ripening, 2 × 10 ⁻³ mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 3 × 10 1-phenyl-5-mercaptotetrazole were used per mol of silver. ^-4 mol, 300 mg potassium iodide
Was added.

(Preparation of silver halide emulsions A2 and A3) With respect to the silver halide emulsion A1, the addition amount of the Rh complex was 9 × 10 ⁻⁸ mol / Ag and 10 × 10 ⁻⁸ mol / Ag, respectively.
Silver halide emulsions A2, A2
3 was prepared.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner containing hydrazine derivative) A gelatin subbing layer of the following Formulation 1 was prepared on a support with a gelatin content of 0.
5 g / m ^2, and a silver halide emulsion layer 1 of formula 2 was further coated thereon so that the silver amount was 1.5 g / m ² and the gelatin amount was 1.0 g / m ^2. Then, the silver halide emulsion layer 2 of the following formula 3 was adjusted to have a silver amount of 1.5 g / m ² and the gelatin amount of 1.0 g / m ^2, and the protective layer coating solution of the following formula 4 was further reduced to a gelatin amount of 0.1 g / m ² . Co-layer coating was carried out simultaneously so as to be 6 g / m ² .

On the opposite undercoat 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 thereon. The amount of gelatin in the backing protective layer of formula 7 is 0.4
g / m ² with the emulsion layer side and the curtain coating method.
A sample was obtained by simultaneous multilayer coating at a speed of 00 m / min.

Formulation 1 (gelatin undercoat layer composition) Gelatin 0.5 g / m ² Dye Exemplified AD-8 (ball mill dispersed into powder having a particle size of 0.1 μm) Amount shown in Table 1 Sodium polystyrene sulfonate 10 mg / m ² (average molecular weight 500000) Redox compound: Exemplified compound No. 22 (Dissolved in ethyl acetate and precipitated at high speed in a gelatin solution while removing ethyl acetate to precipitate crystals) Sodium-iso-amyl-n-decylsulfosuccinate Amount shown in Table 1 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 derivative Exemplified H-6 2 × 10 ⁻³ mol / Ag 1 mol Hydrazine derivative Exemplified H-7 2 × 10 ⁻³ mol / Ag 1 mol Dye Exemplified AD-8 Amount shown in Table 1 Amine compound AM- 1 40 mg / m ² redox compound: Exemplified compound No. The amount compound shown in Table 22 1 e 100mg / m ² Latex polymer f 0.5 g / m ² hardener g 5 mg / m ² Sodium - iso - amyl -n- decyl sulfosuccinate 0.7 mg / m ² Saponin 20mg / 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 (silver halide emulsion layer 2 composition) silver halide emulsion A1 silver Amount equivalent to 1.5 g / m ² Sensitizing dye d-1 0.5 mg / m ² Dodrazin derivative: Exemplified compound H-28 2 × 10 ⁻³ mol / Ag 1 mol Hydrazine derivative: Exemplified compound H-29 2 × 10 ^{− 3} mol / Ag 1 mol Amine 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 70000) 10 mg / m ² Latex polymer f 0.5 g / m ² Gelatin is phthalated gelatin, The coating solution pH was 4.8.

Formulation 4 (Emulsion protective layer composition) Gelatin 0.6 g / m ² Amine compound AM-1 20 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² Redox compound: Exemplified compound R- 21 Amount shown in Table 1 Matting agent: Spherical polymethylmethacrylate having an average particle size of 3.5 μm 25 mg / m ² Amorphous silica having 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 size 0.05 μm) 20 mg / m ² Hardener j 30 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² prescription 5 (backing layer composition) gelatin 0.6 g / m ² sodium-iso-amyl-n-decylsulfosuccinate 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 layer) Gelatin 0.4 g / m ² Matting agent: Monodisperse poly with an average particle size of 5 μm Methyl methacrylate 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 polystyreneate 10 mg / m ² Zinc hydroxide 50 mg / m ²

[0145]

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[0146]

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The obtained sample was brought into close contact with the step wedge, and a wavelength of 633n was obtained as a substitute characteristic of HeNe laser light.
Exposure using a high-intensity photometer equipped with a m filter, and using a processing solution having the following composition, a rapid processing automatic developing machine GR-26SR
(Manufactured by Konica Corp.) under the following treatment conditions.

Incidentally, in order to evaluate the fine halftone dot quality,
Exposure was performed using SG-747RU manufactured by Dainippon Screen Co., Ltd. with halftone dots (FM screening) having a random pattern of 8 μm, and then the same treatment as described above was performed.

(Preparation of Processing Agent) Developer Composition (per 1 liter of solution used) Diethylenetriamine pentaacetic acid / 5 sodium 1 g Sodium sulfite 42.5 g Hydroquinone 20 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 85 g potassium carbonate 55 g benzotriazole 0.2 g potassium bromide 4 g boric acid 8 g diethylene glycol 40 g 1-phenyl-5-mercaptotetrazole 0.03 g potassium sulfite 17.5 g 8-mercaptoadenine 0.078 g water and potassium hydroxide 1 liter To pH 10.4.

Fixer composition (per 1 liter of solution used) 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 (%) Aqueous solution) 25 ml sulfuric acid was used to adjust the pH of the working solution to 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 Digitally processed samples obtained Densitometer PDA-65
(Manufactured by Konica Corporation) was used to create a sensitometry curve, and gamma was measured.

Gamma (γ) is represented by the tangent of the straight line obtained at the densities of 0.1 and 3.0. In the table, the gamma value is 1
When it is 0 or more, a high-contrast image is obtained and it is shown that the photosensitive material is sufficiently practical.

Evaluation of Black Spots The developed sample films thus obtained were visually evaluated using a magnifying glass of 100 times, and in the order of less black spots, 5,
It was classified into 5 ranks of 4, 3, 2, 1. Ranks 1 and 2 are levels that are not practically desirable.

Evaluation of linearity In the SG-747RU, the exposure amount was changed by the halftone dot (FM screening) of a random pattern of 8 μm, and at the exposure amount where the point which should theoretically be 2% was actually reproduced to 2%. Then, what percentage theoretically should be 95% was measured in the halftone dot measurement mode of the Xrite 361 type densitometer. A value close to 95% is preferable.

Evaluation of exposure stability When the SG-747RU was exposed by changing the light amount at a halftone dot (FM screening) of a random pattern of 8 μm, the exposure amount at which the midpoint (target 50%) was 50%. When the double exposure amount was applied, the percentage of increase in the midpoint relative to 50% was measured.

The evaluation results are summarized in Table 1.

Prior to the above-mentioned evaluation, the emulsion layer coated alone (in the above-mentioned formulation except the other emulsion layer) was coated with a filter having a wavelength of 633 nm to obtain 10
^{When the} sensitivity was evaluated by the reciprocal of the exposure amount for giving a density of 4 by sensitometry with high illuminance of ^-5 seconds, the sensitivity of emulsion 2 was -12.5% with respect to emulsion 1.

[0158]

[Table 1]

Example 2 The following sensitizing dye d- was used instead of the sensitizing dyes d-1 and d-2.
A sample was prepared in the same manner as in Example 1 except that 3 and d-4 were used.

The obtained sample was brought into close contact with a step wedge, exposed with a high-intensity sensitometer equipped with a filter having a wavelength of 780 nm as a substitute characteristic of infrared laser light, and a processing solution having the following composition was used to carry out rapid processing. Machine GR-26SR (manufactured by Konica Corporation) was processed under the following processing conditions.

In order to evaluate the fine halftone dot quality,
Table 2 shows the results of the same treatments and evaluations as in Example 1 after exposure was carried out using MTR-1020 manufactured by Dainippon Screen Co., Ltd. with a halftone dot (FM screening) having a random pattern of 8 μm. .

[0162]

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[0163]

[Table 2]

From Tables 1 and 2, it can be seen that the samples of the present invention are excellent in linearity and exposure stability, have high contrast, and generate few black spots.

[0165]

According to the present invention, a silver halide photographic light-sensitive material having a high density and excellent linearity and gradation variability can be obtained.

Claims (2)

[Claims] 1. A support having at least two silver halide emulsion layers on one side, and containing a hydrazine derivative in at least one of the emulsion layers and / or a hydrophilic colloid layer adjacent thereto. Containing a redox compound that releases a development control agent by being oxidized into an emulsion layer closest to the substrate and / or an adjacent hydrophilic colloid layer, and is dispersed in a solid state between the emulsion layer closest to the support and the support. A silver halide photographic light-sensitive material having a layer containing the dye. 2. The silver halide photographic light-sensitive material according to claim 1, which has a gamma (γ) of 10 or more when processed with a developer having a pH of less than 11.0.