JP2684243B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and more particularly to an ultra-high contrast silver halide photographic light-sensitive material used for photoengraving.

(Prior Art) In the field of photoengraving, there is a demand for a photographic photosensitive material having good original reproducibility, a stable processing solution, or a simple replenishment in order to cope with the variety and complexity of printed matter.

Particularly in the line drawing photographing process, the manuscript is made by pasting typesetting characters, handwritten characters, illustrations, halftone pictures, and the like. Therefore, images having different densities and line widths are mixed in an original, and a plate-making camera, a photographic photosensitive material, or an image forming method for finishing these originals with good reproducibility is strongly desired. On the other hand, in plate making of catalogs and large posters, enlargement (enlargement) or reduction (shrinkage) of a halftone picture is widely performed, and in plate making using enlarged halftone dots, the number of lines becomes coarse and blurred. Shooting. In the reduction, the number of lines / inch is larger than that of the original, and a thin point is photographed. Therefore, there is a demand for an image forming method having a wider latitude in order to maintain the reproducibility of halftone.

A halogen lamp or a xenon lamp is used as a light source of a plate making camera. In order to obtain a photographic sensitivity with respect to these light sources, a photographic light-sensitive material is usually subjected to orthosensitization. However, it was found that the ortho-sensitized photographic light-sensitive material is more strongly affected by the chromatic aberration of the lens, and thus the image quality is likely to deteriorate. This deterioration is more remarkable for a xenon lamp light source.

As a system to meet the demand of a wide latitude, a lithographic silver halide light-sensitive material composed of silver chlorobromide (at least a silver chlorobromide content of 50% or more) has an extremely low effective concentration of sulfite ion (usually 0.1 mol / mol). Hereinafter, there is known a method of obtaining a line image or a halftone dot image having a high contrast and a high blackening density in which an image portion and a non-image portion are clearly distinguished by processing with a hydroquinone developer. However, in this method, since the concentration of sulfurous acid in the developer is low, the development is extremely unstable against air oxidation,
In the present situation, various efforts and ingenuity have been made in order to keep the liquid activity stable, and the processing speed is remarkably slow, and the working efficiency is lowered.

Therefore, an image forming system that eliminates the instability of image formation due to the above-described developing method (lith development system) and develops with a processing solution having good storage stability to obtain super-high contrast photographic characteristics is provided. There is a demand, and one of them is U.S. Pat. Nos. 4,166,742, 4,168,977, 4,211,857, 4,2.
24,401, 4,243,739, 4,272,606, 4,311,78
As shown in No. 1, the surface latent image type silver halide photographic light-sensitive material containing a specific acylhydrazine compound was added
11.0 to 12.3 containing 0.15 mol /) or more of sulfite preservative,
A system has been proposed which is processed with a developer having good storage stability to form a super-high contrast negative image having a γ of more than 10. This new image forming system has the characteristic that silver iodobromide and silver chloroiodobromide can also be used in contrast to conventional silver halide chlorobromide having a high silver chloride content in superhigh contrast image formation. is there.

The above image system shows excellent performance in terms of sharp halftone dot quality, processing stability, quickness and original reproducibility, but it is more stable and has good original reproducibility in order to cope with the recent variety of printed materials. An optimized system is desired.

Examples containing a redox compound which releases a development inhibitor when oxidized in a system using hydrazine are disclosed in JP-A-61-213847 and JP-A-64-72140.

On the other hand, examples using silver chlorobromide are disclosed in JP-A-60-83028 and JP-A-60-83028.
-112034, 62-235947, 63-103232, 53-
20921 and 54-37732.

Examples of a system using hydrazine containing an amine compound in a developing solution are disclosed in JP-A-60-218642, JP-A-60-258573, and JP-A-60-258573.
61-267759, 61-230145, 62-212647, JP-A-1-200354, 1-205160, 1-214844, U.S. Pat. , JP-A-60-140340, 61-251846, 62-222241,
62-55642, 62-250439, 62-280733, 63
-124045. An example using an amine compound having an ethylene oxide group is disclosed in JP-A-2-170155, but there is no description of obtaining a stable system using silver chlorobromide.

(Problems to be Solved by the Invention) The first object of the present invention is to reduce the sensitivity, γ and Dmax little even if the pH is lowered or the bromine ion concentration is increased by treating a large amount of film. The object is to provide a silver halide photographic light-sensitive material.

A second object of the present invention is to provide a silver halide photographic light-sensitive material excellent in line drawing or line drawing such as suitability for stretching and contraction.

(Problem for Solving the Problem) The first object of the present invention is to provide at least one support on a support.
Light-sensitive silver halide emulsion layer containing a hydrazine derivative, and the emulsion layer or other hydrophilic colloid layer containing an amine compound having at least two repeating ethylene oxide groups. In the material, the silver halide emulsion is 50 mol% of silver chloride.
The present invention has been achieved by a negative type silver halide photographic light-sensitive material characterized by comprising the above silver halide.

A second object of the present invention is to provide a negative-type silver halide photographic material containing a redox compound which releases a development inhibitor upon being oxidized into an emulsion layer or other hydrophilic colloid layer in the negative-type silver halide photographic light-sensitive material. Achieved by a light-sensitive material.

As the amine compound having at least two repeating ethylene oxide groups used in the present invention, compounds represented by the following general formulas (I), (II) and (III) are preferable.

General formula (I) In the formula, R ₁ and R ₂ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 3 to 30 carbon atoms or 7 carbon atoms.
It represents an aralkyl group of ~ 30. However, when R ₁ and R ₂ simultaneously represent an alkyl group, the carbon number of R ₁ + R ₂ represents 10 or more.

R ₁ and R ₂ do not represent a hydrogen atom at the same time, and may be bonded to each other to form a ring.

n represents an integer of 2 to 50. R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

General formula (II) R _'1 and _{R' 2} represents the same meaning as R ₁ and R _2.

In the general formula (III) YX _n A ₀ -B ₀ ] _m , Y represents a group adsorbing to silver halide, and X is an atom selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. Alternatively, it represents a divalent linking group consisting of an atomic group, A ₀ represents a divalent linking group having at least two alkyleneoxy units, and B ₀ represents an amino group, an ammonium group, or a nitrogen-containing heterocyclic group. m represents 1, 2 or 3, and n represents 0 or 1.

Examples of the group adsorbed to the silver halide represented by Y include a nitrogen-containing heterocyclic compound, a heterocyclic mercapto compound, and an aliphatic mercapto compound.

Next, the compounds represented by the above general formulas (I) and (II) will be described in more detail.

R ₁ and R ₂ may be the same or different and each is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (including those having a substituent. For example, a methyl group, an ethyl group, an n-butyl group. , N-hexyl group, n-octyl group, 2-ethylhexyl group, methoxyethyl group, ethylthioethyl group, dimethylaminoethyl group, n-decyl group, n-dodecyl group,
Phenoxyethyl group, 2,4-di-t-amylphenoxyethyl group, n-octadecyl group, etc., including alkenyl groups having 3 to 30 carbon atoms (including those having a substituent. For example, allyl group, butenyl group, pentenyl group. , Etc.) or carbon number 7 to
30 aralkyl groups (including those having a substituent. For example, a phenethyl group, a benzyl group, a 4-methoxybenzyl group,
4-t-butylbenzyl group, 2,4-di-t-amylphenethyl group, etc.).

R ₁ and R ₂ may be integrated together to form an optionally substituted alkylene and form a ring together with the nitrogen atom. (For example, a pyrrolidine ring, a piperidine ring, a 2-methylpiperidine ring, a hexamethyleneimine ring, etc.).

R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and each is a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms (preferably a lower alkyl group having no substituent. , Methyl group, ethyl group, n-butyl group, etc.).

When R ₁ and R ₂ have a substituent, the substituent is, for example, a halogen atom (eg, chlorine atom, bromine atom, etc.), cyano group, nitro group, hydroxy group, alkoxy group (eg, methoxy group, etc.). , An aryloxy group (eg, phenoxy group, 2,4-di-t-amylphenoxy group, etc.), an alkylthio group (eg, methylthio group,
Etc.), an arylthio group (for example, a phenylthio group, etc.),
Acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.), amino group (eg, unsubstituted amino group, dimethylamino group, etc.), carbonamide group (eg, acetamide group, etc.), sulfonamide group (eg, methanesulfonamide) Group, benzenesulfonamide group, etc.), oxycarbonylamino group (eg methoxycarbonylamino group, etc.), ureido group (eg unsubstituted ureido, 3,
3-dimethylureido group, etc.), thioureido group (eg, unsubstituted thioureido group, 3-phenylthioureido group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), oxycarbonyl group (eg, methoxycarbonyl group, Etc.), carbamoyl group (eg, methylcarbamoyl group, 4-methylphenylcarbamoyl group, etc.), sulfonyl group (eg, methanesulfonyl group, etc.), sulfamoyl group (eg, methylsulfamoyl group, 4-methoxyphenylsulfamoyl group) , Etc.), carboxylic acids or salts thereof, sulfonic acids or salts thereof, and the like.

In the general formulas (I) and (II), preferably R ₁ and R ₂ each represent an alkyl group having 1 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, and R ₃ , R ₄ , R ₅ and R ₆ represents a hydrogen atom, and n represents an integer of 3-20.

In the general formulas (I) and (II), more preferably R ₁ and R ₂
Each represents an alkyl group having 5 to 20 carbon atoms.

Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the compounds of the present invention are not limited thereto.

I-5 (n) C ₄ H ₉ NHCH ₂ CH ₂ O) ₃ H The compound represented by formula (III) will be described.

Examples of the group adsorbing the silver halide represented by Y include a nitrogen-containing heterocyclic compound, a heterocyclic mercapto compound, and an aliphatic mercapto compound.

When Y represents a nitrogen-containing heterocyclic compound or a heterocyclic mercapto compound, general formula (3) or (4) below can be mentioned.

General formula (3) Formula _{(4) MS-ZX n A} 0 -B 0 ] _m general formula (3), l is 0 or 1, X
_n A ₀ -B ₀ ] _m has the same meaning as in formula (1), and Q is a 5- or 6-membered complex consisting of at least one atom selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. Represents the group of atoms necessary to form a ring. This heterocyclic ring may be condensed with a carbon aromatic ring or a heteroaromatic ring.

Examples of the heterocycle formed by Q include substituted or unsubstituted indazoles, benzimidazoles, benzotriazoles, benzoxazoles,
Benzthiazoles, imidazoles, thiazoles,
Oxazoles, triazoles, tetrazoles, azaindenes, pyrazoles, indoles, triazines, pyrimidines, pyridines, quinolines and the like.

M represents a hydrogen atom, an alkali metal atom (eg, sodium atom, potassium atom, etc.), an ammonium group (eg, trimethylammonium group, dimethylbenzylammonium group, etc.), a group which can be M ＝ H or an alkali metal atom under alkaline conditions ( For example, acetyl, cyanoethyl, methanesulfonylethyl, etc.).

These heterocycles may be nitro group, halogen atom (eg, chlorine atom, bromine atom, etc.), mercapto group, cyano group, and substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, propyl group, t-group). Butyl group, cyanoethyl group, methoxyethyl group, methylthioethyl group,
Etc.), aryl group (for example, phenyl group, 4-methanesulfonamidophenyl group, 4-methylphenyl group, 3,4-
Dichlorophenyl group, naphthyl group, etc.), alkenyl group (eg, allyl group, etc.), aralkyl group (eg, benzyl group, 4-methylbenzyl group, phenethyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, Etc.), aryloxy groups (eg phenoxy group, 4-methoxyphenoxy group, etc.), alkylthio groups (eg methylthio group, ethylthio group, methoxyethylthio group), arylthio groups (eg phenylthio group), sulfonyl groups (eg methanesulfonyl) Group, ethanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl group, methylsulfamoyl group, Phenylsulfamoyl group Etc.), carbonamide group (eg, acetamide group, benzamide group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.), acyloxy group (eg, acetyloxy group, Benzoyloxy group, etc.), sulfonyloxy group (eg methanesulfonyloxy group, etc.), ureido group (eg unsubstituted ureido group, methylureido group, ethylureido group, phenylureido group, etc.), thioureido group (eg nothing Substituted thioureido group, methylthioureido group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), heterocyclic group (eg, 1-morpholino group, 1-piperidino group, 2-
Pyridyl group, 4-pyridyl group, 2-thienyl group, 1-pyrazolyl group, 1-imidazolyl group, 2-tetrahydrofuryl group, tetrahydrothienyl group, etc., oxycarbonyl group (for example, methoxycarbonyl group, phenoxycarbonyl group, etc.) ), An oxycarbonylamino group (for example, a methoxycarbonylamino group, a phenoxycarbonylamino group, a 2-ethylhexyloxycarbonylamino group,
And the like, an amino group (eg, an unsubstituted amino group, a dimethylamino group, a methoxyethylamino group, an anilino group, etc.), a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a hydroxy group, and the like.

Examples of the divalent linking group represented by X include -S-, These linking groups are linked to Q via a linear or branched alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group, etc.). May be combined.
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each a hydrogen atom, a substituted or unsubstituted alkyl group (eg, a methyl group, an ethyl group, a propyl group) Group, n-butyl group,
Etc.), substituted or unsubstituted aryl groups (eg, phenyl group, 2-methylphenyl group, etc.), substituted or unsubstituted alkenyl groups (eg, propenyl group, 1-methylvinyl group, etc.), or substituted or unsubstituted (For example, benzyl group, phenethyl group, etc.).

A ₀ is 2 having at least two alkylene units
Represents a valent linking group, preferably Represents

_{R '1, R' 2,} R '3 and _{R' 4} each represent a hydrogen atom, an allyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, n- propyl group, n- butyl group, etc.) , Q
Represents an integer of 2 to 50.

The substituted or unsubstituted amino group of B ₀ is represented by the general formula (5).

General formula (5) (In the formula, R ¹¹ and R ¹² may be the same or different,
Each represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an alkenyl group or an aralkyl group,
These groups are straight-chain (eg, methyl, ethyl, n-propyl, n-butyl, n-octyl, allyl,
3-butenyl group, benzyl group, 1-naphthylmethyl group,
Etc.), branched (for example, isopropyl group, t-octyl group,
Etc.) or cyclic (eg, a cyclohexyl group, etc.).

R ¹¹ and R ¹² may be linked to form a ring, in which one or more heteroatoms (eg, an oxygen atom,
The compound may be cyclized to form a saturated hetero ring containing a sulfur atom, a nitrogen atom, and the like, and examples thereof include a pyrrolidyl group, a piperidyl group, and a morpholino group. Examples of the substituent of R ¹¹ and R ¹² include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom and a bromine atom), a hydroxy group, an alkoxycarbonyl having 20 or less carbon atoms. Groups (e.g., methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, etc.),
Alkoxy group having 20 or less carbon atoms (eg, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), monocyclic aryloxy group having 20 or less carbon atoms (eg, phenoxy group, p-trioxy group, etc.), carbon Number 20 or less acyloxy group (eg acetyloxy group, propionyloxy group etc.), Number 20 carbon or less acyl group (eg acetyl group, propionyl group, benzoyl group, mesyl group etc.), carbamoyl group (eg carbamoyl group, N,
N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), carbon number 20 The following acylamino groups (for example, acetylamino group, propionylamino group, benzoylamino group, mesylamino group, etc.), sulfonamide groups (ethylsulfonamide group, p-toluenesulfonamide group, etc.), carbonamide groups having 20 or less carbon atoms ( Examples thereof include a methylcarbonamide group, a phenylcarbonamide group and the like), a ureido group having 20 or less carbon atoms (for example, a methylureido group, a phenylureido group and the like), an amino group (synonymous with the general formula (5)) and the like.

The ammonium group of B ₀ is represented by the general formula (6).

General formula (6)(Where R¹³, R¹⁴, R^FifteenIs R in the above general formula (5)
¹¹And R¹²Is the same group as Represents anion
For example, halide ions (eg Cl , Br , I What
Etc.), sulfonate ion (for example, trifluoromethane
Sulfonate, paratoluenesulfonate, benzenes
Rufonate, parachlorobenzenesulfonate, etc.),
Sulfite ions (eg, ethyl sulfate, methyl
Lusulfate, etc.), perchlorate, tetrafluo
Roborate and the like. p represents 0 or 1
And 0 when the compound forms an internal salt. ) B₀Is at least one or more nitrogen atoms
A 5- or 6-membered ring containing a child, and a salt thereof is a substituent
May be condensed with another ring
No. Examples of the nitrogen-containing hetero ring include an imidazolyl group,
Examples include a lysyl group and a thiazolyl group.

Preferred examples of the general formula (3) include compounds represented by the following general formulas (7), (8) and (9).

General formula (7) General formula (8) General formula (9) In the formula, X _n A ₀ -B ₀ and M, m have the same meanings as in the general formula (1).

 Next, the general formula (4) will be described in detail.

Z represents a heterocyclic ring composed of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a selenium atom.

The heterocyclic ring represented by Z is preferably a 5- or 6-membered heterocyclic ring, and may be condensed with a carbon aromatic ring or a heteroaromatic ring.

As the heterocycle, preferably a tetrazole, triazole, thiadiazole, oxadiazole, selenazole, imidazole, thiazole, oxazole, benzimidazole, benzthiazole, benzoxazole, benzselenazole, tetraazaindene, triazaindene, pentaazaindene ring can give. Of these, tetrazole and thiadiazole are particularly preferred. Further, these heterocycles may be substituted with the substituents mentioned for Q in the general formula (3).

Further, M and X _n A ₀ −B ₀ ] _m have the same meanings as those in the general formula (3).

Specific examples of the compound represented by formula (III) are shown below, but the invention is not limited thereto.

The compounds represented by the general formulas (I), (II) and (III) of the present invention can be easily prepared by addition reaction of an amine compound to an ethyl oxide compound or substitution reaction of an amine compound with a polyalkylene glycol monohahydrin. Can be synthesized.

The amount of the amino compound represented by the general formulas (I), (II) and (III) added is 1 × 10 ⁻⁷ to 1 × 10 ⁻³ mol / m ² , preferably 1 × 10 ⁻⁶ to 1 × 10 5. ^-4 mol / m ² is good.

When it is contained in a photographic material, it is preferably contained in a silver halide emulsion layer, but it is contained in other non-photosensitive hydrophilic colloid layers (for example, protective layer, intermediate layer, filter layer, antihalation layer, etc.). May be.
Specifically, a hydrophilic colloid solution is used as an aqueous solution when the compound used is water-soluble, or as a solution of an organic solvent miscible with water such as alcohols, esters, and ketones when the compound is poorly water-soluble. May be added.

Further, the general formulas (I) and (II) and the general formula (III) of the present invention
May be used in combination in the light-sensitive material.

The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula (IV).

General formula (IV) In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group,
G ₁ -SO ₂ -group, -SO- group, Represents a thiocarbonyl group or an iminomethylene group, A ₁ ,
Both A _2's represent a hydrogen atom or a hydrogen atom in one and a substituted or unsubstituted alkylsulfonyl group in the other, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted sial group.

In the general formula (IV), the aliphatic group represented by R ₁ is preferably an aliphatic group having 1 to 30 carbon atoms, and particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. This alkyl group may have a substituent.

In formula (IV), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.
Here, the unsaturated heterocyclic group may be condensed with the aryl group.

Preferred as R ₁ is an aryl group, particularly preferably a group containing a benzene ring.

The aliphatic group or the aromatic group of R ₁ may be substituted, and typical substituents include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group,
Aryl group, substituted amino group, ureido group, urethane group,
Aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group , An acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, an imide group, And the like. Preferred substituents are an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably having 7 to 30 carbon atoms), and an alkoxy group (preferably having 1 to 20 carbon atoms). ), A substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 30 carbon atoms),
Examples thereof include a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), and a phosphoric amide group (preferably having 1 to 30 carbon atoms).

In formula (IV), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, those containing a benzene ring ).

G ₁ In the case of, preferred among the groups represented by R ₂ are a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3 methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.) , Aralkyl groups (for example, o-hydroxybenzyl group), aryl groups (for example, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group) Etc.), and a hydrogen atom is particularly preferable.

R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied.

As G in the general formula (IV), Most preferred are groups.

Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule, -G ₁
-R ₂ moiety of atoms may be such as to occur a cyclic structure cyclization reaction to form a containing, include those described in, for example, JP 63-29751 as an example.

A ₁ and A ₂ are most preferably hydrogen atoms.

R ₁ or R _{2 in} the general formula (IV) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inactive for photographic properties, such as an alkyl group, an alkoxy group,
It can be selected from a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (IV) may have a group in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of such adsorbing groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, and the like, U.S. Patent Nos. 4,385,108 and 4,459,347;
-195,233, 59-200,231, 59-201,045, 5
Nos. 9-201,046, 59-201,047, 59-201,048,
59-201,049, JP-A-61-170,733, JP-A-61-270,744
No. 62-948, Japanese Patent Application No. 62-67,508, No. 62-67,501
No. 62-67,510.

Specific examples of the compound represented by the general formula (IV) are shown below. However, the present invention is not limited to the following compounds.

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item23516 (1983
November, p. 346) and references cited therein,
U.S. Pat.Nos. 4,080,207, 4,269,929, 4,276,364
No. 4,278,748, No. 4,385,108, No. 4,459,347,
4,560,638, 4,478,928, UK Patent 2,011,391B,
JP-A-60-179934, JP-A-62-270,948, JP-A-63-29,751
Nos. 61-170,733, 61-270,744, 62-948
No., EP217,310, or US 4,686,167, JP-A-62-17
No. 8,246, No. 63-32,538, No. 63-104,047, No. 63-12
Nos. 1,838, 63-129,337, 63-223,744, 63-2
Nos. 34,244, 63-234,245, 63-234,246, 63-
294,552, 63-306,438, JP-A-1-100,530,
No. 1-105,941, No. 1-105,943, JP-A-64-10,233
No., JP-A-1-90,439, Japanese Patent Application No. 63-105,682, 63
-114,118, 63-110,051, 63-114,119, 6
3-116,239, 63-147,339, 63-179,760,
63-229,163, JP-A-1-18377, 1-18,378.
Nos. 1-18,379, 1-15,755, 1-16,814
Nos. 1-40,792, 1-42615, 1-42616
And those described in Nos. 1-123,693 and 1-126,284 can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1.times.10.sup.- ⁶ mol to 5.times.10.sup.- ² mol, more preferably 1.times.10.sup.- ⁵ mol to 2.times.10.sup.- ⁵ mol per mol of silver halide.
A range of × 10 ^-2 mol is a preferable addition amount.

The redox compound of the present invention that can release a development inhibitor by being oxidized will be described.

The redox group of the redox compound is preferably a hydroquine, a catechol, a naphthohydroquinone, an aminophenol, a pyrazolidone, a hydrazine, a hydroxylamine or a reductone, and more preferably a hydrorazine.

The hydrazines used as a redox compound capable of releasing a development inhibitor by being oxidized according to the present invention are preferably those represented by the following general formulas (R-1) and (R-2).
It is represented by the general formula (R-3). The compound represented by formula (R-1) is particularly preferred.

General formula (R-1) General formula (R-2) General formula (R-3) In these formulas, R ₁ represents an aliphatic group or an aromatic group. G ₁ -SO- group, -SO ₂ - group or Represents G ₂ is a mere bond, -O-, -S- or And R ₂ represents a hydrogen atom or R ₁ .

A ₁ and A ₂ represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. In the general formula (R-1), at least one of A ₁ and A ₂ is a hydrogen atom. A ₃ is synonymous with A ₁ or Represents

A ₄ represents a nitro group, a cyano group, a carboxyl group, a sulfo group or -G ₁ -G ₂ -R _1.

Time represents a divalent linking group, and t represents 0 or 1. PUG represents a development inhibitor.

General formulas (R-1), (R-2) and (R-3) will be described in more detail.

In formulas (R-1), (R-2) and (R-3), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms.
And particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. This alkyl group may have a substituent.

In formulas (R-1), (R-2) and (R-3), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group.

For example, among those having a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, an isoquinoline ring, etc., those containing a benzene ring are preferable.

Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and typical substituents include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, Ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio, sulfonyl, sulfinyl, hydroxy, halogen, cyano, sulfo, aryloxycarbonyl, acyl, alkoxycarbonyl Groups, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, and the like. Preferred substituents are a linear, branched, or cyclic alkyl group (preferably having 1 to 20 carbon atoms). Aralkyl group (preferably having 7 to 30 carbon atoms), aralkyl group Coxy group (preferably having 1 to 30 carbon atoms), substituted amino group (preferably having 1 to 30 carbon atoms)
Amino group substituted with 30 alkyl group), acylamino group (preferably having 2 to 40 carbon atoms), sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having carbon number) Those having 1 to 40, phosphoric acid amide groups (preferably having 1 to 40 carbon atoms) and the like.

As G _{1 in the} general formulas (R-1), (R-2) and (R-3), -SO ₂ - group are preferred, Is most preferred.

A ₁ and A ₂ are preferably hydrogen atoms, A ₃ is a hydrogen atom, Is preferred.

In the general formulas (R-1), (R-2) and (R-3)
Time represents a divalent linking group, and may have a timing adjusting function.

The divalent linking group represented by Time represents a group that releases PUG through the reaction of Time-PUG released from the oxidized form of the redox mother nucleus in one step or more steps.

As the divalent linking group represented by Time, for example, an intramolecular ring closure reaction of a p-nitrophenoxy derivative described in U.S. Pat. No. 4,248,962 (Japanese Patent Application Laid-Open No. 54-145,135) and the like can be used.
U.S. Pat. No. 4,310,612 (Japanese Unexamined Patent Publication No.
Which release PUG by an intramolecular ring-closure reaction after ring opening described in, for example, US Pat. Nos. 4,330,617, 4,446,216, 4,483,919, and JP-A-59-121,328. No. 4,409,323, U.S. Pat. No. 4,421,845, which releases PUG with the formation of an acid anhydride by an intramolecular ring closure reaction of the carboxyl group of the succinic acid monoester or an analog thereof described in Research Disclosure No. 21,228 (December 1981), U.S. Patent No.
4,416,977 (JP-A-57-135,944), JP-A-58-209,
No. 736, No. 58-209,738, etc., which produce quinomonomethane or an analog thereof by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group to release PUG; US Pat. No. 4,420,554 (Japanese Unexamined Patent Publication No.
57-136,640), JP-A-57-135,945 and JP-A-57-188,03.
No. 5,58-98,728 and 58-209,737, which release PUG from the γ-position of enamine by electron transfer of a portion having an enamine structure of a nitrogen-containing heterocyclic ring;
Release of PUG by intramolecular ring reaction of oxy group formed by electron transfer to carbonyl group conjugated with nitrogen atom of nitrogen-containing heterocycle described in 7-56,837; US Pat.
4,146,396, (JP-A-52-90932), JP-A-59-93,4
No. 42, JP-A-59-75475, JP-A-60-249148, with formation of aldehydes described in JP-A-60-249149 and the like.
Those which release PUG; JP-A-51-146,828, 57-179,
No. 842, No. 59-104,641, which release PUG with decarboxylation of carboxyl group; -O-COOCR _a R _b -PUG
(R _a and R _b represent a monovalent group) and releases PUG with decarboxylation and subsequent formation of aldehydes; isocyanate described in JP-A-60-7,429 Examples thereof include those releasing PUG with the formation of the above; those releasing PUG by a coupling reaction with an oxidant of a color developing agent described in US Pat. No. 4,438,193 and the like.

Specific examples of the divalent linking group represented by Time are described in detail in JP-A-61-236,549 and Japanese Patent Application No. 63-98,803.

PUG represents a group having a development inhibiting effect as (Time _t PUG or PUG).

The development inhibitors represented by PUG or (Time _t PUG are known development inhibitors having a heteroatom and bonded through a heteroatom, such as CEKMess and "The Theory of Photographic Process" by THJames
Processes), 3rd Edition, 1966 Macmillan
It is described in company publications, pages 344 to 346.

The development inhibitor represented by PUG may be substituted. Examples of the substituent include those exemplified as the substituent of R ¹ , and these groups may be further substituted.

Preferred substituents are a nitro group, a sulfo group, a carboxyl group, a sulfamoyl group, a phosphono group, a phosphinico group, and a sulfonamide group.

In the general formulas (R-1), (R-2), and (R-3), R ₁ or Time _t PUG is a ballast group commonly used in immobile photographic additives such as couplers. A group which promotes the compounds represented by formulas (R-1), (R-2) and (R-3) to be adsorbed to silver halide may be incorporated.

The ballast group has the general formula (R-1), (R-2), (R-
An organic group that gives a molecular weight sufficient to prevent the compound represented by 3) from substantially diffusing into another layer or the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, It comprises one or more combinations of an amide group, a ureido group, a urethane group, a sulfonamide group and the like. The ballast group is preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

Specific examples of the group for promoting adsorption to silver halide include 4
-Thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3,4 Cyclic thioamide groups such as oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3-imidazoline-2-thione, and chain thioamides Group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (when the carbon atom to which the -SH group is bonded is a nitrogen atom, this is synonymous with a cyclic thioamide group having a tautomeric relationship with the nitrogen atom) Specific examples of this group are the same as those listed above.), A group having a disulfide bond, benzotriazole, triazole, tetrazo 5 to 6 members consisting of a combination of nitrogen, oxygen, sulfur and carbon such as ru, indazole, benzimidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, oxazole, oxazoline, thiadiazole, oxathiazole, triazine, azaindene. Membered nitrogen-containing heterocyclic groups, and heterocyclic quaternary salts such as benzimidazolinium.

These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent of R ₁ .

Hereinafter, specific examples of the compound used in the present invention will be listed, but the present invention is not limited thereto.

As the redox compound used in the present invention, in addition to the above, for example, JP-A-61-213,847 and JP-A-62-260,1
No. 53, Japanese Patent Application No. 1-102,393, No. 1-102,394, No. 1-
Nos. 102,395 and 1-114,455 can be used.

The method for synthesizing the redox compound used in the present invention is described in, for example, JP-A-61-213,847 and JP-A-62-260,153, U.S. Pat.
No. 4,684,604, Japanese Patent Application No. 63-98,803, U.S. Pat.
No. 29, 3,620,746, 4,377,634, 4,332,878
No., JP-A-49-129,536, JP-A-56-153,336, JP-A-56-15
No. 3,342.

The redox compound of the present invention is used in an amount of 1 × 10 ^{−6 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁵ per mol of silver halide.
It is used in the range of １1 × 10 ^-2 mol.

The redox compound of the present invention may be used in a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like.

Further, by a well-known emulsification dispersion method, it is dissolved by using an oil such as dibutyl phthalate, tricresyl phosphate, ate, glyceryl triacetate or diethyl phthalate, an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified. It is also possible to prepare and use a dispersion. Alternatively, a redox compound powder can be dispersed in water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The halogen composition of the monodispersed silver halide emulsion used in the present invention has a silver chloride content of 50 mol% or more and a silver chlorobromide,
It is composed of either silver iodochloride or silver iodochlorobromide. The silver iodide content is at most 3 mol%, more preferably at most 0.5 mol%.

Various methods known in the field of silver halide photographic materials are used for preparing the monodispersed silver halide emulsion used in the present invention. For example, P. Glafkide
s) "Simimy Physik Photographic (C
himie et Physique Photograhique "(published by Paul Montel in 1967) by GFDuffin" Photographic Emulsion Chemis "
try) published by The Focal Press
1966), VLZelikman e
t al) "Making and Coating Pho
tograhic Emulsion) "(The Focal Press
Focal Press) 1964) and the like.

The emulsion of the present invention is preferably a monodisperse emulsion and has a coefficient of variation of 20%.
The ratio is particularly preferably 15% or less.

Where the coefficient of variation is Is defined as

The average grain size of the grains in a monodispersed silver halide emulsion is
It is 0.5 μm or less, and particularly preferably 0.1 μm to 0.4 μm.

As a method of reacting a water-soluble silver salt (aqueous silver nitrate solution) with a water-soluble halogen salt, any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. As one form of the double jet method, pA in the liquid phase where silver halide is formed
A method of keeping g constant, that is, a control double jet method can also be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea.

More preferred are tetrasubstituted thiourea compounds.
Nos. 53-82408 and 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione.

According to the control double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is an effective means.

The monodispersed emulsion preferably has a regular crystal form such as a cubic, octahedral, or tetradecahedral, and particularly preferably a cubic.

In the silver halide grains, the inside and the surface layer may be composed of a uniform phase or may be composed of different phases.

The silver halide emulsion used in the present invention contains a cadmium salt during the formation or physical ripening of silver halide grains.
A sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof may coexist.

In the present invention, a silver halide emulsion particularly suitable as a light-sensitive material for line drawing and halftone dot formation is per mole of silver.
This is an emulsion prepared in the presence of 10 ^-8 to 10 ^-5 mol of an iridium salt or a complex salt thereof.

In the above, it is desirable to add the above amount of iridium salt before the completion of physical ripening in the production process of the silver halide emulsion, particularly at the time of grain formation.

The iridium salt used here is a water-soluble iridium salt or iridium complex salt, for example, iridium trichloride,
Iridium tetrachloride, potassium hexachloroiridate (III), potassium hexachloroiridium (IV),
And ammonium hexachloroiridate (III).

The monodispersed emulsion of the present invention is preferably subjected to chemical sensitization, and known methods such as sulfur sensitization, reduction sensitization, and gold sensitization can be used, and these are used alone or in combination. A preferred chemical sensitization method is gold sulfur sensitization.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. Specific examples are U.S. Pat.Nos. 1,574,944 and 2,278,947.
No. 2,410,689, 2,728,668, 3,501,313,
No. 3,656,955. Preferred sulfur compounds are thiosulfates and thiourea compounds, and the pAg at the time of chemical sensitization is preferably 8.3 or less, more preferably 7.3 to 8.0. Moisar, Klein Gelat
The method of combining polyvinylpyrrolidone and thiosulfate as reported by ine.Proc.Syme.2nd, 301-309 (1976) et al. also gives good results.

Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and iridium may be contained. Specific examples are U.S. Patent No. 2,448,060,
It is described in British Patent 618,061 and the like.

Gelatin is advantageously used as a binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives,
Graft polymer of gelatin and other polymers, albumin, protein hydroxyethyl cellulose such as casein,
Carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sugar derivatives such as sodium alginate, starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as imidazole and polyvinylpyrazole can be used.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

In the present invention, a sensitizing dye having an absorption maximum in the visible region described in JP-A-55-52050, pp. 45-53 (for example, a cyanine dye, a merocyanine dye, etc.) can also be added. As a result, spectral sensitization can be performed on the wavelength side of the intrinsic sensitivity region of silver halide.

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. With sensitizing dye,
A dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and which exhibits supersensitization may be contained in the emulsion.

Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Rese
Arch Disclosere) Volume 176 17643 (issued in December 1978) No. 23
It is described in section J on page IV.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitro. Benzotriazoles, etc .; Mercaptopyrimidines; Mercaptotriazines; Thioketone compounds such as oxazolinethione; Azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7 ) Tetrazaindenes), pentaazaindenes, etc .; with antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Many compounds known Te may be added. Among these, preferred are benzotriazoles (eg, 5-methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole). Further, these compounds may be contained in the treatment liquid. Furthermore, JP-A-62-3024
Compounds that release the inhibitor during development as described in 3,
It can be contained for the purpose of stabilizing or preventing black spots.

The photographic light-sensitive material of the present invention may contain a developing agent such as a hydroquinone derivative or a phenidone derivative for various purposes such as a stabilizer and an accelerator.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes, (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, active vinyl compounds (1,3,5-triacryloyl-). Hexahydro-S-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, etc.), etc. They can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, slipperiness improvement, emulsification / dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, high contrast For various purposes such as sensitization), various surfactants may be contained.

For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol) Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone, glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), and alkyl esters such as fatty acid esters of polyhydric alcohols. Agent: alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfo Acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethyl alkylphenyl ethers, polyoxyethylene alkyl phosphorus Carboxy groups, such as esters
Anionic surfactants containing an acidic group such as a sulfo group, a phospho group, a sulfate group, and a phosphate group; amino acids;
Amphoteric surfactants such as aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphoric acid esters, alkylbetaines and amine oxides; complex compounds such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium and imidazolium Cationic surfactants such as ring quaternary ammonium salts, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

Particularly, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412.

It is preferable to use a fluorinated surfactant described in JP-A-60-80849 or the like for antistatic.

The photographic light-sensitive material of the present invention includes a hydroquinone derivative (a so-called DIR-) which releases a development inhibitor in a photographic emulsion layer or other hydrophilic colloid layer in accordance with the density of an image during development.
(Hydroquinone).

Examples thereof are U.S. Pat.No. 3,379,529 and U.S. Pat.
20,746, U.S. Patent 4,377,634, U.S. Patent 4,332,878
JP-A-49-129,536, JP-A-54-67,419, JP-A-56-153,336, JP-A-56-153,342, JP-A-59-27
No. 8,853, No. 59-90435, No. 59-90436, No. 59-13880
No. 8 and the like.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide, or polymethyl methacrylate for the purpose of preventing adhesion to a photographic emulsion layer or other hydrophilic colloid layers.

The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of dimensional stability. For example, use is made of a polymer having, as a monomer component, an alkyl (meth) acrylate, an alkoxyacryl (meth) acrylate, a glycidyl (meth) acrylate, or the like alone or in combination, or a combination thereof with acrylic acid, methacrylic acid, or the like. be able to.

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention preferably contain a compound having an acid group. Examples of the compound having an acid group include salicylic acid, acetic acid, organic acids such as ascorbic acid and acrylic acid, maleic acid,
Examples thereof include polymers or copolymers having an acid monomer such as phthalic acid as a repeating unit. These compounds are described in JP-A-61-223834 and JP-A-61-228437.
Nos. 62-25745 and 62-55642 can be referred to. Among these compounds, particularly preferred are ascorbic acid as a low molecular compound, and a high molecular compound composed of an acid monomer such as acrylic acid and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene. It is a water-dispersible latex of a copolymer.

The emulsions used in this invention are coated on a suitable support such as glass, acetic acid, cellulose film, polyethylene terephthalate film, paper, baryta-coated paper, polyolefin-coated paper.

To obtain ultra-high contrast and high sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or a US patent
It is not necessary to use a highly alkaline developing solution close to pH 13 described in 2,419,957, and a stable developing solution can be used.

That is, the silver halide light-sensitive material of the present invention contains 0.15 mol / or more of sulfite ion as a preservative, and has a pH of 10.5
With a developer having a pH of from 12.3 to 12.3, particularly from 11.0 to 12.0, a negative image having a sufficiently high contrast can be obtained.

The developing agent used in the developing solution used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes in that good halftone dot quality can be easily obtained. Combinations of pyrazolidones or combinations of dihydroxybenzenes and p-aminophenols may be used.

As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
Although there are 2,5-dimethylhydroquinone and the like, hydroquinone is particularly preferred.

Examples of the developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-4-pyrazolidone and 1-phenyl-4-methyl-4. -Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5
-Methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone and the like.

Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. , 2-methyl-p-aminophenol and p-benzylaminophenol, among which N-methyl-p
-Aminophenol is preferred.

The developing agent is preferably used usually in an amount of 0.05 mol / to 0.8 mol /. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / to 0.5 mol /, and the latter is used in an amount of 0.06 mol / or less. preferable.

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
The sulfite is preferably 0.15 mol / mol or more, and particularly preferably 0.5 mol / mol or more. The upper limit is preferably up to 2.5 mol /.

Alkaline agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic, and potassium phosphate tribasic.
Contains pH adjusters and buffers. The pH of the developer is set between 10.5-12.3.

As additives used in addition to the above components, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, toluethylene glycol, dimethylformamide, methyl cellosolve , Organic solvents such as hexylene glycol, ethanol, methanol: 1-phenyl-5-mercaptotetrazole, indazole compounds such as 5-nitroindazole, fogging of benztriazole compounds such as 5-methylbenztriazole, inhibitors or the like. Black pepper inhibitor: may be contained, and if necessary, toning agent, surfactant, defoaming agent, water softener, hardener, amino compound described in JP-A-56-106244, etc. May be included.

The developing solution of the present invention is disclosed in JP-A-56-2 as a silver stain inhibitor.
The compounds described in 4,347 can be used. Compounds described in Japanese Patent Application No. 60-109,743 can be used as a solubilizing agent to be added to the developer. Also used for developer
The compound described in JP-A-60-93,433 or the compound described in Japanese Patent Application No. 61-27808 can be used as the pH buffer.

As the fixing agent, those having a commonly used composition can be used. As a fixing agent, thiosulfates and thiocyanates, and organic sulfur compounds known to have an effect as a fixing agent can be used. The fixing solution may contain water-soluble aluminum (for example, aluminum sulfate, bright bun, etc.) as a hardener. Here, the amount of the water-soluble aluminum salt is usually 0.4 to 2.0 g to Al /. Further, a trivalent iron compound can be used as an oxidizing agent as a complex with ethylenediaminetetraacetic acid.

The development temperature is usually selected between 18 ° C and 50 ° C, but is more preferably between 25 ° C and 43 ° C.

(Examples) Next, the present invention will be described more specifically based on examples. The following formulation was used for the developer.

(Example 1) (Preparation of emulsion of the present invention) Emulsion A: 0.13 M silver nitrate aqueous solution and 1 × 1 per 1 mol of silver
An aqueous solution of halogen salt containing 0.04M potassium bromide and 0.09M sodium chloride containing (NH ₄ ) ₃ RhCl ₆ corresponding to 0 ^-7 mol, sodium chloride, and 1,3-dimethyl-2-imidazolidinethione Nucleation was carried out by adding to the aqueous gelatin solution with stirring by a double jet method at 38 ° C. for 12 minutes to obtain silver chlorobromide grains having an average grain size of 0.15 μm and a silver chloride content of 70 mol%. Then likewise
0.87M silver nitrate aqueous solution, 0.26M potassium bromide, 0.65
A halogen salt aqueous solution containing M sodium chloride was added by a double jet method over 20 minutes.

Thereafter, 1 × 10 ^-3 mol of KI solution was added to perform conversion, washed with water by a flocculation method according to a conventional method, added with 40 g of gelatin, adjusted to pH 6.5 and pAg 7.5, and further, thiosulfuric acid was added per mol of silver. 5 mg sodium and 8 chloroauric acid
mg, and heated at 60 ° C for 60 minutes, subjected to chemical sensitization treatment,
As a stabilizer, 150 mg of 1,3,3a, 7-tetrazainden was added. The obtained grains have an average size of 0.27 μm and a silver chloride content of 70.
It was a mol% silver chlorobromide cubic grain. (Coefficient of variation 10
%).

Emulsion B: 0.13M silver nitrate aqueous solution and 1 × 10
^-7 mol equivalent of (NH ₄ ) ₃ RhCl ₆ containing 0.052M potassium bromide and 0.078M sodium chloride in halogen salt solution, sodium chloride and 1,3-dimethyl-2-imidazolidinethione Nucleation was performed by adding to an aqueous gelatin solution at 45 ° C. for 12 minutes with stirring by the double jet method to obtain silver chlorinated silver particles having an average particle size of 0.15 μm and a silver chloride content of 60 mol%. Then likewise
0.87M silver nitrate aqueous solution, 0.34M potassium bromide and 0.52M
A halogen salt aqueous solution containing M sodium chloride was added by a double jet method over 20 minutes.

After that, 1 × 10 ^-3 mol KI solution was added and conversion was performed, followed by washing with water by the flocculation method according to a conventional method, adding 40 g of gelatin to adjust the pH to 6.5 and pAg 7.5, and sodium thiosulfate per mol of silver. 5 mg and chloroauric acid 8
mg, and heated at 60 ° C for 60 minutes, subjected to chemical sensitization treatment,
4-hydroxy-6-methyl-1,3,3a, 7- as a stabilizer
Tetrazaindene 150 mg was added. The resulting grains were cubic silver chlorobromide grains having an average grain size of 0.27 μm and a silver chloride content of 60 mol%. (Coefficient of variation 10%).

(Preparation of Comparative Emulsion) Emulsion C: 0.13 M silver nitrate aqueous solution and 1 × 10 1 per mol of silver
-An aqueous solution of halogen salt containing 0.07M potassium bromide and 0.052M sodium chloride containing (NH ₄ ) ₃ RhCl ₆ equivalent to ^-7 mol was added to a gelatin aqueous solution containing sodium chloride at 45 ° C with stirring. Nucleation was performed for 12 minutes by the double jet method to obtain silver chlorobromide grains having an average grain size of 0.15 μm and a silver chloride content of 70 mol%. Subsequently, a silver salt aqueous solution containing 0.87 M silver nitrate aqueous solution, 0.522 M potassium bromide and 0.348 M sodium chloride was similarly added by a double jet method over 20 minutes.

Then, 1 × 10 ^-3 mol of KI solution was added and conversion was performed, followed by washing with water by the flocculation method according to a conventional method, adding 40 g of gelatin to adjust the pH to 6.5 and pAg 7.5, and further thiol per mol of silver. 5 mg of sodium sulfate and 8 mg of chloroauric acid were added, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization treatment, and 150 mg of 1,3,3a, 7-tetrazaindene was added as a stabilizer. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.27 μm and a silver chloride content of 40 mol%. (Variation coefficient 11%).

Emulsion D: 1 mol aqueous silver nitrate solution in the presence of ammonia in a gelatin aqueous solution kept at 50 ° C., and potassium iodide and potassium bromide aqueous solution containing 1.2 × 10 ⁻⁷ mol (NH ₄ ) ₃ RhCl ₆ per 1 mol silver. Were added simultaneously for 60 minutes, and the pAg was kept at 7.8 during that time to prepare a cubic monodisperse emulsion having an average grain size of 0.25 μm and an average silver iodide content of 1 mol%, and desalted by the flocculation method to give 40 g of gelatin. PH = 6.0 pAg = 8.
Prepared in 5, added sodium thiosulfate 5mg and chloroauric acid 6mg, heated at 60 ℃ for 60 minutes, subjected to chemical sensitization treatment, 4-hydroxy-6-methyl-1,3,3a, 7- as a stabilizer Tetrazaindene 150 mg was added.

(Variation coefficient 9%) These emulsions were divided into 1 × 10 ^-3 mol of 5-{[3- (4-sulfobutyl) -5 as a sensitizing dye per mol of silver.
-Chloro-2-benzooxazolidylidene] ethylidene} -1-hydroxyethoxyethyl-3- (2-pyridyl) -2-thiohydantoin K salt was added, and further 2
× 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole, 5 × 10 ^-4 mol of a short-wave cyanine dye represented by the following structural formula (a), a water-soluble latex represented by (b) (200 mg / m ² ). And a dispersion of polyethyl acrylate (200 mg / m ² ) 1,3-divinyl-sulfonyl-2-propanol (200 mg / m ² ) as a hardener, the hydrazine compound IV-19 of the present invention (5 × 10 ⁻³ mol) / Mol Ag), IV-7 (1 x
10 ^-4 mol / mol Ag) and an amine compound were added as shown in Table 1.

These emulsions and gelatin as a protective layer 1.0 g / m ² ,
Amorphous SiO ₂ matting agent with particle size of about 3.5μ 40 mg / m ² , methanol silica 0.1 g / m ² , polyacrylamide 100 mg /
m ² , hydroquinone 200 mg / m ² , silicone oil, and a fluorosurfactant represented by the following structural formula as a coating aid And a layer containing sodium dodecylbenzenesulfonate were simultaneously applied to prepare Samples 1 to 32 as shown in Table 1.

The back layer and the back layer protective layer were applied according to the following formulation.

(Back layer formulation)

Gelatin 3 g / m ² Latex Polyethyl acrylate 2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / m ² Dye Mixture of dyes [a], [b] and [c] Dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ² [Back protective layer] Gelatin 0.8 g / m ² Polymethylmethacrylate fine particles (average particle size 4.5μ) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² Dodecylbenzenesulfonic acid sodium salt 15 mg / m ² Fluorosurfactant 5 mg / m ² Sodium acetate 40 mg / m ² The evaluation was performed by the following test method.

(Photo Characteristics) Photo characteristics 1 are the results obtained by performing a 30 ° C. treatment at 34 ° C. using the FG-660F automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) with the developer having the above formulation.

 GR-F1 was used as the fixing solution.

Photographic characteristic 2 is 100% blackened Fujiris Orthofilm GA
-100 is a result obtained by processing 100 sheets of all size (50.8 cm × 61 cm) with a developing solution in the same manner as in Photographic Properties 1.

Here, the sensitivity is a relative value of the reciprocal of the exposure amount that gives a density of 1.5 in the development at 34 ° C. for 30 seconds.

Where γ is Defined by

As is clear from Table 1, Samples 2 to 5 and 10 to 13 of the present invention have good photographic characteristics 1 and 2.

Example 2 Emulsion A was divided and the same additives as in Example 1 were added,
Further, the hydrazine compound of the present invention IV-13 (1 × 10 ⁻³ mol / mol Ag), IV-7 (1 × 10 ⁻⁴ mol / mol Ag), and
Amine compounds were added as in Table 2.

(Preparation of Redox Compound-Containing Layer Emulsion) A 1.0 M silver nitrate aqueous solution and 3 × 10 ⁻⁷ mol of (NH ₄ ) ₃ RhCl ₆ per 1 mol of silver, 0.3 M potassium bromide and 0.74 M
An aqueous solution of a halogen salt containing sodium chloride is added to a gelatin aqueous solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione by a double jet method at 45 ° C. for 30 minutes while stirring to obtain an average particle size of 0.28.
Silver chlorobromide grains having a particle size of 70 μm and a silver chloride content of 70 mol% were obtained. After that, it is washed with flocculation according to the usual method,
Gelatin (40 g) was added to adjust the pH to 6.5 and pAg to 7.5, and sodium thiosulfate (5 mg) and chloroauric acid (8 mg) were further added per 1 mol of silver. The mixture was heated at 60 ° C for 60 minutes for chemical sensitization treatment, and then a stabilizer. As the amount, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added. The obtained grains were silver chlorobromide cubic grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%).

This emulsion was divided and used as a sensitizing dye in an amount of 1 per mole of silver.
× 10 ^-3 mol of 5-{[3- (4-sulfobutyl) -5chloro-1-benzoxazolidylidene] ethylidene}-
1-hydroxyethoxyethyl-3- (2-pyridyl)
-2-thiohydantoin K salt was added, and further 2 × 10 ^-4
Mol of 1-phenyl-5 main mercaptotetrazole, a dispersion of polyethyl acrylate and 50 mg / m ^2, 1,2-bis (vinyl sulfonyl acetamide) ethane 40 mg / m ^2, the redox compound of the present invention in Table 2 Was added.

The bottom layer of hydrazine-containing layer (Ag3.6g / m ² , gelatin 2g /
m ² ) and a layer containing a redox compound (Ag 0.4 g / m ² , gelatin 0.5 g / m ² ) via an intermediate layer (gelatin 0.5 g / m ² ).
m ² ) and gelatin 1.0 g / m ² as a protective layer on this, amorphous SiO ₃ matting agent 40 mg / m ^{2 with} a particle size of about 3.5 μ, methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² ,
Hydroquinone 200 mg / m ² and silicone oil and fluorine surfactant represented by the following structural formula as a coating aid And a layer containing sodium dodecylbenzene sulfonate were simultaneously applied to prepare samples as shown in Table 2 to evaluate photographic performance and image quality.

As is clear from Table 2, the samples 34 to 45 of the present invention have sensitivity γ
Decrease of 35 to 45 including redox compound
Has significantly improved image quality.

 The image quality of the line drawing was evaluated as follows.

After photographing a manuscript consisting of 7th grade Mincho typeface and Gosic typeset letters with reflection density in the range of 0.5 to 1.2 with the Dainippon Screen camera (DSC351), under the same conditions as the photographic characteristics,
This is the result of performing development processing (34 ° C., 30 ″).
Performed in five stages, "5" represents the best and "1" represents the worst quality. "5" or "4" is practical and "3" is bad, but practically available, "2" or "1" is practically impossible.

Example 3 Each sample of Examples 1 and 2 was processed in exactly the same manner as in Examples 1 and 2 except that the following developing solution A was used, and similar results were obtained.

At this time, add potassium hydroxide to adjust the pH to 11.7.

Claims (2)

(57) [Claims] 1. A photosensitive silver halide emulsion layer containing at least one hydrazine derivative on a support, and an amine compound having at least two repeating ethylene oxide groups in the emulsion layer or other hydrophilic colloid layers. A negative-working silver halide photographic light-sensitive material, characterized in that the silver halide emulsion comprises 50 mol% or more of silver chloride. 2. An emulsion layer or other hydrophilic colloid layer,
The silver halide photographic light-sensitive material according to claim 1, which contains a redox compound which releases a phenomenon suppressor when oxidized.