JP2687177B2 - Silver halide photographic material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a super-high contrast silver halide photographic light-sensitive material used for photolithography.

(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 has been found that the ortho-sensitized photographic material is more strongly affected by the chromatic aberration of the lens, so that the image quality is liable to deteriorate. This deterioration is more remarkable for a xenon lamp light source.

As a system that responds to a wide range of latitude, a lith-type silver halide light-sensitive material made of silver chlorobromide (at least a silver chloride content of 50% or more) has an extremely low effective concentration of sulfite ion (usually 0.1 mol / l or less). ) A method is known in which 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, is obtained by treating with a hydroquinone developer. However, in this method, since the concentration of sulfurous acid in the developer is low, development is extremely unstable against air oxidation, and various efforts and efforts have been made to keep the solution activity stable. Was extremely slow, and the work efficiency was reduced at present.

For this reason, an image forming system that eliminates instability of image formation by the above-described developing method (lith developing system), develops with a processing solution having good storage stability, and obtains ultra-high contrast photographic characteristics is provided. U.S. Pat. Nos. 4,166,742, 4,168,977, 4,221,857,
4,224,40, 4,243,739, 4,272,606, 4,311,
No. 781, a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound is added,
A system has been proposed which forms a super-high contrast negative image in which γ exceeds 10 by treating with a developer having a storage stability of 0.15 mol / l or more at pH 11.0 to 12.3 and having a good storage stability. . This new image forming system can use only silver chlorobromide having a high silver chloride content in conventional ultra-high contrast image formation, but can also use silver iodobromide and silver chloroiodobromide. There is.

The above image system has excellent performance in terms of sharp halftone dot quality, processing stability, speed and original reproducibility, but is more stable and improved in original reproducibility to deal with the recent variety of printed matter. A desired system is desired.

Examples of a system using hydrazine containing a redox compound which releases a development inhibitor upon being oxidized are disclosed in JP-A Nos. 61-213847 and 64-72140. On the other hand, an example containing a thioamide compound is disclosed in JP-A-53-137133.
No. 61-47943 and Japanese Patent Application No. 62-278692.

(Problems to be Solved by the Present Invention) A first object of the present invention is to provide a silver halide photographic light-sensitive material excellent in image quality such as line drawing or drawing and contraction characteristics.

A second object of the present invention is to provide a silver halide photographic light-sensitive material which is less susceptible to decrease in sensitivity, γ and Dmax even if pH is lowered by treating a large amount of film and bromine ion concentration is increased. Is.

(Means for Solving Problems) In the silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on the support, the above-mentioned object of the present invention is the emulsion layer or other hydrophilic colloid layer. And a hydrazine derivative, a compound having a thioamide bond, and at least one redox compound that releases a development inhibitor by being oxidized, respectively.

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 hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines and reductones, and more preferably hydrazines.

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.

In these formulas, R ¹ represents an aliphatic group or an aromatic group. G ₁ is -SO- group, -SO ₂ - group or Represents G ₂ is a mere bond, -O-, -S- or Represents 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 tail, carboxyl group, sulfo group or -G ₁ -G ₂ -R ₁ - represents a.

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. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. The alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, and a carbonamide group.

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

For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring.

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 group,
Urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy Group, carbonamido group, sulfonamide group, carboxyl group, phosphoric acid amide group, etc., and preferable substituents are linear, branched or cyclic alkyl groups (preferably having 1 to 20 carbon atoms) and aralkyl groups. (Preferably a monocyclic or bicyclic C1-C20 alkyl moiety),
Alkoxy group (preferably having 1 to 30 carbon atoms), substituted amino group (preferably amino group substituted with an alkyl group having 1 to 30 carbon atoms), acylamino group (preferably having 2 to 40 carbon atoms) , Sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms), phosphoric acid amide group (preferably having 1 to 40 carbon atoms), etc. .

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

A ₁ and A ₂ are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or the sum of Hammett's substituent constants is -0.5).
A phenylsulfonyl group substituted as described above),
An acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is −0.5 or more, or a linear or branched or cyclic unsubstituted or substituted fat Group acyl groups (substituents include, for example, halogen atoms, ether groups, sulfonamide groups, carbonamide groups, hydroxyl groups, carboxy groups, and sulfonic acid groups) are preferred.

A hydrogen atom is most preferable as A ₁ and A ₂ .

A ₃ is a hydrogen atom, Is most 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. t represents 0 or 1.

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

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.
U.S. Pat. No. 4,310,612 (Japanese Unexamined Patent Publication No.
-53,330) and 4,358,526 and the like, which releases PUG by an intramolecular ring closure reaction after ring cleavage; U.S. Pat. Nos. 4,330,617, 4,446,216, 4,483,919, and JP-A-59-121,328. Release of PUG with formation of acid anhydride by intramolecular ring closure reaction of carboxyl group of succinic acid monoester or analog thereof described; U.S. Pat.Nos. 4,409,323 and 4,421,845, Research Disclosure No. 21,228 (December 1981), US Patent No. 4,41
No. 6,977 (JP-A-57-135,944), JP-A-58-209,736
No. 58-209, 738, etc. to produce quinomonomethane or an analog thereof by electron transfer via a double bond conjugated to an aryloxy or heterocyclic oxy group
US Pat. No. 4,420,554 (Japanese Unexamined Patent Publication No. 57-1)
No. 36,640), JP-A-57-135,945, JP-A-57-188,035,
Nos. 58-98,728 and 58-209,737 which release a PUG from the γ-position of enamine by electron transfer of a portion having an enamine structure of a nitrogen-containing heterocyclic ring;
No. 4,146,396, which releases PUG by an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated to a nitrogen atom of a nitrogen-containing heterocyclic ring described in US Pat.
No. 52/90932, 59-93,442, 59-
75475, JP-A-60-249148, JP-A-60-249149, etc., which release PUG with formation of aldehydes; JP-A-51-146,828, JP-A-57-179,842; 59-104,6
No. 41, which releases PUG with decarboxylation of the carboxyl group; -O-COOCR _a R _b -PUG (R _a and R _b represent monovalent groups) and Those releasing PUG with carbonic acid and subsequent formation of aldehydes; JP-A-60-7,429
Examples of the compound that releases PUG with formation of an isocyanate described in U.S. Pat. No. 4,438,193 and the like that releases PUG by a coupling reaction with an oxidant of a color developing agent described in U.S. Pat. No. 4,438,193.

The divalent group represented by Time in the general formulas (R-1), (R-2) and (R-3) is preferably the following general formula (T-
From 1), it is represented by the general formula (T-6). In these, ** indicates the site where Time binds to PUG, and * indicates the other site.

Wherein W is an oxygen atom, a sulfur atom or R ₁₁ and R ₁₂ represent a hydrogen atom or a substituent, R ₁₃ represents a substituent, and t represents 1 or 2. When t is 2, two Represents the same or different. R ₁₁ and R
_{When 12} represents a substituent and typical examples of R ₁₃ are R ₁₄ group, R ₁₄ CO— group, R ₁₄ SO ₂ — group, Or And the like. Here, R ₁₄ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₁₅ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom.

Each of R ₁₁ , R ₁₂ and R ₁₃ represents a divalent group and is also included when they are linked to each other to form a cyclic structure. General formula (T
Specific examples of the group represented by -1) include the following groups.

* -OCH ₂ -** ＊ －SCH ₂ － ＊＊ Formula (T-2) * -Nu-Link-E-** In the formula, Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, and Nu represents Link is a group that can be more nucleophilically attacked to cleave the bond with **
Nu represents a linking group that sterically relates to E so that an intramolecular nucleophilic substitution reaction can occur. General formula (T-2)
Specific examples of the group represented by are, for example, the following.

In the formula, W, R ₁₁ , R ₁₂ and t have the same meanings as described for (T-1). Specific examples include the following groups.

In the formula, W and R ₁₁ have the same meanings as described in the general formula (T-1). Specific examples of the group represented by the general formula (T-6) include the following groups.

Further, as the Time, the general formula (T-1) to the general formula (T-
Groups formed by combining a plurality of groups represented by 6) are also useful. Preferred examples thereof are shown below. *, *
* Has the same meaning as in formulas (T-1) to (T-6).

Specific examples of the divalent linking group represented by Time are also described in detail in JP-A-61-236,549, JP-A-64-88451 and JP-A-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 Macmilla
n) It is described in pages 344 to 346 of the company. Specifically, mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, mercaptopyrimidines, mercaptobenzimidazoles, mercaptobenzthiazoles, mercaptobenzoxazoles, mercaptothiadiazoles, benztriazoles, benzimidazoles, indazole. Examples thereof include adenines, adenines, guanines, tetrazoles, tetraazaindenes, triazaindenes, and mercaptoarenes.

The development inhibitor represented by PUG may be substituted. Examples of the substituent include the following, but these groups may be further substituted.

For example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group. Group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, sulfoxy group, phosphono Group, phosphinico group, phosphoric acid amide group and the like.

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.

 The main development inhibitors are shown below.

1 Mercaptotetrazole derivative (1) 1-phenyl-5-mercaptotetrazole (2) 1- (4-hydroxyphenyl) -5-mercaptotetrazole (3) 1- (4-aminophenyl) -5-mercaptotetrazole (4) 1- (4-carboxyphenyl) -5-mercaptotetrazole (5) 1- (4-chlorophenyl) -5-mercaptotetrazole (6) 1- (4-methylphenyl) -5-mercaptotetrazole (7) 1- ( 2,4-Dihydroxyphenyl) -5-mercaptotetrazole (8) 1- (4-sulfamoylphenyl) -5-mercaptotetrazole (9) 1- (3-carboxyphenyl) -5-mercaptotetrazole (10) 1 -(3,5-Dicarboxyphenyl) -5-mercaptotetrazole (11 1- (4-methoxyphenyl) -5-mercaptotetrazole (12) 1- (2-methoxyphenyl) -5-mercaptotetrazole (13) 1- [4- (2-hydroxyethoxy) phenyl] -5-mercapto Tetrazole (14) 1- (2,4-dichlorophenyl) -5-mercaptotetrazole (15) 1- (4-Dimethylaminophenyl) -5-mercaptotetrazole (16) 1- (4-Nitrophenyl) -5-mercapto Tetrazole (17) 1,4-bis (5-mercapto-1-tetrazolyl) benzene (18) 1- (α-naphthyl) -5-mercaptotetrazole (19) 1- (4-sulfophenyl) -5-mercaptotetrazole (20) 1- (3-Sulfophenyl) -5-mercaptotetrazole (21) 1- (β-naphthyl) -5-merka Putotetrazole (22) 1-Methyl-5-mercaptotetrazole (23) 1-Ethyl-5-mercaptotetrazole (24) 1-Propyl-5-mercaptotetrazole (25) 1-octyl-5-mercaptotetrazole (26) 1 -Dodecyl-5-mercaptotetrazole (27) 1-cyclohexyl-5-mercaptotetrazole (28) 1-palmityl-5-mercaptotetrazole (29) 1-carboxyethyl-5-mercaptotetrazole (30) 1- (2,2 -Diethoxyethyl) -5-mercaptotetrazole (31) 1- (2-aminoethyl) -5-mercaptotetrazole hydrochloride (32) 1- (2-diethylaminoethyl) -5-mercaptotetrazole (33) 2- ( 5-mercapto-1-tetrazolyl) ethyltrimethylammoni Mukurorido (34) 1- (3-phenoxycarbonyl-phenyl) -
5-mercaptotetrazole (35) 1- (3-maleimidophenyl) -6-mercaptotetrazole 2 mercaptotriazole derivative (1) 4-phenyl-3-mercaptotriazole (2) 4-phenyl-5-methyl-3-mercapto Triazole (3) 4,5-diphenyl-3-mercaptotriazole (4) 4- (4-carboxyphenyl) -3-mercaptotriazole (5) 4-methyl-3-mercaptotriazole (6) 4- (2-dimethyl Aminoethyl) -3-mercaptotriazole (7) 4- (α-naphthyl) -3-mercaptotriazole (8) 4- (4-sulfophenyl) -3-mercaptotriazole (9) 4- (3-nitrophenyl) -3-Mercaptotriazole 3 mercaptoimidazole induction Body (1) 1-phenyl-2-mercaptoimidazole (2) 1,5-diphenyl-2-mercaptoimidazole (3) 1- (4-carboxyphenyl) -2-mercaptoimidazole (4) 1- (4-hexyl Carbamoyl) -2-mercaptoimidazole (5) 1- (3-nitrophenyl) -2-mercaptoimidazole (6) 1- (4-sulfophenyl) -2-mercaptoimidazole 4 mercaptopyrimidine derivative (1) Thiouracil (2) Methylthiouracil (3) Ethylthiouracil (4) Propylthiouracil (5) Nonylthiouracil (6) Aminothiouracil (7) Hydroxythiouracil 5 Mercaptobenzimidazole derivative (1) 2-Mercaptobenzimidazole (2) 5- Carboxy-2-me Lucaptobenzimidazole (3) 5-Amino-2-mercaptobenzimidazole (4) 5-Nitro-2-mercaptobenzimidazole (5) 5-Chloro-2-mercaptobenzimidazole (6) 5-Methoxy-2-mercapto Benzimidazole (7) 2-mercaptonaphthoimidazole (8) 2-mercapto-5-sulfone benzimidazole (9) 1- (2-hydroxyethyl) -2-mercaptobenzimidazole (10) 5-caproamide-2-mercaptobenz Imidazole (11) 5- (2-ethylhexanoylamino) -2-
Mercaptobenzimidazole 6 Mercaptothiadiazole derivative (1) 5-methylthio-2-mercapto-1,3,4-thiadiazole (2) 5-ethylthio-2-mercapto-1,3,4-thiadiazole (3) 5- (2 -Dimethylaminoethylthio) -2-
Mercapto-1,3,4-thiadiazole (4) 5- (2-carboxypropylthio) -2-mercapto-1,3,4-thiadiazole (5) 5-phenoxycarbonylmethylthio-5-mercapto-1,3, 4-thiadiazole 7 mercaptobenzthiazole derivative (1) 2-mercaptobenzthiazole (2) 5-nitro-2-mercaptobenzthiazole (3) 5-carboxy-2-mercaptobenzthiazole (4) 5-sulfo-2-mercapto Benzthiazole 8 mercaptobenzoxazole derivative (1) 2-mercaptobenzoxazole (2) 5-nitro-2-mercaptobenzoxazole (3) 5-carboxy-2-mercaptobenzoxazole (4) 5-sulfo-2-mercaptobenz Oxazole 9 benztriazo Derivative (1) 5,6-dimethylbenzotriazole (2) 5-butylbenzotriazole (3) 5-methylbenzotriazole (4) 5-chlorobenzotriazole (5) 5-bromobenzotriazole (6) 5,6 -Dichlorobenzotriazole (7) 4,6-Dichlorobenzotriazole (8) 5-Nitrobenzotriazole (9) 4-Nitro-6-chloro-benzotriazole (10) 4,5,6-Trichlorobenzotriazole (11) 5-Carboxybenzotriazole (12) 5-sulfone benzotriazole Na salt (13) 5-methoxycarbonylbenzotriazole (14) 5-aminobenzotriazole (15) 5-butoxybenzotriazole (16) 5-ureidobenzotriazole ( 17) Benzotriazole (18) 5-Phenoki Carbonylbenzotriazole (19) 5- (2,3-dichloropropyloxycarbonyl) benzotriazole 10 Benzimidazole derivative (1) Benzimidazole (2) 5-chlorobenzimidazole (3) 5-nitrobenzimidazole (4) 5- n-Butylbenzimidazole (5) 5-methylbenzimidazole (6) 5-chlorobenzimidazole (7) 5,6-dimethylbenzimidazole (8) 5-nitro-2- (trifluoromethyl) benzimidazole 11 Indazole derivative (1) 5-nitroindazole (2) 6-nitroindazole (3) 5-aminoindazole (4) 6-aminoindazole (5) indazole (6) 3-nitroindazole (7) 5-nitro-3-chloroindazole (8) 3-Chloro-5-itreindazole (9) 3-carboxy-5-nitroindazole 12 tetrazole derivative (1) 5- (4-nitrophenyl) tetrazole (2) 5-phenyltetrazole (3) 5- (3-carboxy Phenyl) -tetrazole 13 tetrazaindene derivative (1) 4-hydroxy-6-methyl-5-nitro-1,
3,3a, 7-Tetraazandene (2) 4-mercapto-6-methyl-5-nitro-1,
3,3a, 7-Tetraazandene 14 mercaptoaryl derivative (1) 4-nitrothiophenol (2) thiophenol (3) 2-carboxythiophenol Further, general formulas (R-1), (R-2), ( In R-3), R ₁ or Time _t PUG is a ballast group or a general formula (R-1), (R-2) or (R-2) which is commonly used in a non-moving photographic additive such as a coupler. A group which promotes adsorption of the compound represented by -3) 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 A cyclic thioamide group such as oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzthiazoline-2-thione, thiotriazine, 1,3-imidazoline-2-thione, chain thioamide Group, an aliphatic mercapto group, an aromatic mercapto group, a heterocyclic mercapto group (when the carbon atom to which the --SH group is bound is a nitrogen atom, it is synonymous with the cyclic thioamide group having a tautomeric relationship with this. , Specific examples of this group are the same as those listed above.), A group having a disulfide bond, benzotriazole, triazole, tetrazo Le, indazole, benzimidazole, imidazole, benzothiazole,
Nitrogen, oxygen, such as thiazole, thiazoline, benzoxazole, oxazole, oxazoline, thiadiazole, oxathiazole, triazine, azaindene,
Examples thereof include a 5- or 6-membered nitrogen-containing heterocyclic group composed of a combination of sulfur and carbon, and a heterocyclic quaternary salt such as benzimidazolinium.

These may be further substituted with a suitable substituent.

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

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

As the redox compound used in the present invention, in addition to those described above, for example, JP-A-61-213847 and JP-A-62-260,1.
No. 53, Japanese Patent Application No. 1-102,393, No. 1-102,394, No. 1-102,39
Those described in No. 5 and No. 1-114,455 can be used.

The method for synthesizing the redox compound used in the present invention is described, for example, in JP-A-61-213,847, JP-A-62-260,153, U.S. Pat.
684,604, Japanese Patent Application No. 63-98,803, U.S. Patent No. 3,379,529
Nos. 3,620,746, 4,377,634, 4,332,878,
It is described in JP-A-49-129,536, JP-A-56-153,336, JP-A-56-153,342 and the like.

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, oil such as dibutyl phthalate, tricresyl phosphate, glycerin triacetate or diethyl phthalate is dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. It is also possible to create and use things. 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 hydrazine derivative used in the present invention is preferably a compound represented by the following general formula (I).

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, a carbamoyl group or an oxycarbonyl group, and G ₁ represents Carbonyl group, sulfonyl group, sulfoxy group, Or an iminomethylene group, wherein B ₁ and B ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. Represents a group.

In the general formula (I), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, and particularly preferably has 1 to 30 carbon atoms.
20 linear, branched or cyclic alkyl groups. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. The alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, and a carbonamide group.

The aromatic group represented by R ₁ in the general formula (I) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring.

Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and typical examples of the substituent 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, Acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group,
Alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group,
Sulfo group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group,
Examples thereof include an acyloxy group, a carbonamido group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, an imide group, and the like, and a preferable substituent is a linear, branched, or cyclic alkyl group (preferably having a carbon number. 1 to 20), aralkyl group (preferably having 1 to 3 carbon atoms in the alkyl moiety), alkoxy group (preferably having 1 to 20 carbon atoms), substituted amino group (preferably Is an amino group substituted with an alkyl group having 1 to 20 carbon atoms, and an acylamino group (preferably having 2 to 2 carbon atoms).
30), a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 carbon atom)
.About.30), phosphoric acid amide group (preferably having 1 to 30 carbon atoms), and the like.

The alkyl group represented by R ₂ in formula (I) is preferably an alkyl group having 1 to 4 carbon atoms, which is a halogen atom, a cyano group, a carboxy group, a sulfo group, an alkoxy group, a phenyl group, a sulfonyl group. It may have a substituent such as.

As the aryl group, a monocyclic or bicyclic aryl group is preferable, and for example, those containing a benzene ring. The aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group, a sulfonyl group, or the like.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

The aryloxy group is preferably a monocyclic one, or the substituent includes a halogen atom and the like.

As the amino group, an unsubstituted amino group and a group having 1 to 10 carbon atoms
Are preferred, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, or the like.

The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms, or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or an aryloxycarbonyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group or the like.

Preferred among the groups represented by R ₂ are a hydrogen atom and an alkyl group (for example, when G ₁ is a carbonyl group).
Methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc., aralkyl group (for example,
and an aryl group (for example, a phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, a 4-methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferable.

When G ₁ is a sulfonyl group, R ₂ is an alkyl group (eg, methyl group) or an aralkyl group (eg, o).
A hydroxyphenylmethyl group), an aryl group (e.g., a phenyl group) or a substituted amino group (e.g.,
And a dimethylamino group.

When G ₁ is a sulfoxy group, preferred R ₂ is a cyanobenzyl group, a methylthiobenzyl group or the like, and G ₁ is In this case, R ₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group or a phenyl group, and particularly preferably a phenoxy group.

When G ₁ is an N-substituted or unsubstituted iminomethylene group, preferred R ₂ is a methyl group, an ethyl group or a substituted or unsubstituted phenyl group.

As the substituent for R _2, the substituents listed for R ₁ can be applied.

G in the general formula (I) is most preferably a carbonyl group.

R ₂ also splits the G ₁ -R ₂ moiety from the rest of the molecule,
It may be one that causes a cyclization reaction to form a cyclic structure containing an atom of the G ₁ -R ₂ moiety, and is specifically one that can be represented by the general formula (a). .

In the general formula (a) -R ₃ -Z ₁ formula, Z ₁ is nucleophilically attacked to G _1, G ₁ -R ₃ -Z
The _first part is a group capable of splitting from the remainder molecule, R ₃ is R ₂
It is a compound in which one hydrogen atom is removed from the above, and Z ₁ can nucleophilically attack G ₁ to form a cyclic structure with G ₁ , R ₃ and Z ₁ .

More specifically, Z easily undergoes a nucleophilic reaction with G ₁ when the hydrazine compound of the general formula (I) produces the next reaction intermediate due to oxidation or the like, R ₁ -N = N-G ₁ -R _3- Z ₁ R ₁ —N═N is a group capable of splitting N group from G ₁ , and specifically includes OH, SH or NHR ₄ (R ₄ is a hydrogen atom, an alkyl group, an aryl group, —COR ₅ , or —SO ₂ R ₅ and R ₅ may be a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or the like), or a functional group which directly reacts with G ₁ such as COOH (wherein , OH, SH, NHR ₄ , and -COOH may be temporarily protected so as to generate these groups by hydrolysis of alkali etc.) (Wherein R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group), a nucleophile such as a hydroxide ion or a sulfite ion is reacted to produce G ₁
It may be a functional group capable of reacting with.

The ring formed by G ₁ , R ₃ and Z ₁ is preferably a 5-membered or 6-membered ring.

Among the compounds represented by the general formula (a), preferred are the compounds represented by the general formulas (b) and (c).

In the formula, R _b ^{1 to} R _b ⁴ are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms), aryl groups (preferably having carbon atoms). 6 to 12) etc., and may be the same or different.
B is an atom necessary to complete a 5- or 6-membered ring which may have a substituent, m and n are 0 or 1, and
(N + m) is 1 or 2.

As the 5- or 6-membered ring formed by B, for example,
A cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and the like.

Z ₁ has the same meaning as in formula (a).

In the formula, R _c ¹ and R _c ² represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a halogen atom, and may be the same or different.

R _c ³ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

 p represents 0 or 1. q represents 1-4.

R _c ¹ , R _c ² and R _c ³ may combine with each other to form a ring as long as Z ₁ has a structure capable of intramolecular nucleophilic attack on G ₁ .

R _c ¹ and R _c ² are preferably a hydrogen atom, a halogen atom or an alkyl group, and R _c ³ is preferably an alkyl group or an aryl group.

q preferably represents 1-3, and when q is 1, p is 1
Or 2, p is 0 or 1 when q is 2, p is 0 or 1 when q is 3, CR when q is 2 or 3
_c ¹ R _c ² may be the same or different.

Z ₁ has the same meaning as in formula (a).

A ₁ and A ₂ are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or a sum of substituent constants of hamet is -0.5).
A phenylsulfonyl group substituted as described above),
An acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of the substituent constants of a hamet is −0.5 or more, or a linear or branched or cyclic unsubstituted or substituted fat Group acyl group (eg, a substituent includes a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group). As B ₁ and B ₂ , a hydrogen atom is most preferable.

R ₁ or R _{2 in} the general formula (I) may have a ballast group incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. Can be.

R ₁ or R _{2 in} the general formula (I) may have a group in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of such an adsorbing group include thiourea group, heterocyclic thioamide group, mercapto heterocyclic group, triazole group and the like U.S. Patent Nos. 4,385,108 and 4,459,347;
59-195,233, 59-200,231, 59-201,045, 59
-201,046, 59-201,047, 59-201,048, 59-2
01,049, JP 61-170,733, 61-270,744, 62
-948, Japanese Patent Application No. 62-67,508, 〃 62-67,501, 〃 62-67,
Examples thereof include the groups described in No. 510.

Specific examples of the compound represented by the general formula (I) 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 those described 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, U.S. Patent 2,011,391B,
JP-A-60-179734, JP-A-62-270,948, JP-A-63-29,751,
JP-A-61-170,733, JP-A-61-270,744, JP-A-62-948, EP
217,310, Japanese Patent Application No. 61-175,234, 〃61-251,482, 〃6
1-268,249, 〃61-276,283, 〃62-67528, 〃62-6
7,509, 〃 62-67,510, 〃 62-58,513, 〃 62-130,81
No. 9, 〃 62-143,467, 〃 62-166,117, or US 4,68
6,167, Japanese Patent Application No. 62-178,246, Japanese Patent Application No. 63-234,244,
63-234,245, 63-234,246, 63-294,552,
63-306,438, Japanese Patent Application No. 62-166,117, 〃62-247,478,
〃 63-106,682, 〃 63-114,118, 〃 63-110,051 and 〃
63-114,119, 〃63-116,239, 〃63-147,339, 〃63
-179,760, 〃63-229,163, Japanese Patent Application 1-18,377, 〃1-
18,378, 〃1-18,379, 〃1-15,755, 〃1-16,814
No. 1, 〃 1-40,792, 〃 1-42,615, 〃 1-42,616 can be used.

In the present invention, when the hydrazine derivative represented by the general formula (I) is contained in a photographic light-sensitive material, it is preferable that the hydrazine derivative be contained in a silver halide emulsion layer, but other non-light-sensitive hydrophilic colloid layers (for example, a protective layer) , An intermediate layer, a filter layer, an antihalation layer, etc.). 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. When it is added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added after chemical ripening to before coating. Particularly, it is preferable to add it to a coating solution prepared for coating.

In the present invention, the hydrazine derivative represented by the general formula (I) is preferably contained in an amount of 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide, particularly preferably 1 × 10 ^-5 to 4 × 10 ^-1 mol. ^-3 mol is preferably contained.

Next, as the thioamide compound used in the present invention, a compound represented by the following general formula (III) is preferable.

In the formula, R ₁₃ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic residue. Q is a mere bond, a sulfur atom or a selenium atom as a divalent group, an oxygen atom as a divalent group, a disulfide group (-SS-) NR ₁₄ , Or represents NR ₁₄ CS. However, R ₁₄ has the same meaning as R ₁₃ .

R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue or an amino group. A 5-membered or 6-membered heterocycle may be formed between R ₁₃ and R ₁₄ , R ₁₁ and R ₁₂ , or R ₁₁ and R ₁₃ . However, when a 5-membered or 6-membered heterocycle is formed between R ₁₁ and R ₁₃ , R ₁₂ and R ₁₄
Neither represents a hydrogen atom.

The alkyl group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ has 1 to 20 carbon atoms and includes a substituted one. Examples of the substituent include a halogen atom (for example, chlorine atom), a cyano group, a carboxy group, a hydroxy group, an alkyloxy group having 2 to 6 carbon atoms (for example, acetoxy group), and 2 to 2 carbon atoms.
There are 22 alkoxycarbonyl groups (eg, ethoxycarbonyl group, butoxycarbonyl group, aryl group (monocyclic or bicyclic group, which may be substituted. For example, phenyl group, tolyl group, p-sulfophenyl group) and the like. Examples of preferred alkyl groups are: methyl groups, ethyl groups, propyl groups (n- or i-), butyl groups (n-,
i- or t-), amyl (may have a branch, the same applies hereinafter), hexyl group, octyl group, dodecyl group, pentadecyl group, heptadecyl group, chloromethyl group, 2-chloroethyl group, 2-cyanoethyl group, carboxy Methyl group,
2-carboxyethyl group, 2-hydroxyethyl group, 2
-Acetoxyethyl group, acetoiciethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, 2
-Methoxycarbonylethyl group, benzyl group, o-nitrobenzyl group, p-sulfobenzyl group.

The aryl group represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ is a monocyclic or bicyclic, preferably monocyclic aryl group and includes a substituted one. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group,
Nonyl group), alkoxy group having 1 to 20 carbon atoms (eg methoxy group, ethoxy group), hydroxy group, halogen atom (eg chlorine atom, bromine atom), carboxy group, sulfo group and the like. Specific examples of the aryl group include a phenyl group,
p-tolyl group, p-methoxyphenyl group, p-hydroxyphenyl group, p-chlorophenyl group, 2,5-dichlorophenyl group, p-carboxyphenyl group, o-carboxyphenyl group, 4-sulfophenyl group, 2,4 -Disulfophenyl group, 2,5-disulfophenyl group, 3-sulfophenyl group, 3,5-disulfophenyl group and the like.

As the heterocyclic residue of R ₁₁ , R ₁₂ , R ₁₃ or R ₁₄ ,
It is preferably a 5- to 7-membered one, for example, pyrrolidine, pyrrole, tetrahydrofuran, furan, tetrahydrothiophene, thiophene, thiazole, thiadiazoline, oxazole, oxazoline, imidazole, imidazoline, triazole, tetrazole, thiadiazole, oxadiazole, benzothiazole. , Benzoxazole, benzimidazole, morpholine, pyridine, quinoline, quinoxaline, azepine and the like. These may be substituted with the groups described as substituents for R ₁ to R ₃ .

The 5- or 6-membered ring formed by R ₁₃ and R ₁₄ or R ₁₁ and R ₁₂ includes, for example, a piperidine ring, a piperazine ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, and the like. Is the piperidine ring,
A pyrrole ring, a piperazine ring and a morpholine ring.

The 5- or 6-membered heterocyclic ring formed between R ₁₁ and R ₁₃ is, for example, a rhodanine ring, a thiazoline ring, a thiazolidine ring, a selenazoline ring, an oxazoline ring, an oxazolidine ring, an imidazoline ring, an imidazolidine ring, a pyrazoline ring, Pyrazolidine ring, 1,3,4-thiadiazoline ring, 1,3,4
-Oxadiazoline ring, 1,3,4-triazoline ring, tetrazoline ring, thiohydantoin ring, dihydropyridine ring, dihydropyrimidine ring, dihydrotriazine ring and the like. These heterocycles of course include those in which a 5- to 7-membered carbon ring or heterocycle is condensed. That is, benzothiazoline nucleus, naphthothiazoline nucleus, dihydronaphthothiazoline nucleus, tetrahydrobenzothiazoline nucleus, etc. for thiazole ring; benzoselenazoline nucleus, etc. for selenazole ring; benzoxazoline nucleus, naphthoxazoline nucleus, etc. for oxazoline ring; benzimidazoline ring for imidazoline ring Nuclei, dihydroimidazolopyrimidine nuclei, etc .; triazoline rings, dihydrotriazolopyridine nuclei, dihydrotriazolopyrimidine nuclei, etc .; pyrazoline rings, dihydropyrazolopyridine nuclei, dihydropyrazolopyrimidine nuclei, etc .; dihydropyrimidine rings, dihydropyrazolopyrimidine nuclei, etc. , Dihydropyrrolopyrimidine nuclei, dihydrotriazolopyrimidine nuclei, and the like.

Various substituents can be present on the carbon atoms of these heterocyclic nuclei. For example, an alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, n-butyl group, t
-Butyl group, heptyl group, heptadecyl group), carbon number 1
~ 20 alkoxy groups (eg methoxy group, ethoxy group, dodecyloxy group, heptadecyloxy group), alkylthio groups having 1 to 20 carbon atoms (eg methylthio group, ethylthio group, butylthio group), hydroxy group, mercapto group, amino Group (including not only unsubstituted but also substituted amino group, alkyl-substituted amino group such as dimethylamino group, methylamino group, diethylamino group, butylamino group, benzylamino group; aryl-substituted group such as anilino group and diphenylamino group) Amino group; acetylamino group,
Cabryloylamino group, benzoylamino group, methylsulfonylamino group, benzenesulfonylamino group, p-
Acylamino group such as toluenesulfonylamino group; acetylthioamide group, thioamide group such as propionylthioamide group), aryl group (eg phenyl group, naphthyl group, tolyl group), alkenyl group having 2 to 20 carbon atoms (eg allyl group, Methallyl group), an aralkyl group having 1 to 4 carbon atoms in the alkyl moiety (eg, benzyl group,
Phenethyl group), halogen atom (eg chlorine, bromine), cyano group, carboxy group, sulfo group, carbamoyl group (including substituted ones, for example, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group,
Ethylcarbamoyl group, phenylcarbamoyl group), thiocarbamoyl group (including substituted ones, for example, thiocarbamoyl group, methylthiocarbamoyl group, dimethylthiocarbamoyl group, ethylthiocarbamoyl group,
Phenylthiocarbamoyl group), C2-C22 alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (eg phenoxycarbonyl group), C2-C22 alkylcarbonyl group (For example, an acetyl group, a cabryloyl group), an oxygen atom, or the like. The alkyl group further includes a carboxy group, a sulfo group, an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group), an acyloxy group (for example, an acetoxy group), an aryl group (for example, a phenyl group, and a nitrophenyl group which may be substituted. ) May be substituted.

R ₁₂ is present on the substitutable fluorine atom in the heterocyclic chain.
Can have substituents as shown for.

When Q represents NR ₁₄ , the alkyl group represented by R ₁₄ has 1 to 20 carbon atoms and includes those substituted. Examples of the substituent for the alkyl group are a halogen atom, a cyano group, a carboxy group, a sulfo group, a sulfato group, a phospho group, a carbamoyl group, an aminosulfonyl group, a hydroxy group, an alkoxy group having 1 to 20 carbon atoms (for example, a methoxy group, Ethoxy group, propoxy group, butoxy group: Substituted groups are also included, for example, hydroxy group,
An alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, propoxy group), an acyloxy group having 2 to 8 carbon atoms (eg, acetoxy group, propionoxy group),
A sulfo group, a sulfoalkoxy group having 1 to 6 carbon atoms (eg, 2-sulfoethoxy group, 3-sulfopropoxy group) or the like), an acyloxy group having 2 to 22 carbon atoms (eg, acetoxy group, propionoxy) Group), an alkenyl group having 2 to 22 carbon atoms (for example, a vinyl group), an alkoxycarbonyl group having 2 to 22 carbon atoms (for example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a dodecyloxycarbonyl group), an aryl group (a single group). The ring or bicyclic ring may have a substituent, for example, a phenyl group, a p-sulfophenyl group, a heterocyclic residue (eg, a thiazole ring residue, an oxazole ring residue, an imidazole ring residue, a thiadiazole ring residue). Group, oxadiazole ring residue, triazole ring residue, tetrazole ring residue,
Pyrimidine ring residue, etc.

Especially The group represented by is advantageous. ).

Specific examples of the alkyl group represented by R ₁₂ are as follows: methyl group, ethyl group, propyl group (n- or i)
-), Butyl group (n-, sec-, i- or t-), n-
Hexyl group, dodecyl group, heptadecyl group, chloromethyl group, 2-chloroethyl group, 2-cyanoethyl group, carboxymethyl group, 2-carboxyethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4 -Sulfobutyl group, 2-sulfatoethyl group, 2
-Phosphoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 3-methoxypropyl group, 2-ethoxyethyl group, 2- (2-hydroxyethoxy) ethyl group, 2- (2- Acetoxyethoxy) ethyl group, 2- (2-sulfoethoxy) ethyl group, 2- {2- (3-sulfopropoxy) ethoxy} ethyl group, 2-acetoxyethyl group, 4-propionyloxybutyl group, allyl group, methoxy Carbonylmethyl group, 2- (methoxycarbonyl) ethyl group, 4- (ethoxycarbonyl) butyl group, butoxycarbonylmethyl group, benzyl group, 2-phenylethyl group, p-sulfobenzyl group, 2- (2-mercapto-3) -Benzimidazolyl) ethyl group.

Among the compounds represented by the general formula (III), more preferable compounds are represented by the following general formula (IIIa).

Q ¹ represents an atomic group required to complete a 5- or 6-membered heterocycle. R ₁₄ has the same meaning as in formula (III). However, R ₁₄ does not represent a hydrogen atom, and an atom adjacent to the thioketo group in the atomic group represented by Q ¹ is not bonded to a hydrogen atom.

Specific examples of the heterocycle completed by Q ¹ are the same as those shown for the heterocycle formed by R ₁₁ and R ₁₃ .

The heterocycle completed by Q ¹ has a divalent substituent such as an oxo group (═O), a thioxo group (═S) ethylidene group (CH ₃ CH═), a substituted ethylidene group (eg, a benzoxazolilidene ethylidene group). , Thiazolinylidene ethylidene group, pyridylidene ethylidene group, quinolilidene ethylidene group, etc.), heterocyclic divalent residue (for example, benzoxazolilidene group, benzthiazolilidene group, thiazolinylidene group, pyridylidene group, quinolilidene group, etc.) ) And the like.

The compound represented by the general formula (III) is, for example, Japanese Patent Publication No.
8-34,169 (Compound-No. 1 to 8, 31, 32), Pharmaceutical Journal 74 , 1365-1369 (1954) (Compound Example-No. 9), Beins
tein XIII, 394, IV121 (Compound Examples-No. 12 and 13), JP-B-47-18008 (Compound Example-No. 19), JP-B-48-34168 (Compound Example-No. 25), etc. Can be synthesized by the method.

Specific examples of the thioamide compound used in the present invention are shown below.

In the present invention, the compound represented by the general formula (III) is preferably contained in the silver halide emulsion layer, but other non-photosensitive hydrophilic colloid layers (eg protective layer,
Intermediate layer, filter layer, antihalation layer, etc.). 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. When it is added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but is preferably added after chemical ripening and before coating. Particularly, it is preferable to add it to a coating solution prepared for coating.

The content of the compound represented by the general formula (III) of the present invention is the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion, and the fog. It is desirable to select an optimal amount depending on the kind of the preventive compound, etc., and a test method for the selection is well known to those skilled in the art. Usually, it is preferably used in the range of 10 ^-6 to 1 × 10 ^-2 mol, particularly 10 ^-5 to 5 × 10 ^-3 mol per mol of silver halide.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide and silver iodochlorobromide, but silver iodobromide is preferred. The content of silver iodide is preferably 10 mol% or less, more preferably 0.1 to 3.5 mol%.

The average grain size of the silver halide used in the present invention is preferably fine grains (for example, 0.7 μ or less), particularly 0.5
μ or less is preferred. The particle size distribution is basically not limited, but is preferably monodispersed. The term "monodisperse" as used herein means that at least 95% by weight or the number of particles is composed of a particle group having a size within ± 40% of the average particle size.

Silver halide grains in photographic emulsions are cubic, octahedral, 14
It may have a regular crystal such as a tetrahedron or a rhombodecahedral, and a cubic or a tetradecahedron is particularly preferable. Further, it may have irregular crystals such as spheres, plates, flat plates having an aspect ratio of 3 to 20, or a composite form of these crystal forms.

The silver halide grains may have a uniform phase in the inside and the surface layer or may have different phases. Two or more kinds of silver halide emulsions formed separately may be used as a mixture.

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, and the like may coexist.

The silver halide particularly suitable for use in the present invention is prepared in the presence of 10 ⁻³ to 10 ⁻⁵ mol of iridium salt or its complex salt per mol of silver, and the silver iodide content on the surface of the grain is the average grain size. The silver haloiodide has a higher silver iodide content. Use of an emulsion containing such a silver haloiodide provides photographic characteristics with higher sensitivity and higher gamma.

In the above, it is desirable to add the above-mentioned amount of iridium salt before the physical ripening in the production process of the silver halide emulsion, particularly during 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 emulsion of the present invention may not be chemically sensitized, but may be. As the method of chemical sensitization, known methods such as sulfur sensitization, reduction sensitization, and gold sensitization can be used, and they are used alone or in combination. The preferred chemical sensitization method is 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
Symp. 2nd, 301-309 (1970), et al., using polyvinyl pyrrolidone and thiosulfate in combination 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.

Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer, and specific examples thereof are described in U.S. Pat. Nos. 2,487,850 and 2,518,6.
No. 98, 2,983,609, 2,983,610, and 2,694,637.

The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, those having chemical sensitization, Those with different conditions) may be used in combination.

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 the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-divided product 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, pages 45 to 53 (for example, a cyanine dye or a merocyanine dye) can be added. As a result, spectral sensitization can be performed on the longer wavelength side than 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,
The emulsion may contain 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.

Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Rese
arch Disclosure) Volume 176 17643 (Issued 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; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7 ) Tetrazaindenes), pentaazaindenes, etc .; as antifoggants or stabilizers such as benzenethiosulfonate, benzenesulfonate, benzenesulfonate, etc. It can be added known many compounds. Among these, preferably benzotriazole (for example, 5-methyl-benzotriazole) and nitroindazoles (for example, 5-
Nitroindazole). Further, these compounds may be contained in the treatment liquid. Further, the compounds described in JP-A-62-30243, which release an inhibitor during development, can be incorporated for the purpose of stabilizing or preventing black spots.

The photographic light-sensitive material of the present invention can 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 vanadium, chromium acetate, etc.), aldehydes, (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, 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 (mocochloric acid, etc.), etc. 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 condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyethylene glycol alkyl). Nonionic surfactants such as amines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, and alkyl esters. ; Alkyl carboxylates, alkyl sulphonates, alkyl benzene sulphonates Salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphorus A carboxy group, such as acid 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.

Further, for antistatic, it is preferable to use a fluorine-containing surfactant described in JP-A-60-80849.

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-5
6-153,336, JP-A-56-153,342, JP-A-59-278,853
No. 59-90435, No. 59-90436, No. 59-138808 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. Regarding these compounds, JP-A Nos. 61-223834 and 61-228437.
Nos. 62-25745 and 62-55642 specifications 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 emulsion used in the present invention is 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
There is no need to use a highly alkaline developer close to pH 13 described in 2,419,975, and a stable developer can be used.

That is, the silver halide light-sensitive material of the present invention contains sulfite ions as a preservative in an amount of 0.15 mol / l or more, and has a pH of 10.5 to
With a developer having a pH of 12.3, especially pH 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.

As the developing agents of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-4-pyrazolidone, 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 / l to 0.08 mol / l. Also, dihydroxybenzenes and 1-
When a combination with phenyl-3-pyrazolidones or p-amino-phenols is used, the former is used in an amount of 0.05 mol / l to
It is preferred to use 0.5 mol / l and the latter in an amount of 0.06 mol / l or less.

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 at least 0.15 mol / l, particularly preferably at least 0.5 mol / l. The upper limit is preferably up to 2.5 mol / l.

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, potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve Organic solvents such as hexylene glycol, ethanol, and methanol: 1-phenyl-5-mercaptotetrazole, indazole-based compounds such as 5-nitroindazole, benztriazole-based compounds such as 5-methylbenztriazole, and antifoggants or black Anti-potting agent (black pepper): may be contained, and if necessary, a toning agent, a surfactant, an antifoaming agent, a water softener, a hardener, an amino compound described in JP-A-56-106244, and the like. May be included.

JP-A-56-24, as a silver stain inhibitor in the developer of the present invention,
The compound described in No. 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. Further pH used for developer
As the buffer agent, the compounds described in JP-A-60-93,433 or the compounds described in Japanese Patent Application No. 61-28708 can be used.

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-Al / l. 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.

(Developer formulation) Hydroquinone 45.0g N-methyl-P-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 18.0g Potassium hydroxide 55.0g 5-Sulfosalicylic acid 45.0g Boric acid 25.0g Potassium sulfite 110.0g Ethylenediaminetetraacetic acid Disodium salt 1.0 g Potassium bromide 6.0 g 5-Methylbenzotriazole 0.6 g n-Butyl-diethanolamine 15.0 g Water was added 1 (pH = 11.6). Example-1 Controlled particle size was measured using the double jet method.
A 25 μm cubic monodisperse silver iodobromide emulsion (coefficient of variation 0.15, silver iodide 0.5 mol%, iodine distribution uniform) was prepared. K ₃ IrCl ₆ was added to this silver iodobromide emulsion so as to contain 4 × 10 ^-7 mol / Ag mol.

This emulsion was desalted by the flocculation method and then kept at 50 ° C. to serve as a sensitizing dye, the compound (a) shown below was used in an amount of 5 × 10 ⁻⁴ mol of silver and 10 ⁻³ mol of potassium iodide per mol of silver. The solution was added, and the mixture was allowed to stand for 15 minutes and then cooled.

In this emulsion, 4-hydroxy-2-methyl-1,3,3a, 7-tetrazaindene, 5-methylbenztriazole, the following compound (b) and a stabilizer were added as stabilizers. (B) was added so as to be coated at 5 mg / m ² . As a hydrazine compound (I-19) (1 x 10 ^-5 mol / mol Ag)
(I-5) (5 × 10 ^-5 mol / mol Ag) was added, and further polyethylene glycol having an average molecular weight of 600 was added so as to be 75 mg / m ² , and the polyethylene glycol dispersion was added to gelatin in a solid form. 30 wt% ratio, 1,3-divinyl-
In addition to sulfonyl-2-propanol, it was coated on a polyethylene terephthalate film to give silver of 3.6 g / m ² . Gelatin 1.2 g / m ² as a protective layer thereon, irregular an SiO ₂ matting agent 40 mg / m ² of particle size about 3.mu., methanol silica 0.1 g / m ^2, polyacrylamides 100 mg / m ^2, hydroquinone 200 mg / m ² And 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 as shown in Table 1.

 The back layer was applied according to the following formulation.

(Back layer formulation)

Gelatin 4g / m ² Matting agent polymethyl methacrylate (particle size 3.0
4.0μ) 10mg / m ² latex Polyethyl acrylate 2g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40mg / m ² Fluorosurfactant Gelatin hardener 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 The evaluation used the following test method.

(Photographic Properties) Photographic properties 1 are the results of processing at 38 ° C. for 30 ″ using an FG-660F automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) with the developer having the above formulation.

Photograph characteristic 2 is 100% blackened Fujiris Ortho Film GA-
The results are obtained by processing 150 sheets of 100 large all sizes (50.8 cm × 61 cm) with a developer in the same manner as in Photographic Properties 1.

〔image quality〕

1. Evaluation of stretched image quality (1) Manuscript preparation SCAN, a monochrome scanner manufactured by Fuji Photo Film Co., Ltd.
A transparent image of a person consisting of halftone dots and a step wedge in which the halftone percentage was changed stepwise were created using ART30 and special sensitive material SF-100. At this time, the screen frequency was set to 150 lines / inch.

(2) Photographing The original was set on a plate making camera C-440 manufactured by Dainippon Screen Co., Ltd. so that the magnification was equal, and the Xe lamp was irradiated to expose the evaluation sample to exposure.

At this time, the exposure was performed such that 95% of the step wedge of the original became 5%. The filter of the present invention was installed between the original and the light source.

(3) Evaluation As shown in (2), the exposure amount is adjusted and the gradation reproducibility (hardness of halftone dots) of the shard portion of the sample in which the halftone dot% on the small dot side (highlight portion) is matched is good. Five-level evaluation (5 to 1) was performed in order from the ones.

2.Evaluation of image quality of line drawing Same as the photographic characteristics after taking an image of type 7 Mincho and Gothic typeset letters with reflection density in the range of 0.5 to 1.2 using Dainippon Screen camera (DSC351) Under the condition of
This is the result of development processing (38 ° 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.

Claims (5)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the emulsion layer or other hydrophilic colloid layer has a hydrazine derivative, a compound having a thioamide bond, and A silver halide photographic light-sensitive material comprising at least one redox compound which releases a development inhibitor upon being oxidized. 2. The redox compound according to claim 1, wherein said redox group includes hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines, and reductones. The silver halide photographic light-sensitive material according to the above 1). 3. The silver halide photographic material according to claim 1, wherein the redox compound has a hydrazine as a redox group. 4. A redox compound represented by the following general formula (R-
1) The silver halide photographic light-sensitive material according to claim 1, which is at least one compound selected from compounds represented by (R-2) and (R-3). . In these formulas, R ₁ represents an aliphatic group or an aromatic group. G ₁ is -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 And 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. 5. A redox compound represented by the following general formula (R-1)
Claims (1) characterized by the following:
The silver halide photographic light-sensitive material according to the above item. (Wherein A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a sulfinic acid residue or (In the formula, R ₀ represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an aryloxy group;
Represents 1 or 2. ). Time represents a divalent linking group, and t represents 0 or 1. PUG represents a development inhibitor. G ₁ is a carbonyl group, Sulfonyl group, sulfoxy group, (R ₁ represents an alkoxy group or an aryloxy group), an iminomethylene group, or a thiocarbonyl group. R represents an aliphatic group, an aromatic group or a heterocyclic group. )