JPH0996885A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material for printing plate making which has high sensitivity and high gamma without causing any black spots, any processing fluctuation due to running and any dot fluctuation due to irregular exposure, and to provide an image forming method therefor. SOLUTION: This silver halide photographic sensitive material consists of a base body and a gelatin base coating layer, at least one silver halide emulsion layer and a hydrophilic colloid layer formed on the base body. The silver halide emulsion layer contains a redox compd. which can release a development inhibitor by oxidation. The silver halide particles in the silver halide emulsion layer are core/shell type silver halide particles each having two or more laminar structure. The core as the innermost layer contains at least one of Rh, Ru and Os with a higher content than in the shell part as the outer layer.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In recent years, a screening system for forming an image with a smaller halftone dot than before, such as high definition and FM screening, has begun to spread in the printing plate making scanner market. Such screening methods include:
An ultra-high contrast type photosensitive material which is easy to ride with small dot density is preferable, and further development is desired.

[0003] In the photographic material for printing plate making, many photographic techniques have been proposed as photographic techniques for obtaining a super-high contrast image reproduction. For example, US Pat. No. 4,269,929 discloses a silver halide photographic material containing a hydrazine derivative. It is known, and Japanese Patent Application Laid-Open No. 4-98239 discloses a silver halide photographic light-sensitive material containing a nucleation accelerator.

[0004] However, while these prior arts can provide a high contrast, they have a serious drawback that spot-like black spots called black spots are easily generated in unexposed portions.

Further, in the prior art, there is a problem that the movement of the halftone dots becomes large due to the process variation (development level) due to the fatigue of the developing solution during running or the exposure variation. In particular, in the recent high-definition and FM screening methods, since a minute halftone dot is used, a photosensitive material that does not move in response to fluctuations in developer level and exposure variation and that does not generate black spots is used. It was strongly desired.

[0006]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a silver halide photograph for printing plate making having high sensitivity, high gamma, no generation of black spots, and halftone fluctuation due to processing fluctuation due to running and exposure fluctuation. It is to provide a light-sensitive material, a silver halide photographic light-sensitive material for printing plate making which is suitable for high definition and FM screening, and an image forming method thereof.

[0007]

As a result of intensive studies, the present inventors have found that the above object can be solved by the following.

(1) A silver halide photographic material comprising a gelatin subbing layer on a support, at least one silver halide emulsion layer and a hydrophilic colloid layer,
A core / shell containing a redox compound capable of releasing a development inhibitor by being oxidized to the silver halide emulsion layer side, and the silver halide grains of the silver halide emulsion layer have a laminated structure of two or more layers. Type silver halide grains,
A halogen characterized by being a core / shell type silver halide grain in which at least one kind of metal compound containing Rh, Re, Ru, Os is present in the innermost layer core portion at a higher content than in the outer layer shell portion. Silver halide photographic light-sensitive material.

(2) The silver halide photographic light-sensitive material according to item (1), wherein the metal compound contained in the silver halide grains is a compound containing Rh.

(3) The silver halide photographic light-sensitive material as described in the item (1) or (2), characterized in that the constituent layer of the silver halide photographic light-sensitive material contains a hydrazine derivative.

(4) The silver halide photographic light-sensitive material according to item (3), wherein the silver halide photographic light-sensitive material constituent layer contains at least one solid disperse dye.

(5) A silver halide photograph according to item (4), which is characterized in that a high tone image having a gamma of 10 to 30 is formed by processing with a developing solution having a pH of 9.5 to 11.0. Image forming method of photosensitive material.

The present invention will be specifically described below.

Metal compounds containing Rh, Re, Ru, and Os used in the silver halide photographic light-sensitive material of the present invention are disclosed in JP-A-63-2042, JP-A-1-285941 and JP-A-1-285941.
It is added in the form of a water-soluble complex salt described in Nos. -20852 and 2-20855. Particularly preferred are hexacoordination complexes shown below.

[ML ⁶ ] ^-n (wherein M represents Rh, Re, Ru or Os, L represents a bridging ligand, and -n represents 0, 1, 2 or 3). In this case, the counter ion has no significance, and an ammonium or alkali metal ion is used. Further, preferred ligands include halide ligands, cyanide ligands,
Cyan oxide ligands, nitrosyl, thionitrosyl ligands and the like can be mentioned. Next, examples of specific complexes used in the present invention are shown. These metal complexes are powder or NaC
It is desirable to dissolve it together with 1 or KCl and add it to the halogen solution during grain formation.

[RhCl ₆ ] ^-3 , [RhCl ₅ (H
₂ O)] ^-2 , [RhBr ₅ (NO)] ^-2 , [RhCl
₅ (NS)] ^-2 , [RhCl ₄ (NO) (CN)] ⁻¹ ,
[RhCl ₄ (NO) (CN) ₄ ] ^-2 , [ReC
l ₆ ] ^-3 , [ReBr ₆ ] ^-3 , [ReCl ₅ (N
O)] ^-2 , [Re (NS) Br ₃ ] ^-2 , [Re (NO)
(CN) ₃ ] ^-2 , [RuCl ₆ ] ^-3 , [RuCl ₄ (H
₂ O) ₂ ] ^-1 , [RuCl ₅ (NO)] ^-2 , [RuBr
₅ (NS)] ^-2 , [OsCl ₆ ] ^-3 , [Os (NO) (C
N) _3] ^-2, silver halide grains in the ^-2 invention [Os (NS) Br ^5] may be doped with other heavy metal salts due to the high sensitivity. Especially K ₃ IrCl ₆ , K
Doping of an Ir salt or an Fe salt such as ₄ [Fe (CN) ₆ ] is advantageously performed.

Next, a core having a laminated structure according to the present invention /
The shell type emulsion will be described.

The laminated structure may have two or more layers and 10 or less layers,
Further, two or more layers and five or less layers are preferable. It is distinguished from the laminated structure referred to here by the difference in the content of the metal compound selected from Rh, Re, Ru or Os. The content of the metal compound forming this layer was 1 × with respect to 1 mol of silver.
The range of 10 ⁻⁹ to 1 × 10 ⁻⁵ mol is preferable, and further 1 ×
The range of 10 ⁻⁸ to 1 × 10 ⁻⁶ mol is preferable. Of these metals, Rh compounds are most preferred in the present invention. You may use these metal compounds in combination of 2 or more types. The content of the metal compound is highest in the innermost layer core in the core / shell particles as compared with the outermost shell by weight ratio, and the ratio of the amount of the innermost layer core: the amount of the outer layer shell is 1.1: 1 to 100: 1, and most preferably 1.2 to 20.

Next, the core / shell type silver halide grain having a laminated structure of the present invention will be described. The silver halide composition may be silver bromide, silver iodobromide, or a silver iodochlorobromide emulsion containing a small amount of silver chloride. The halogenated grains may be of any crystal type as long as they have the constitution of the present invention. For example, they may be single crystals such as cubic, octahedral, and tetrahedral, and may have various shapes. Twin particles may be used.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. The monodisperse referred to here, when measuring the average particle diameter by a conventional method,
Silver halide grains in which at least 95% of the grains by number or weight are within ± 40%, preferably within ± 30% of the average grain size.

The crystal structure of silver halide may have different silver halide compositions inside and outside. For example, a core portion of high silver iodide is coated with a shell layer of low silver iodide to form a clear multilayer. It may be a core / shell type monodisperse emulsion having a structure.

The method for producing the above core / shell type emulsion is known, and is described in, for example, J. Photo. Sci, 24.198. (1
976), U.S. Pat. Nos. 2,592,250 and 3,50
5,068, 4,210,450, 4,44
4,877 or JP-A-60-143331 can be referred to.

The method for producing the above-mentioned monodisperse emulsion is known, and is described in, for example, J. Photo. Sci, 12.242-251, (19
63), JP-A-48-36890, and JP-A-52-1636.
No. 4, No. 55-142329, No. 58-49938
No. 1,413,748, U.S. Pat.
No. 4,628, 3,655,394 and the like.

For the emulsion used in the silver halide photographic light-sensitive material of the present invention, for example, a seed crystal is used as a method for obtaining the above monodisperse emulsion, and the seed crystal is used as a growth nucleus to supply silver ions and halide ions. A grown emulsion may be used.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be tabular grains having an aspect ratio (ratio of grain size / grain thickness) of 3 or more.

The redox compound used in the present invention on the silver halide emulsion layer side and capable of releasing a development inhibitor by being oxidized will be described.

The redox compound of the present invention comprises hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones as redox groups,
It has hydrazines, reductones, α-aminoketones and the like.

Preferred redox compounds are compounds having a --NHNH-- group as a redox group and the following general formulas [I], [II], [III], [IV], [V] or [VI].
Is a compound represented by.

[0029]

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[0030]

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The compound having a --NHNH-- group as a redox group is represented by the following general formula [RE-a] or [RE-
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. Or, represents an optionally substituted alkyl group. Examples of the aryl group represented by T and V include a benzene ring and a naphthalene ring, and these rings may be substituted with various substituents. A preferable substituent is a linear or branched alkyl group (preferably Are those having 2 to 20 carbon atoms such as methyl, ethyl, isopropyl group, dodecyl group, etc., alkoxy groups (preferably those having 2 to 21 carbon atoms, such as methoxy group, ethoxy group, etc.), aliphatic acylamino groups (preferably Those having an alkyl group having 2 to 21 carbon atoms, such as acetylamino group, heptylamino group, etc., and aromatic acylamino groups, and the like. In addition to these, substituted or unsubstituted aromatic rings such as those described above are also included. -CONH-, -O-,-
It also includes those linked by a linking group such as SO ₂ NH-, -NHCONH-, and -CH ₂ CHN-. As PUG, 5-nitroindazole, 4-nitroindazole, 1
-Phenyltetrazole, 1- (3-sulfophenyl)
Tetrazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 5-nitroimidazole, 4
-Nitroimidazole and the like. These development inhibiting compounds contain N or S at the CO site of T-NHNH-CO-.
Can be connected directly via a heteroatom such as, or via an alkylene, phenylene, aralkylene, or aryl group, and further via a heteroatom such as N or S. Other,
A hydroquinone compound having a ballast group and a development-inhibiting group such as triazole, indazole, imidazole, thiazole or thiadiazole introduced therein can also be used. For example, 2- (dodecylethylene oxide thiopropionamide) -5- (5-nitroindazole-
2-yl) hydroquinone, 2- (stearylamide)
-5- (1-phenyltetrazole-5-thio) hydroquinone, 2- (2,4-di-t-amylphenoxypropionamide) -5- (5-nitrotriazole-
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.

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 addition of the above redox compound, alcohols such as methanol and ethanol, glycols such as ethylene glycol, triethylene glycol, propylene glycol, ethers, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, esters such as ethyl acetate, acetone and It can be added after being dissolved in ketones such as 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 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 the redox compound added may be from 10 ^-6 to 10 ^-1 mol, and preferably from 10 ^-4 to 10 ^-2 mol, per 1 mol of silver halide.

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

[0036]

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[0037]

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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 redox compounds represented by the above general formulas [I] to [VI] will be described below.

In the general formulas [I] to [VI], R ₁ represents an alkyl group, an aryl group or a heterocyclic group. R ₂ and R ₃ represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group. R ₄ represents a hydrogen atom. R ₅ to R ₉ 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 represents an atomic group necessary for forming a 5- or 6-membered heterocycle. W is N (R
₁₀ ) R ₁₁ or OH, wherein R ₁₀ and R ₁₁ are a hydrogen atom,
It represents an alkyl group, an aryl group or a heterocyclic group. COUP
Represents a coupler residue capable of causing a coupling reaction with an oxidized form of an aromatic primary amine developing agent, and * represents a coupling site of the coupler. Tm represents a timing group.
m ₁ and p ₁ represent an integer of 0 to 3. q ₁ represents an integer of 0 to 4. n represents 0 or 1. PUG represents a development inhibitor.

In the above general formulas [I] to [VI], R ₁
Examples of the alkyl group, aryl group and heterocyclic group represented by R _{5 to} R ₁₁ include a methyl group, p-methoxyphenyl group and pyridyl group. Among the acyl group, carbamoyl group, cyano group, nitro group, sulfonyl group, aryl group, oxalyl group, heterocyclic group, alkoxycarbonyl group and aryloxycarbonyl group represented by R ₂ and R ₃ , an acyl group and carbamoyl group are preferable. 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, for example, a halogen atom (a chlorine atom, a bromine atom, etc.), an alkyl group (for example, a 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) ), An aryl group (for example, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), an alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group, butoxy group, etc.), an aryloxy group (for example, 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 ( For example, a methanesulfonylamino group, Zen sulfonylamino 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.) An alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), a sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), an acyl group (eg, Acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), hydroxyl group, nitro group, imide group (for example, phthalimido group, etc.),
Heterocyclic groups (for example, a pyridyl group, a benzimidazolyl group, a benzothiazolyl group, a benzoxazolyl group, etc.) are exemplified. Examples of the coupler residue represented by COUP include the following. Examples of cyan coupler residues include phenol couplers and naphthol couplers. Examples of magenta couplers include 5-pyrazolone couplers, pyrazolone couplers, cyanoacetylcoumarone couplers, open chain acylacetonitrile couplers, and indazolone couplers. Examples of the yellow coupler residue include a benzoylacetanilide coupler, a pivaloylacetanilide coupler, and a malondianilide coupler.
Colorless coupler residues include open-chain or cyclic active methylene compounds (eg, indanone, cyclopentanone, malonic acid diester, imidazolinone, oxazolinone, thiazolinone, etc.).

Further, among the coupler residues represented by COUP, those which are preferably used in the present invention can be represented by the general formula (Coup-1) to the general formula (Coup-8).

[0042]

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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.

[0044]

[Chemical 6]

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 respectively represent An aliphatic group,
Represents an aromatic group or a heterocyclic group. One of R ₂₀ and R ₂₁ may be a hydrogen atom. a is an integer of 1 to 4, b is 0
Represents an integer of 5; When a and b are plural, R ₁₈ may be the same or different, and R ₁₉ may be the same or different.

[0046]

[Chemical 7]

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.

[0048]

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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.

[0050]

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R ₂₇ and R ₂₈ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

The timing group represented by Tm is preferably —OCH ₂ — or another divalent timing group, for example, US Pat. Nos. 4,248,962 and 4,409,3.
No. 23, or No. 3,674,478, Research
Disclosure, No. No. 21228 (198
December, 1), or those described in JP-A-57-56837, JP-A-4-438 and the like.

Preferred development inhibitors for PUG are, for example, US Pat. No. 4,477,563 and JP-A-60-2186.
No. 44, No. 60-221750, No. 60-23365.
No. 0, or the development inhibitor described in No. 61-11743.

The general formula [I] used in the present invention is as follows.
Specific examples of the compound represented by [VI] are listed below, but the present invention is not limited thereto.

[0055]

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[0056]

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[0057]

[Chemical 12]

[0058]

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[0059]

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[0060]

[Chemical 15]

[0061]

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[0062]

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General formula [I] preferably used in the present invention
The compound represented by [VI] 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 [I] to [VI] are used by dissolving them in a suitable water-miscible organic solvent such as alcohols, ketones, dimethylsulfoxide, dimethylformamide and methylcellosolve. it can. Also, it can be added as an emulsified dispersion using a known oil. Further, the compound powder can be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or ultrasonic waves by a method known as a solid dispersion method.

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

The silver halide photographic light-sensitive material of the present invention exhibits a particularly remarkable effect when a hydrazine compound is used as a contrast adjusting agent in the constituent layers. The hydrazine compound that can be used in the present invention is preferably a compound represented by the following general formula [H].

[0067]

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

Among the compounds represented by the general formula [H], the compound represented by the following general formula [Ha] is more preferable.

[0070]

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In the formula, R ¹ is an aliphatic group (eg octyl group, decyl group), aromatic group (eg phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or heterocyclic group (eg pyridyl group, thienyl group, Represents a furyl group),
These groups are preferably further substituted with an appropriate substituent. Further, R ¹ preferably contains at least one ballast group or silver halide adsorption promoting group.

The anti-diffusion group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group is an alkyl group having 8 or more carbon atoms and relatively inert to photographic properties. , Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like. The silver halide adsorption promoting group is thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, or JP-A-64-9.
No. 0439, for example. 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 preferably both are 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, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group,
Represents a carbamoyl group or an oxycarbonyl group. Most preferred R ² is —COOR ₃ group and —CON (R ₄ ).
(R ₅₎ groups (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).

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

[0075]

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[0076]

[Chemical 21]

[0077]

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[0078]

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[0079]

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

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
It can be synthesized by the method described in 9,248.

The addition amount may be any amount for making the contrast high (contrast adjustment 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 kind of the inhibitor, etc. From 10 ^-6 to 10 ^-1 per mol of silver halide
It is in the range of moles, preferably in the range of 10 ^-5 to 10 ^-2 moles. The hydrazine compound used in the present invention can be used in any layer as long as it is on the silver halide emulsion layer side, but it is preferably used in the silver halide emulsion layer or its adjacent layer. The optimum 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 mol per mol of silver halide. Is preferable,
Particularly, the range of 10 ⁻⁵ to 10 ⁻² mol is preferable.

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].

[0084]

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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,
Represents a substituted aryl group. R ₁₁ , R ₁₂ and R ₁₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. 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.

[0086]

[Chemical formula 26]

[0087]

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[0088]

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[0089]

[Chemical 29]

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.

[0091]

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[0092]

[Chemical 31]

Specific examples of other preferred nucleation promoting compounds include the compounds (2-1) to (2-20) and 6-2587 described in JP-A-6-258751.
The compounds of (3-1) to (3-6) described in No. 51.
The nucleation accelerator used in the present invention can be used in any layer as long as it is on the side of the silver halide emulsion layer, but is preferably used in the silver halide emulsion layer or a layer adjacent thereto. The optimum addition amount varies depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of inhibitor, etc., but is generally 10 ^-6 to 10 ^-1 per mol of silver halide. A molar range is preferred, especially 10 ^-5 to 1
A range of 0 ^-2 mol is preferred.

The silver halide photographic light-sensitive material of the present invention contains at least one solid disperse dye in its constituent layers. Various dyes are used in silver halide photographic light-sensitive materials for the purpose of improving sharpness and safelight property.

Since this dye is water-soluble and its photographic properties such as sensitivity and gamma are deteriorated due to its diffusibility, a fine particle solid dispersion method of dye has been recently used.

Compounds represented by the following general formulas [1] to [6] are preferably used as the dye in the solid fine particle dispersion method which can be used in the present invention.

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In the formula, A and A'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.
Represent, X_FourAnd Y₁Can be the same or different, that
Each represents an electron-withdrawing group, L ₁, L₂And L_ThreeAre each
Represents a methine group. m₂Represents 0 or 1, t is 0, 1, or
Represents 2 and p₂Represents 0 or 1. However, the general formula
The dyes represented by [I] to [VI] are carboxy in the molecule.
Group, sulfonamide group and sulfamoyl group
Has at least one group.

The acidic nuclei represented by A and A'in the general formulas [1] to [3] are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolone, Examples thereof include isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone and 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 and the like. Is mentioned.

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. , A furyl group, a thienyl group and the like. The aryl group and the heterocyclic group include those having a substituent, and examples of the substituent include those exemplified as the substituents such as the amino group and the heterocyclic group of the compounds of the above general formulas [1] to [5]. In addition, these substituents may have two or more kinds in combination.

Preferred substituents are alkyl groups having 1 to 8 carbon atoms (for example, methyl, ethyl, t-butyl, octyl, 2-hydroxyethyl, 2-methoxyethyl groups, etc.), hydroxy groups, cyano groups, halogen atoms ( For example, a fluorine atom, a chlorine atom, etc., an alkoxy group having 1 to 6 carbon atoms (eg, methoxy, ethoxy, 2-hydroxyethoxy, methylenedioxy, butoxy group, etc.), a substituted amino group (eg, dimethylamino, diethylamino, di (n −
(Butyl) amino, N-ethyl-N-hydroxyethylamino, N-ethyl-N-methanesulfonamidoethylamino, morpholino, piperidino, pyrrolidino group, etc.), carboxy group, sulfonamide group (for example, methanesulfonamide, benzenesulfonamide) Group, etc.), a sulfamoyl group (eg, sulfamoyl, methylsulfamoyl,
Phenylsulfamoyl group), and these substituents may be combined.

The electron withdrawing groups represented by X ₄ and Y ₁ in the general formulas [4] and [5] may be the same or different,
Substituent constant Hammett's σp value (Toshio Fujita eds., "Chemical Region Special Issue No. 122, Structure-Activity Relationship of Drugs", 96-1
Page 03 (1979), Nankodo, and the like. ) Is preferably 0.3 or more, for example, a cyano group, an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl, 4-hydroxyphenoxycarbonyl group). Etc.), carbamoyl group (for example, carbamoyl, dimethylcarbamoyl, phenylcarbamoyl, 4-carboxyphenylcarbamoyl group, etc.), acyl group (for example, methylcarbonyl, ethylcarbonyl, butylcarbonyl, phenylcarbonyl, 4-ethylsulfonamidocarbonyl group, etc.), Alkylsulfonyl group (eg methylsulfonyl, ethylsulfonyl group, butylsulfonyl group, octylsulfonyl group, etc.), arylsulfonyl group (eg phenyl Ruhoniru group, 4-chlorosulfonyl group, etc.).

L ₁ , L ₂ and L _{3 of the} general formulas [1] to [5]
The methine group represented by includes those having a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, hexyl group, etc.), an aryl group (eg, phenyl, tolyl, 4 -Hydroxyphenyl group),
Aralkyl groups (eg, benzyl, phenethyl groups, etc.), heterocyclic groups (eg, pyridyl, furyl, thienyl groups, etc.), substituted amino groups (eg, dimethylamino, diethylamino,
And an alkylthio group (eg, methylthio group).

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 that are preferably used are shown below, but the dyes are not limited to these.

[0105]

[Chemical 33]

[0106]

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[0107]

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Other preferable specific examples of the compounds represented by the general formulas [1] to [6] include Japanese Patent Application No. 5-27.
No. 7011, pages 19 to 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 Nos. 52-92716 and 55-55.
-155350, 55-155351, 63-
No. 197943, No. 3-182743, World Patent W
The method described in O88 / 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,
Dispersion of the compound by lowering the pH to weakly acidic to precipitate a fine particle solid, or by simultaneously mixing a weak alkaline solution of the compound and an acidic aqueous solution while adjusting the pH to produce a fine particle solid. You can get things.

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 used in the present invention is produced in the presence of an aqueous dispersion medium, it is preferable to allow a surfactant to coexist during or after the dispersion.
As such a surfactant, an anionic surfactant,
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 and alkyl esters of sugars. Particularly preferred are the above-mentioned anionic surfactants. Specific examples of the surfactant include, for example, Japanese Patent Application No. 5-
The compounds 1 to 32 described in No. 277011, pp. 46 to 32 are mentioned, but not limited thereto.

The amount of the anionic activator and / or the nonionic activator to be used is not uniform depending on the kind of the activator or the conditions of the dispersion liquid of the dye, but usually 0.1 to 2000 mg is preferable per 1 g of the dye. , More preferably 0.5 to 1000 mg, particularly preferably 1 to 50
0 mg may be sufficient.

The concentration of the dye in the dispersion is from 0.01 to
It is preferably used so as to be 50% by weight, and more preferably 0.1 to 30% by weight. The surfactant may be added at the position where it is added before the dispersion of the dye is started, and if necessary, it may be further added to the dye dispersion after the dispersion is completed. These anionic activators and / or nonionic activators may be used alone or in combination of two or more.

The solid fine particle dispersion used in the present invention is preferably dispersed so as to have an average particle size of 0.01 to 5 μ, more preferably 0.01 to 1 μ, and particularly preferably 0.01. Is 0.5 μ. The coefficient of variation 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 The solid fine particle dispersion used in the present invention is a hydrophilic colloid used as a binder of a photographic constituent layer before the start of dispersion or after the end of dispersion. It can be added. It is advantageous to use gelatin as the hydrophilic colloid, but other than that, for example, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, and phthalated gelatin, and graft of gelatin with a monomer having a polymerizable ethylene group. Polymers, carboxymethyl cellulose, hydroxymethyl cellulose, cellulose derivatives such as cellulose sulfate, polyvinyl alcohol,
Partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide, poly-
Synthetic hydrophilic polymers such as N-vinylpyrrolidone and polymethacrylic acid, agar, gum arabic, alginic acid, albumin, casein and the like can be used. These may be used in combination of two or more.

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 preferably added so as to be 2%, more preferably 0.5 to 8%.

The solid fine particle dispersion used in the present invention is
It can also be used as a layer constituting a photographic material such as a silver halide emulsion layer, an emulsion layer upper layer, an emulsion layer lower layer, a protective layer, a support undercoat layer, a backing layer and the like. 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. To enhance the effect of improving the safelight property,
It is preferably added to the layer above the emulsion layer.

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

In the present invention, photosensitive and non-photosensitive emulsion layers and non-emulsion layers (hydrophilic colloid layer, hydrophobic polymer layer)
It may also contain a dye dispersed in solid form.
It may be contained in any layer on the side opposite to the emulsion layer with respect to the support. A water-soluble dye may be contained in any layer. The addition amount of the dye dispersed in a solid state in the present invention is preferably an amount that can obtain an absorbance of 0.001 to 2.0 in at least a part of the wavelength region of the light source used for exposure, and particularly preferably. The above absorbance is 0.005
The amount is 1.5. Further, in the present invention, dyes having other absorption wavelengths can be used together in any layer.

The silver halide photographic light-sensitive material of the present invention is most effectively used as an output light-sensitive material, and the light source is an Ar laser, He-Ne laser, red laser diode, infrared semiconductor laser, red LED. Although a laser is typical, any other laser such as a blue laser such as a He—Cd laser can be used. Further, the effect of the present invention is not limited to the laser output sensitive material,
It is also effective in applications such as shooting sensitive materials and return sensitive materials.

The silver halide photographic light-sensitive material of the present invention has a pH value of
Is developed with a developing solution of 9.5 to 11.0 to form a high-contrast image with gamma of 10 to 30.

A particularly preferred pH is in the range of 9.5 to 10.5. In the present invention, when the pH is 9.5 or less, a high-contrast image cannot be formed, and when the pH is 11.0 or more, fog is generated in the unexposed portion and the image cannot be used.

The developing agents that can be used in the image forming method of the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,
5-dimethylhydroquinone, etc., 3-pyrazolidones (for example, 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)- Three
-Aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-
Methylphenyl) -3-aminopyrazoline, etc.), transition metal complex salts (Ti, V, Cr, Mn, Fe, Co, Ni,
It is a complex salt of a transition metal such as Cu, and these may be in a form having a reducing power for use as a developing solution.
i ³⁺ , V ²⁺ , Cr ²⁺ , Fe ^{2+ and the} like are in the form of complex salts, and as the ligand, an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and its Examples thereof include salts, phosphoric acids such as hexametapolyphosphoric acid and tetrapolyphosphoric acid, and salts thereof. ) Or the like can be used alone or in combination, but a combination of 3-pyrazolidones and dihydroxybenzenes, a combination of aminophenols and dihydroxybenzenes or a combination of 3-pyrazolidones and ascorbic acid, amino It can be used in a combination of phenols 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.

Sulfite used as a preservative in the developer,
Examples of metabisulfite include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l. Particularly preferably, it is at least 0.4 mol / liter. If necessary, the developer may contain an alkali agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg, carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.), and a solubilizing agent. Agents (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, defoamers, antifoggants Agents (for example, halides such as potassium bromide, sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (for example ethylenediaminetetraacetic acid or its alkali metal salts) , Nitrilotriacetate, polyphosphate, etc., development accelerators (eg Country patent 2,304,025
, A compound described in JP-B-47-45541), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof), or an antifoaming agent. The pH of the developer is preferably adjusted to 8.5 to 12.0, particularly preferably 9.0 to 10.9.

The silver halide photographic light-sensitive material of the present invention may be developed with a developer containing no dihydroxybenzene compound. In this case, it is preferable to contain a compound represented by the following general formula (A).

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In the formula, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k is 1, X is -CO-
Or represents -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

In this case, a compound represented by the following general formula (Aa) in which R ₁ and R ₂ are bonded to each other to form a ring is preferable.

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In the formula, R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, It represents an amide group or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents O, S or NR ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

The alkyl group in formula (A) or (Aa) is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, a lower alkoxy group is preferable as the alkoxy group, a phenyl group or a naphthyl group is preferable as the aryl group, and these groups may have a substituent. Often, the substitutable group includes a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, a sulfonamide group and the like as a preferable substituent.

Specific examples of the compound represented by the general formula (A) or the general formula (Aa) are shown below.

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[0134]

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These compounds are typically ascorbic acid, erythorbic acid or derivatives derived from them, and they are available as commercial products or can be easily synthesized by known synthetic methods.

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 that acts as a hardening agent, such as aluminum chloride, aluminum sulfate, and potassium alum, can be added to the fixing solution.

If desired, the fixer may contain preservatives (eg sulfite, bisulfite), pH buffer (eg acetic acid), p.
Compounds such as an H adjuster (for example, sulfuric acid) and a chelating agent capable of softening water can be included. In the developing process, washing is performed after fixing, but the washing layer may be a system in which fresh water is supplied at a rate of several liters per minute depending on the treatment, or washing water is circulated, chemicals, filters, ozone, light, etc. And a method of reusing the washing bath as a stabilizing bath containing a stabilizing agent and replenishing a small amount of the stabilizing solution according to the amount to be treated.

The mother liquor or replenisher for the developing solution, fixing solution, stabilizing solution is usually supplied by diluting the working solution or the concentrated solution immediately before. The stock of the mother liquor and the replenisher may be in the form of a working solution or a concentrated solution, a viscous liquid in a semi-kneaded state having a high viscosity, or a system in which a simple substance or a mixture of solid components is dissolved at the time of use. When a mixture is used, a method in which components that are difficult to react with each other are adjacently packed in layers and then vacuum-packaged, and then opened and dissolved at the time of use, or a method of tableting can be used. In particular, the method of adding the tablet-formed product to the dissolution layer or the direct treatment layer is a workability,
The method is extremely excellent in terms of space saving and preservability, and can be used particularly preferably. In the development processing of the present invention, the development temperature can be set within a normal temperature range of 20 to 50 ° C.

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

According to the present invention, in order to shorten the developing time, the total processing time (Dry to Dry) from the insertion of the leading edge of the film into the automatic developing machine until the film comes out from the drying zone is 10 when the processing is performed by using the automatic developing machine. It is preferably -60 seconds.

The halogen composition of the silver halide photographic light-sensitive material of the present invention is preferably silver chlorobromide containing 60 mol% or more of silver chloride or silver chloroiodobromide containing 60 mol% or more of silver chloride. .

The average grain size of silver halide is preferably 0.7 μm or less, and more preferably 0.5 to 0.1 μm. Average particle size is a term that is commonly used by professionals in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or can be approximated to a sphere. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for obtaining the average particle size, see (C. E. K. Mees & T. H. James.
Written by: the theory of the photo
graphic process), 3rd edition, 36-4
See page 3 (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. Further, it is preferable that the particle size distribution is narrow, and in particular, the total number of particles is 9% within a particle size range of ± 40% of the average particle size.
A so-called monodisperse emulsion containing 0%, preferably 95%, is preferable.

As the method for reacting the soluble silver salt of the silver halide emulsion with the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in the liquid phase in which silver halide is produced as one form of the double jet method
Can be kept constant, that is, a so-called controlled double jet method can be used. According to this method,
A silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Regarding Laminate Structure The silver halide grains used in the present invention are grains having a laminate structure. The laminated structure is preferably 2 layers or more and 10 layers or less, more preferably 2 layers or more and 5 layers or less. It is distinguished from the laminated structure here by the different doping ratio of the metal selected from Rh, Re, Ru and Os. This content is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁵ mol, more preferably 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁶ mol, per mol of silver (forming the layer). Ranges are preferred.

In the present invention, Rh is most preferable as the metal compound. The metal compounds may be used alone or in combination of two or more.

In the present invention, the silver halide grain has a particle size of
Multiple types of particles with different sensitivity, crystal habit, photosensitizing wavelength, halogen composition, monodispersity, amount and type of doping agent, potential, pH, production conditions such as desalting method, surface state, chemical sensitization state, etc. Can be used together. In that case, these silver halide grains may be contained in the same layer, or may be contained in a plurality of different layers.

For details of the silver halide emulsion and its preparation method, see RD. No. No. 17643, pages 22 to 23 (December 1978) or cited.

For the silver halide photographic light-sensitive material of the present invention, generally known sulfur sensitization, Se, Te sensitization, reduction sensitization and noble metal sensitization methods are appropriately selected and used alone or in combination. Can be sensitized. Note that chemical sensitization may not be performed.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, rhodanins and polysulfide compounds can be used in addition to the sulfur compounds contained in gelatin. As the Se sensitizer, triphenylselenophosphine or the like is preferably used. A wide variety of selenium compounds can be used as the selenium sensitizer. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N,
N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-
Heptafluoropropylcarbonylselenourea, N,
N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.) , Selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.),
Selenides (triphenylphosphine selenide,
Diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas,
These are selenoamides, selenoketones, and selenides.

The temperature of chemical ripening using a selenium sensitizer is 4
The range is preferably from 0 to 90 ° C, more preferably from 45 ° C to 80 ° C. The pH is 4-9 and the pAg is 6
The range of -9.5 is preferable. Solid dispersion As a method of adding these sensitizers, if they are water-soluble, they can be added as they are, but if they are poorly soluble in water, various methods can be adopted. For example, there is a method in which a sulfur sensitizer and / or a selenium sensitizer and / or a tellurium sensitizer are sufficiently mixed in advance with a gelatin solution and then added. Alternatively, a method of dissolving in a low-boiling organic solvent in which a sensitizer is dissolved and then emulsifying and dispersing in the presence of a surfactant to add the sensitizer can also be adopted. In this method, it is preferable to remove the low-boiling organic solvent after emulsification and dispersion. Further, JP-A-4-
According to the method disclosed in No. 140739, it is also possible to add the compound in the form of an emulsified dispersion of a mixed solution with a water-insoluble and organic solvent-soluble polymer. Among the noble metal sensitization methods, the gold sensitization method is a typical example of the noble metal sensitization methods in which a method of arbitrarily dispersing the average particle size from 0.01 to 6 μ by high-speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion or the like can be adopted. In this case, a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained.

As the reduction sensitizer, stannous salts, amines,
Formamidinesulfinic acid, silane compounds and the like can be used. In the present invention, an oxidizing agent for silver can be used in the process for producing the light-sensitive material. As an oxidant that can be used, for example, as an inorganic oxidant,
Hydrogen peroxide (water), hydrogen peroxide adduct (eg NaB
O ₂ · H ₂ O ₂ · 3H ₂ O, 2NaCO ₃ · 3H ₂ O ₂ , Na ₄
P ₂ O ₇ · 2H ₂ O ₂ , 2Na ₂ SO ₄ · H ₂ O ₂ · 2H ₂ O, etc., peroxy acid salts (eg K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ ,
K ₄ P ₂ O ₈ ), peroxy complex compounds (for example, K
₂ [Ti (O ₂ ) C ₂ O ₄ ] .3H ₂ O, 4K ₂ SO ₄ .Ti
(O ₂ ) ・ OH ・ SO ₄・ 2H ₂ O, Na ₂ VO (O ₂ )
_{(C 2 O 4) 2 ·} 6H 2 O , etc.), etc. permanganate (e.g. KMnO _4), chromates (e.g., K ₂ CrO)
And oxyacid salts, halogen elements such as iodine and bromine, perhalogen acid salts (for example, potassium periodate), high-valent metal salts (for example, potassium ferricyanide), and thiosulfonates. Further, as the organic oxidant,
Examples thereof include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release an active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B, etc.).

Particularly preferred oxidizing agents are ozone, hydrogen peroxide and its adducts, inorganic oxidizing agents of halogen elements, quinones and organic oxidizing agents which release active halogen.

The addition amount of the oxidizing agent is preferably 10 ^-7 to 10 ^-1 mol per mol of silver halide. More preferred is 10 ^-6 to 10 ^-2 mol, and particularly preferred is 10 ^-5 to 10 ^-3 mol.

The silver halide photographic light-sensitive material of the present invention comprises
A dispersion of a water-insoluble or sparingly soluble synthetic polymer may be included for the purposes of improving dimensional stability, reducing silver sludge, and the like. For example, alkyl (meth) acrylate, alkoxy acryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene alone or in combination, or acrylic acid, A polymer having a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid or the like as a monomer component can be used. A monomer having a plurality of ethylenically unsaturated groups may be used as a monomer component. These monomers may have a water-soluble group such as a hydroxyl group, a sulfone group, a carboxyl group and an amide group, and a primary to quaternary amino group,
Phosphonium groups, aliphatic, aromatic, -NR ₁ NR ₂ -R ₃
(R ₁ , R ₂ and R ₃ may be different from each other, a hydrogen atom, an aliphatic group, an aromatic group, a sulfinic acid residue, a carbonyl group, an oxalyl group, a carbamoyl group, an amino group, a sulfonyl group and a sulfoxy group. , An iminomethylene group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group and the like), a cation group or the like. As a synthesis method, in addition to a usual synthesis method, polymerization may be performed in the presence of a water-soluble organic substance such as gelatin or polyvinyl alcohols. After completion of the synthesis, shelling may be performed with gelatin or a silane coupling agent.

Various other additives can be used in the light-sensitive material of the present invention. Examples thereof include desensitizers, plasticizers, slip agents, development accelerators, oils and colloidal silica. For these additives and the aforementioned additives,
Specifically, RD. No. 17643, pages 22-31,
And the like can be used.

In the light-sensitive material used in the present invention, the emulsion layer may be a single layer or a multi-layer consisting of two or more layers. In the case of a multilayer, an intermediate layer or the like may be provided therebetween. Further, it may have a non-photosensitive emulsion. As the non-emulsion layer, any number of layers may be provided as necessary between the support and the emulsion layer closest to the support, between a plurality of emulsion layers, and outside the emulsion layer farthest from the support. Can be. In these layers, a water-soluble or water-insoluble dye, an imagewise or non-imagewise development modifier (inhibitor or accelerator), a contrast modifier, a physical property modifier, etc., dissolved in an aqueous solution or an organic solvent, Alternatively, it may be contained in the form of being dispersed in the form of solid fine particles (which may or may not be protected by oil).

The hydrophilic colloid layer of the silver halide photographic light-sensitive material according to the present invention is specifically a non-light-sensitive silver halide emulsion layer which is light-sensitive or has substantially no photographic sensitivity,
It refers to all the constituent layers of the silver halide photographic light-sensitive material such as a protective layer, an undercoat layer, an intermediate layer, a filter layer, an ultraviolet absorbing layer, an antihalation layer and an antistatic layer.

[0159]

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

Example 1 (Preparation of Silver Halide Emulsion A1) An average particle size of 0.0 mol% of silver chloride was 70 mol% and the balance was silver bromide by the simultaneous mixing method.
9μ silver chlorobromide core particles were prepared. In the presence of the metal complex shown in Table 1 at the time of mixing the core particles, at 40 ° C.,
While maintaining the pH at 3.0 and the silver potential (EAg) at 165 mV, the silver nitrate aqueous solution and the water-soluble halide solution were simultaneously mixed. EAg was lowered to 125 mV with sodium chloride to the obtained core particles, and a shell was attached using a double-mix method. At that time, K ₂ IrCl ₆ was added to the halide solution in an amount of 3 × 10 ^-7 mol per mol of silver and the metal complex shown in Table 1.

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 (silver chloride 70 The emulsion was a cubic crystal consisting of mol%, silver iodide 0.2 mol%, and the balance silver bromide. Next, JP-A-2-28
No. 0139, denatured gelatin (in which the amino group in gelatin is substituted with phenylcarbamyl, for example, Compound G-
Desalting was performed using 8). EAg after desalting is 190 at 50 ° C
It was mv.

In the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1.5 × 10 ^-3 mol per mol of silver, and potassium bromide in an amount of 8.5 × 10 5.
PH 5.6, EAg12 with addition of ^-4 mol and citric acid
Adjusted to 3 mv.

Then, 1 × 10 ⁻³ mol of sodium p-toluenesulfonylchloramide trihydrate (chloramine T) was added and reacted, and then solid-dispersed inorganic sulfur (S
8) Compound (manufactured by Seishin Enterprise Co., Ltd .; PM-1200)
To which saponin was added to have an average particle size of 0.5μ and 1.5 × 10 ^-5 mol of chloroauric acid was added, and the temperature was adjusted to 55
After chemical aging at maximum temperature at 50 ℃, 50 ℃
Then, 100 mg of the spectral sensitizing dye d-1 and 5 mg of trihexylamine were added, and the temperature was further lowered to 40 ° C., and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added 2 × per mol of silver. 10 ^-3 mol, 1-phenyl-5
After adding 3 × 10 ^-4 mol of mercaptotetrazole and 5 × 10 ^-3 mol of potassium iodide, the pH was adjusted with citric acid.
Was adjusted to 5.1 to obtain silver halide emulsion A1.

(Preparation of Silver Halide Emulsion A2) With respect to silver halide emulsion A1, the reaction temperature was raised to 50 ° C. to make the grain size 0.19 μ, and K ₃ RhCl ₆ in the shell portion was 6 × 10 ^−8.
A silver halide emulsion A2 was prepared in exactly the same manner as A1 except that the mole ratio was changed. When the same chemical sensitization is performed, A2
Emulsion is 40% more sensitive than emulsion A1.

(Preparation of a silver halide photographic light-sensitive material containing a hydrazine derivative for a printing plate making scanner) A gelatin subbing layer having the following formulation 1 was used on a support with a gelatin content of 0.45.
g / m so that the ^2, amount of silver 1.5 g / m ² of silver halide emulsion layers 1 Formulation 2 thereon, the amount of gelatin is 0.6
So that 5 g / m ^2, as further silver amount 1.5 g / m ² of silver halide emulsion layers 2 of Formula 3 thereon, the amount of gelatin is 0.65 g / m ^2, further following formulation 4 Simultaneous multi-layer coating was performed so that the coating amount of the protective layer coating solution was 0.7 g / m ² . On the other side of the undercoating layer, a backing layer of the following formulation 5 was provided with a gelatin amount of 1.5 g / m ^2, and a backing protective layer of the following formulation 6 was provided thereon with a gelatin amount of 0.8 g / m 2. ^The emulsion layer side and the emulsion layer side were simultaneously multilayer-coated at a speed of 200 m / min by a curtain coating method so as to obtain a layer 2 and then cooled and set. Then, the backing layer side was simultaneously multilayer-coated and cooled and set at -1 ° C. A sample was obtained by simultaneously drying both sides.

Formulation 1 (Gelatin subbing layer composition) Gelatin 0.45 g / m ² saponin 56.5 mg / m ² redox compound (compound shown in Table 1) (Dissolved in ethyl acetate and dispersed in gelatin solution, then acetic acid 25 mg / m ² solid disperse dye (compound shown in Table 1) 50 mg / m ² sodium polystyrene sulfonate (average molecular weight 500000) 15 mg / m ² fungicide z 0 0.5 mg / m ² Formulation 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A1 Silver amount 1.5 g / m ² equivalent amount Sensitizing dye d-1 150 mg / Ag 1 mol Hydrazine compound H-1 2 × 10 ^-3 mol / Ag 1 mol Amino compound AM-1 7 mg / m ² compound a 100 mg / m ² 2-pyridinol 1 mg / m ² polymer latex L1 (particle size 0.25 μ) 0.25 g / m ² hardener h1 5 mg / m ² sodium-iso-amyl-n-decyl sulfosuccinate 0.7 mg / m ² sodium naphthalene sulfonate 8 mg / m ² saponin 20 mg / m ² hydroquinone 20 mg / m ² 2-mercapto-6-hydroxypurine 2 mg / m ² 2-mercaptopyridine 1 mg / m ² colloidal silica (average particle size 0.05 μ) 150 mg / m ² ascorbic acid 20 mg / m ² EDTA 25 mg / m ² polystyrene The sodium sulfonate 15 mg / m ² coating solution pH was 5.2.

Formulation 3 (composition of silver halide emulsion layer 2) Silver halide emulsion A2 Silver amount 1.5 g / m ² equivalent amount Sensitizing dye d-2 100 mg / Ag 1 mol Hydrazine compound H-2 4 × 10 ⁻³ Mol / Ag 1 mol amino compound AM-1 7 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 1.7 mg / m ² 2-mercapto-6-hydroxypurine 1 mg / m ² nicotinic acid amide 1 mg / m ² Gallic acid n-propyl ester 50 mg / m ² Mercaptopolyimide 1 mg / m ² EDTA 50 mg / m ² Styrene-maleic acid copolymer (molecular weight 70,000) 10 mg / m ² Polymer latex L2 (JP-A-5-66512 Example 3) Type Lx-3 composition (9)) 0.25 g / m ² colloidal silica (average particle size 0.05 μ) 150 mg / m ² The gelatin used 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 14 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² Matting agent: Average particle size 3 0.5 µ spherical polymethylmethacrylate 25 mg / m ² average particle diameter 8 µ indeterminate silica 12.5 mg / m ² surfactant S-1 26.5 mg / m ² lubricant (silicone oil) 4 mg / m ² compound a 50 mg / m ² polymer latex L3 (particle size 0.10 μ) 0.25 g / m ² colloidal silica (average particle size 0.05 μ) 150 mg / m ² dye f1 20 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² hardener h2 30 mg / m ² sodium polystyrenesulfonate 10 mg / m ² fungicide z 0.5 mg / m ² formulation 5 (backing layer Adult) Gelatin 0.6 g / m ² Sodium - iso - amyl -n- decyl sulfosuccinate 5 mg / m ² Polymer latex L3 0.3 g / ^{m 2} Colloidal silica (average particle size 0.05 .mu.m) 100
mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100 mg / m ² 1-Phenyl-5-mercaptotetrazole 10 mg / m ² Hardener h3 100 mg / m ² Zinc hydroxide 50 mg / m ² EDTA 50 mg / m ² Formulation 6 (backing protective layer) Gelatin 0.4 g / m ² Matting agent: Monodisperse polymethylmethacrylate with average particle size 5 μ 50 mg / m ² Average particle size 3 μ Indeterminate silica 12.5 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant S-1 1 mg / m ² Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100 mg / m ² dye SF2 (solid dispersion) 20 mg / m ² compound a 50 mg / m ² hardener h2 20 mg / m ² polystyrene Sodium sulfonate 10 mg / m ² Solid dispersion dye was acid deposition in addition after dissolution in an alkali, and 1.2 equivalents of citric acid to acid groups.

[0169]

[Chemical 40]

[0170]

Embedded image

[0171]

Embedded image

The details of the obtained sample are shown in Table 1 below.
Samples A and B were prepared in the same manner as above except that the hydrazine compound was removed from the silver halide emulsion layers 1 and 2.

[0173]

[Table 1]

(Developer composition) Per 1 liter of working solution Diethylenetriamine pentaacetic acid / 5 sodium salt 1 g Sodium sulfite 42.5 g Potassium sulfite 17.5 g Potassium carbonate 55 g Hydroquinone 20 g 1-Phenyl-4-methyl-4-hydroxymethyl-3 -Pyrazolidone 0.85 g Potassium bromide 4 g 5-Methylbenzotriazole 0.2 g Boric acid 8 g Diethylene glycol 40 g 8-Mercaptoadenine 0.3 g KOH was added in an amount to bring the pH to 10.4.

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

(Processing conditions) (Process) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Water washing 20 minutes normal temperature 20 seconds Squeeze / dry 50 ° C. 30 seconds Total 100 seconds (Evaluation of sensitivity and gamma) Exposure is light source With a laser sensitometer using a 633 nm He-Ne laser as
Step exposure is performed while changing the light amount in 10 ^-7 seconds, and the automatic developing machine GR-27 (Konica Corporation) is used under the above developing conditions.
Manufactured). The obtained developed sample was used for PDA-
65 (Konica Digital Densitometer).

The sensitivities shown in Table 1 are those of Sample No. It was expressed as relative sensitivity when the sensitivity at a sample concentration of 2.5 with the new solution of 1 was 100. Further, gamma is represented by tangents of densities of 0.1 and 3.0, and it is shown that a super-high contrast image can be obtained only when the gamma value in the table is 10 or more.

Evaluation of performance against changes in developer level (change in performance due to new solution and running solution)
While replenishing the above per m ² , 100 sheets of large size film that blackened 80% of the area per day were processed, and this was run for 8 days, and a total of 800 sheets were processed to improve the performance after running. Compared.

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

(Evaluation of gradation variability) The evaluation with respect to the fluctuation of the exposure amount was carried out by exposing the halftone dots corresponding to 50% by the SG747RU with a random pattern of 8 μ (FM screen) while changing the laser output to expose the optimum exposure amount. From the laser output value, the change width of halftone dots with respect to the exposure width of ± 20% was evaluated. The smaller the value, the smaller the change and the better. The above results are shown in Table 2 below.

[0181]

[Table 2]

As is clear from the results shown in Table 2, all the samples according to the present invention have high sensitivity and high gamma, and black spots are not generated. Further, it was excellent in that the change in gradation was small even when the exposure amount was changed. Furthermore, it can be seen that the deterioration of the performance due to running is small and the sample of the present invention is greatly improved.

Example 2 The sensitizing dye of Example 1 was replaced by d-8 instead of d-1 and d-2.
Was used per 1 mol of silver, and a sample was prepared in the same manner as in Example 1 except that an infrared laser diode light source of 670 nm was used as the exposure method. Table 3 shows the obtained evaluation results. For evaluation of gradation variability, exposure was performed using Avantra 25.

[0184]

[Table 3]

As is clear from the results shown in Table 3, even when the infrared laser diode light source is used, the sample according to the present invention has high sensitivity and high gamma as in the case of Example 1, and the process variation due to the exposure amount and running. Also, it was excellent in that there was little deterioration due to fluctuations in performance.

[0186]

As demonstrated in the examples, according to the present invention, a silver halide photographic light-sensitive material for plate-making can be obtained which has high contrast and high sensitivity and suppresses the generation of black spots. Further, according to the present invention, there can be obtained a silver halide photographic light-sensitive material for printing plate making and a method for forming an image thereof which are free from fluctuations in processing due to running and fluctuations in exposure.

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Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material comprising a gelatin subbing layer on a support, and at least one silver halide emulsion layer and a hydrophilic colloid layer, wherein the silver halide emulsion layer side is provided. A silver halide grain containing a redox compound capable of releasing a development inhibitor when oxidized, and the silver halide grain of the silver halide emulsion layer is a core / shell type silver halide grain having a laminated structure of two or more layers. And a core / shell type silver halide grain in which at least one kind of metal compound containing Rh, Re, Ru, Os is present in the core portion of the innermost layer in a higher content than in the shell portion of the outer layer. Silver halide photographic light-sensitive material. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the metal compound contained in the silver halide grains is a compound containing Rh. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the constituent layer of the silver halide photographic light-sensitive material contains a hydrazine derivative. 4. The silver halide photographic light-sensitive material according to claim 3, wherein said silver halide photographic light-sensitive material constituting layer contains at least one solid disperse dye. 5. The silver halide photographic light-sensitive material according to claim 4, wherein a high tone image having a gamma of 10 to 30 is formed by processing with a developing solution having a pH of 9.5 to 11.0. Image forming method.