JP2709642B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material and a method for forming an ultra-high contrast negative image using the same, and particularly to a silver halide photographic material used in a photomechanical process. The present invention relates to a super-high contrast negative type photographic light-sensitive material suitable for a light-sensitive material.

(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 meets the demands of a wide latitude, the effective concentration of sulphite ions in a lithographic silver halide photosensitive material composed of silver chlorobromide (at least silver chloride content of 50% or more) is extremely low (usually 0.1 mol / l or less). There is known a method of obtaining a line image or a halftone 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, 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.

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,
4,224,401, 4,243,739, 4,272,606, 4,31
As shown in No. 1,781, the surface latent image type silver halide photographic material to which a specific acylhydrazine compound is added contains a sulfite preservative of 0.15 mol / l or more at pH 11.0 to 12.3, and is well preserved. After processing with a stable developer, γ
Systems have been proposed for forming over 10 ultra-high contrast negative images. 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.

Although the above imaging system shows excellent performance in terms of sharp halftone dot quality, processing stability, speed and original reproducibility, the original reproducibility has been further improved to cope with the recent variety of printed matter. A system is desired.

JP-A-61-213847 and U.S. Pat. No. 4,684,604 disclose a photosensitive material containing a redox compound which releases a photographically useful group by oxidation, and an attempt to extend the gradation reproduction range is disclosed.
However, in a super-high contrast processing system using a hydrazine derivative, these redox compounds have a harmful effect of hindering the contrast, and their characteristics cannot be utilized.

(Object of the Invention) Accordingly, an object of the present invention is to firstly provide a photosensitive material for plate making capable of obtaining a high contrast image by using a highly stable developer. Provided is a photosensitive material. Thirdly, it is an object of the present invention to provide a plate-making photosensitive material having a wide halftone gradation with a high contrast material using a hydrazine nucleating agent.

(Constitution of the Invention) It is an object of the present invention to provide at least one photosensitive silver halide emulsion layer containing a hydrazine derivative and the photosensitive halogen containing a redox compound capable of releasing a development inhibitor when oxidized. This has been attained by a silver halide photographic material characterized by having a hydrophilic colloid layer different from the silver halide layer.

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 hydroquinone, a catechol, a naphthohydroquinone, an aminophenol, a pyrazolidone, a hydrazine, a hydroxylamine, or a reductone, and more preferably a hydrazine.

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 the general formulas (R-1), (R-2) and (R-3), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, and particularly preferably has 1 to 20 carbon atoms. Is a linear, branched or cyclic alkyl group. 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.

In the general 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 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, 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 1 to 20 carbon atoms in the alkyl portion) Monocyclic or bicyclic)),
An alkoxy group (preferably having 1 to 30 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 30 carbon atoms), an acylamino group (preferably having 2 to 40 carbon atoms) , A sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having 1 to 40 carbon atoms), a phosphoric amide group (preferably having 1 to 40 carbon atoms) and the like. .

In general formulas (R-1), (R-2) and (R-3)
G ₁ -SO ₂ - group are preferred, 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 Time-PUG released from the oxidized form of the redox nucleus through one or more steps of 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 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;
7-56,837 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; U.S. Pat. -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 and No. 59-104,641, which release PUG with decarboxylation of carboxyl group; -0-COOCR _a R _b -PUG
(R _a and R _b each represent a monovalent group), which release PUG with decarboxylation and subsequent formation of aldehydes; isocyanates described in JP-A-60-7,429. And PUG is released by the coupling reaction of a color developer with an oxidized product 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-1)
From the general formula (T-6). In these *
* Indicates the site where Time binds to PUG, and * indicates the other site.

General formula (T-1) Wherein W is an oxygen atom, a sulfur atom or R ₁₁ and R ₁₃ 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 ₁₂
Is a substituent, and typical examples of R ₁₃ are each 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 includes the case where they are linked to form a cyclic structure. General formula (T
Specific examples of the group represented by -1) include the following groups.

General 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 an electrophilic group. Link is a group that can undergo a more nucleophilic attack and cleave the bond with the ** mark.
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.

General formula (T-3) 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 meaning as described in formula (T-1). Specific examples 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 these divalent linking groups represented by Time are also described in detail in JP-A-61-236,549, JP-A-64-88451, 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, Macmilla
n) It is described in pages 344 to 346 of the company. Specifically, mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, mercaptopyrimidines, mercaptobenzimidazoles, mercaptobenzthiazoles, mercaptobenzoxazoles,
Mercaptothiadiazoles, benztriazoles,
Benzimidazoles, indazoles, adenines,
Guanines, tetrazoles, tetraazaindenes,
Triazaindenes, mercaptoarenes and the like can be mentioned.

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, aralkyl, alkenyl, alkynyl, alkoxy, aryl, substituted amino, acylamino, sulfonylamino, ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio 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, sulfooxy group, phosphono group A phosphinico group, a 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 phosphine group, and a sulfonamide group.

 The main development inhibitors are shown below.

1 Mercaptotetrazole derivative (1) 1-ferul-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-mercaptotetrazole (14) 1- (2,4-dichlorophenyl) -5-mercaptotetrazole (15) 1- (4-dimethylaminophenyl) -5-mercaptotetrazole (16) 1- (4-nitrophenyl) -5-mercaptotetrazole (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-mercaptotetrazole (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-di) (Ethoxyethyl) -5-mercaptotetrazole (31) 1- (2-aminoethyl) -5-mercaptotetrazole hydrochloride (32) 1- (2-diethylaminoethyl) -5-mercaptotetrazole (33) 2- (5- Mercapto-1-tetrazolyl) ethyltrimethylammonium chloride (34) 1- ( - phenoxycarbonyl) -5
-Mercaptotetrazole (35) 1- (3-maleimidophenyl) -6-mercaptotetrazole 2 mercaptotriazole derivative (1) 4-phenyl-3-mercaptotriazole (2) 4-phenyl-5-methyl-3-mercaptotriazole (3) 4,5-diphenyl-3-mercaptotriazole (4) 4- (4-carboxyphenyl) -3-mercaptotriazole (5) 4-methyl-3-mercaptotriazole (6) 4- (2-dimethylamino Ethyl) -3-mercaptotriazole (7) 4- (α-naphthyl) -3-mercaptotriazole (8) 4- (4-sulfophenyl) -3-mercaptotriazole (9) 4- (3-nitrophenyl)- 3-mercaptotriazole 3 mercaptoimidazole derivative (1) 1-phenyl-2-mercaptoimidazole (2) 1,5-diphenyl-2-mercaptoimidazole (3) 1- (4-carboxyphenyl) -2-mercaptoimidazole (4) 1- (4-hexylcarbamoyl) -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- Mercapto benzimi Sol (3) 5-amino-2-mercaptobenzimidazole (4) 5-nitro-2-mercaptobenzimidazole (5) 5-chloro-2-mercaptobenzimidazole (6) 5-methoxy-2-mercaptobenzimidazole ( 7) 2-mercaptonaphthimidazole (8) 2-mercapto-5-sulfobenzimidazole (9) 1- (2-hydroxyethyl) -2-mercaptobenzimidazole (10) 5-caproamide-2-mercaptobenzimidazole (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) 2-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-mercaptobenzothiazole 8 mercaptobenzoxazole derivative (1) 2-mercaptobenzoxazole (2) 5-nitro-2-mercaptobenzoxazole (3) 5-carboxy-2-mercaptobenzoxazole (4) 5-sulfo-2-mercaptobenzoki Sazole 9 benzotriazole 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-sulfobenzotriazole Na salt (13) 5-methoxycarbonylbenzotriazole (14) 5-aminobenzotriazole (15) 5-butoxybenzotriazole (16) 5-ureidobenzo Triazole (17) Benzotriazole (18) 5 -Phenoxycarbonylbenzotriazole (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) 4-chlorobenzimidazole (7) 5,6-dimethylbenzimidazole (8) 5-nitro-2- (trifluoromethyl) benzimidazole 11 Indazole derivatives (1) 5-nitroindazole (2) 6-nitroindazole (3) 5-aminoindazole (4) 6-aminoindazole (5) indazole (6) 3-nitroindazole (7) 5-nitro-3- Chloroindazole (8) -Chloro-5-nitroindazole (9) 3-carboxy-5-nitroindazole 12 tetrazole derivative (1) 5- (4-nitrophenyl) tetrazole (2) 5-phenyltetrazole (3) 5- (3-carboxyphenyl) ) -Tetrazole 13 tetrazaindene derivative (1) 4-hydroxy-6-methyl-5-nitro-1,3,
3a, 7-Tetraazaindene (2) 4-mercapto-6-methyl-5-nitro-1,3,3
3a, 7-Tetraazaindene 14 mercaptoaryl derivative (1) 4-nitrothiophenol (2) thiophenol (3) 2-carboxythiophenol Further, general formulas (R-1), (R-2) and (R- In 3), R ₁ or Time _t PUG may be a ballast group commonly used in immobile photographic additives such as couplers, or a compound represented by formulas (R-1), (R-2) or (R-3). ) May be incorporated with a group which promotes the adsorption of the compound represented by the formula (1) on silver halide.

The ballast group has the general formula (R-), (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 amino groups, ureido groups, urethane groups, sulfonamide groups 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 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 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.

The layer containing the redox compound of the present invention is provided above or below the photosensitive emulsion layer containing a hydrazine nucleating agent. The layer containing the redox compound of the present invention may further contain light-sensitive or light-insensitive silver halide emulsion grains. Gelatin or synthetic polymer (polyvinyl acetate, polyvinyl alcohol, etc.) between the layer containing the redox compound of the present invention and the photosensitive emulsion layer containing the hydrazine nucleating agent
May be provided.

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

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 Carbamoyl group, sulfonyl group, sulfoxy group, Or A ₁ and A ₂ are each a hydrogen atom 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 Represents a group.

In the general formula (I), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms.
Is a linear, branched or cyclic alkyl group. 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.

In the general formula (I), 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 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, 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,
An acyloxy group, a carboxamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, an imide group, and the like are mentioned. Preferred substituents are a linear, branched or cyclic alkyl group (preferably having 1 carbon atom). To 20), an aralkyl group (preferably a monocyclic or bicyclic alkyl moiety having 1 to 3 carbon atoms), 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 20 carbon atoms)
30), a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 carbon atom)
~ 30), phosphoric amide group (preferably 1 carbon
~ 30).

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

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 single ring, and the substituent is a halogen atom or 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.

Among the groups represented by R ₂ , when G ₁ is a carbonyl group, a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl) Group, phenylsulfonylmethyl group, etc.), aralkyl group (for example, o
-Hydroxybenzyl group), an aryl group (for example,
Phenyl, 3,5-dichlorophenyl, o-methanesulfonamidophenyl, 4-methanesulfonylphenyl) and the like, and a hydrogen atom is particularly preferable.

When G ₁ or a sulfonyl group, R ₂ is an alkyl group (eg, a methyl group), an aralkyl group (eg, o
-Hydroxyphenylmethyl group), an aryl group (eg, a phenyl group) or a substituted amino group (eg,
And the like.

When G ₁ is a sulfoxy group, preferably R ₂ is a cyanamibenzyl group, a methylthiobenzyl group or the like, and G ₁ is In the case of R ₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, a phenyl group,
Phenoxy groups are preferred.

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

Further, R ₂ disrupts the G ₁ -R ₂ moiety from the remainder molecule, -G ₁ -
A cyclization reaction that generates a cyclic structure containing an atom of the R ₂ moiety may be performed, and specifically, the cyclization reaction 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, is a group that may disrupt the G ₁ -R ₂ -Z ₁ moiety from the remainder molecule, R ₃ than that removing one hydrogen atom from R _2, Z ₁ is a nucleophilic attack to G _1, G _1,
R ₃ and Z ₁ can form a cyclic structure.

More specifically, Z ₁ easily undergoes a nucleophilic reaction with G ₁ when the next reaction intermediate is generated by oxidation or the like of the hydrazine compound of the general formula (I), and R ₁ -N = NG ₁ —R ₃ —Z ₁ R ₁ —N = N is a group capable of splitting an N group from G ₁ , specifically, OH, SH or NHR ₄ (R ₄ is a hydrogen atom, an alkyl group, an aryl group, —COR ₃ Or —SO ₂ R ₅ , wherein R ₅ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.), a functional group that directly reacts with G ₁ such as COOH, Here, OH, SH, NHR ₄ , and —COOH may be temporarily protected so as to generate these groups by hydrolysis of alkyl or the like.) (R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group) and react with G ₁ by reacting with a nucleophilic agent such as a hydroxyl ion or a sulfite ion. It may be a functional group capable of performing the above.

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

General formula (b) Wherein, R _b ¹ ~R _b ⁴ is a hydrogen atom, (preferably those having 1 to 12 carbon atoms) alkyl groups, (those of preferably 2 to 12 carbon atoms) alkenyl group, an aryl group (preferably having a carbon number of 6 ~
12) 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,
(N + m) is 1 or 2.

As the 5- or 6-membered ring formed by B, for example,
Cyclohexenes, cycloheptenes, benzene rings, naphthalene rings, pyridine rings, quinoline rings and the like.

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

General formula (c) In the formula, R _c ¹ and R _c ² represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, or the like, 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 is 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 each} represent a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably phenylsulfonyl group or phenylsulfonyl substituted such that the sum of Hammett's substituent constants is -0.5 or more; Group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group), a benzoyl group substituted so that the sum of Hammett's substituent constants becomes -0.5 or more, or a straight-chain, branched or cyclic unsubstituted group And a substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group,
Examples thereof include a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group. ).

A ₁ and A ₂ are most preferably hydrogen atoms.

R ₁ or R _{2 in} the general formula (I) may have a ballast group 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, which is relatively inert to photographic properties, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, and an alkylphenoxy group. You can choose from.

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, hetero group thioamide group, mercapto heterocyclic group, triazole group and the like US Pat. Nos. 4,385,108; 4,459,347;
No. 195,233, No. 59-200,231, No. 59-201,045, No. 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
And the groups described in JP-A Nos. 62-67,510.

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, UK Patent 2,011,391B,
JP-A-60-179934, JP-A-62-270,948, JP-A-63-29,751
No., JP-A-61-170,733, JP-A-61-270,744, JP-A-62-94
No. 8, EP 217,310, Japanese Patent Application No. 61-175,234, No. 61-251,4
No. 82, No. 61-268,249, No. 61-276,283, No. 62-6675
No. 8, 62-67,509, 62-67,510, 62-58,513
Nos. 62-130,819, 62-143,467, 62-166,11
No. 7, US Pat. No. 4,686,167, JP-A Nos. 62-178,246 and 6
3-234,244, 63-234,245, 63-234,246,
No. 63-294,552, No. 63-306,438, Japanese Patent Application No. 62-166,117
Nos. 62-247,478, 63-105,682, 63-114,11
No. 8, No. 63-110,051, No. 63-114,119, No. 63-116,2
No. 39, No. 63-147,339, No. 63-179,760, No. 63-229,
No. 163, Japanese Patent Application Nos. 1-18,377, 1-18,378, 1-1
No. 8,379, No. 1-15,755, No. 1-16,814, No. 1-40,
Nos. 792, 1-42,615 and 1-42,616 can be used.

In the present invention, when a hydrazine derivative 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, Antihalation layer). 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 the completion of chemical ripening and between the coating surfaces. Particularly, it is preferable to add it to a coating solution prepared for coating.

The content of the hydrazine derivative of the present invention depends on 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 layer, the type of antifoggant compound and the like. It is desirable to select the optimal amount accordingly, and the methods of testing for that selection are well known to those skilled in the art. Usually, it is preferably used in the range of 10 ^-6 mol to 1 × 10 ^-1 mol, particularly 10 ^-5 to 4 × 10 ^-2 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, silver iodochlorobromide and the like.

The average grain size of the silver halide used in the present invention is preferably fine grains (for example, 0.7 μm or less), particularly 0.5 μm.
The following 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 group of particles having a size within ± 40% of the average particle size.

The silver halide grains in the photographic emulsion may have regular crystals such as cubic and octahedral, and irregular such as spherical and tabular.
It may be one having a suitable crystal or one having a complex form of these crystal forms.

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. 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.

In the emulsion layer of the present invention, or other hydrophilic colloid layer,
A water-soluble dye may be contained as a filter dye or for various purposes such as prevention of irradiation.
As the filter dye, a dye for further lowering the photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the inherent sensitivity range of silver halide, and safety against safelight light when handled as a light room photosensitive material Dyes having substantial light absorption mainly in the range of 350 nm to 600 nm are used to increase the light absorption.

These dyes are added to the emulsion layer depending on the purpose,
Alternatively, it is preferable to add and fix a non-photosensitive hydrophilic colloid layer above the silver halide emulsion layer, that is, a non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with the mordant before use.

Different by the molar extinction coefficient of the dye, but usually 10 ^-2 g / m ² ~
It is added in the range of 1 g / m ² . Preferably 50mg~500mg / m ²
It is.

Specific examples of dyes are described in detail in Japanese Patent Application No. 61-209169, some of which are as follows.

The dye is dissolved in an appropriate solvent [eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof] for the non-photosensitive hydrophilic colloid layer of the present invention. It is added to the coating solution.

These dyes can be used in combination of two or more kinds.

The dye of the present invention is used in an amount necessary to enable handling in a bright room.

The amount of the specific dye is generally ^{10 -3 g / m 2 ~1g /} m 2,
In particular it is possible to find the preferred amount in the range of ^{10 -3 g / m 2 ~0.5g /} m 2.

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 polymers of gelatin with other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sodium alginate;
Sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and various kinds of copolymers such as polyvinylpyrazole. Synthetic hydrophilic polymeric substances can be used.

As the gelatin, besides lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and enzymatic hydrolyzate of gelatin can also be used.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be. As methods of chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these can be used alone or in combination with chemical sensitization. Is also good.

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.

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.

As the reduction sensitizer, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used.

A known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention.

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, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindene) ), Pentaazaindenes; and many other compounds known as antifoggants or stabilizers, such as benzenethiosulfonate, benzenesulfonate, benzenesulfonamide, and the like. Rukoto can. Among these, preferred are benzotriazoles (eg, 5-methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole). Further, these compounds may be contained in the treatment liquid.

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, etc.), aldehydes, 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 and the like 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 interfaces such as alkylamines 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 of sugars. Activator; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfo Acid salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene Anionic surfactants containing an acidic group such as a carboxy group, a sulfo group, a phospho group, a sulfate group, or a phosphate group, such as alkyl phosphates; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfate or Amphoteric surfactants such as phosphates, alkyl betaines, and amine oxides; alkylamine salts,
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, 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, a polymer latex such as polyalkyl acrylate can be contained for dimensional stability.

Examples of development accelerators suitable for use in the present invention or accelerators for nucleation transmission development include JP-A-53-77616 and JP-A-54-377.
In addition to the compounds disclosed in Nos. 32, 53-137, 133, 60-140,340, and 60-14959, various compounds containing an N or S atom are effective.

 Next, specific examples are listed.

The optimum amount of these accelerators varies depending on the type of the compound, but is 1.0 × 10 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ^−3.
It is desirable to use it in the range of 0.1 g / m ² . These accelerators are dissolved in a suitable solvent (H ₂ O), such as alcohols such as methanol and ethanol, acetone, dimethylformamide, and methylcellosolve, and added to the coating solution.

 A plurality of these additives may be used in combination.

In order to obtain ultra-high contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or U.S. Pat.
It is not necessary to use a highly alkaline developer close to pH 13 described in No. 5, 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.

There is no particular limitation on the developing agent that can be used in the method of the present invention, and examples thereof include dihydroxybenzenes (eg, hydroquinone) and 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-). 3-pyrazolidone), aminophenols (for example, N
-Methyl-p-aminophenol) or the like can be used alone or in combination.

The silver halide light-sensitive material of the present invention particularly contains dihydroxybenzenes as a main developing agent and 3
-Suitable to be processed with a developer containing pyrazolidones or aminophenols. Preferably in this developer dihydroxybenzenes 0.05 to 0.5 mol / l,
The 3-pyrazolidones or aminophenols are used together in a range of 0.06 mol / l or less.

Further, as described in U.S. Pat. No. 4,269,929, the development speed can be increased by adding amines to the developer to shorten the development time.

Other developers include pH buffers such as sulfites, carbonates, borates and phosphates of alkali metals, bromides,
It can contain a development inhibitor such as iodide and an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles) or an antifoggant. Also, if necessary, a water softener, a dissolution aid, a color tone agent,
It may contain a development accelerator, a surfactant (especially preferably the above-mentioned polyalkylene oxides), an antifoaming agent, a hardener, and a film silver stain inhibitor (eg, 2-mercaptobenzimidazole sulfonic acid).

As the fixing solution, those having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thioacinate, an organic sulfur compound known to have an effect as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The processing temperature in the process according to the invention is usually chosen between 18 ° C and 50 ° C.

Although it is preferable to use an automatic developing machine for photographic processing, according to the method of the present invention, even if the total processing time from when the photosensitive material is put into the automatic developing machine until it comes out is set to 90 seconds to 120 seconds. Thus, a photographic characteristic of a negative tone with a sufficiently high contrast can be obtained.

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. Furthermore, compounds described in JP-A-60-93,433 or compounds described in Japanese Patent Application No. 61-28708 can be used as a pH buffer used in the developer.

 Hereinafter, the present invention will be described in detail with reference to Examples.

 In the examples, a developer having the following formulation was used.

Comparative Example 1 (Preparation of photosensitive emulsion) 4 × 10 ^-7 per mol of silver was added to an aqueous gelatin solution kept at 50 ° C.
An aqueous silver nitrate solution and an aqueous solution of potassium iodide and potassium bromide were added simultaneously over 60 minutes in the presence of moles of potassium iridium (III) chloride and ammonia, and the pAg between them was kept at 7.8 to obtain an average particle size of 0.28 μm. A cubic monodispersed emulsion having an average silver iodide content of 0.3 mol% was prepared. The emulsion was desalted by flocculation, and then 40 g of inert gelatin per mole of silver was added.
5,5'-dichloro-9-ethyl- as sensitizing dye
3,3'-Bis (3-sulfopropyl) oxacarbocyanine and a KI solution of 10 ^-3 mol per mol of silver were added, and the mixture was aged for 15 minutes and then cooled.

(Coating of photosensitive emulsion layer) This emulsion was redissolved, and the following hydrazine derivative was added at 40 ° C. to give methylhydroquinone 0.02 mol / Ag mol, Further, 5-methylbenztriazole, 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene, the following compounds (a), (b) and 30 wt% of polyethyl acrylate based on gelatin and the following compound (c) as a gelatin hardener were added: It was coated on a polyethylene terephthalate film (150 μ) having an undercoat layer (0.5 μ) of a vinylidene chloride copolymer so as to have a silver amount of 3.4 g / m ² .

(Coating of Protective Layer) As a protective layer, 1.5 g / m ^{2 of} gelatin and 0.3 g / m ² of polymethyl methacrylate particles (average particle size 2.5 μm) were coated thereon using the following surfactant.

Surfactant Comparative Examples 2 to 4 The redox compounds 6, 14 and
21 were each added at 2.0 × 10 ⁻⁵ mol / m ^2, and the other conditions were the same as in Comparative Example 1.

Example 1 1.5 g of gelatin was placed between the photosensitive emulsion layer of Comparative Example 1 and the support.
/ m ² and the redox compound of the present invention shown in Table 1 2.0 × 10 ⁻⁵
A gelatin U layer containing mol / m ² was provided.

Optical wedges and contact screens (Fujifilm, 150L)
After exposure through a chain dot type), 34 ℃ with the next developer
It was developed for 30 seconds, fixed, washed with water and dried.

Table 1 shows the measurement results of the halftone gradation of the obtained sample. The halftone was expressed by the following equation.

* Halftone = Exposure to give 95% halftone dot area ratio (logE95
%) — Exposure dose giving a dot area ratio of −5% (logE5%) The sample of the present invention has a remarkably wider halftone gradation than the comparative example. In Comparative Examples 2 to 4, the contrast was significantly reduced to 10 or less, whereas the sample of the present invention maintained high contrast.

The shape of the halftone dot is irregular in the sample of Comparative Example 1 with conspicuous irregularities, and the samples of Comparative Examples 2 to 4 have a low optical density and are in a blurred state.
The samples of the examples of the present invention had smooth shapes and were halftone dots having a high optical density.

Example 2 The same procedure as in Example 1 was carried out except that a layer having the following composition was used as the gelatin U layer of Example 1.

As a result of the exposure and development processing in the same manner as in Example 1, halftone dots of good quality and halftone gradation were further widened.

Example 3 The following layers were sequentially coated on a polyester film (150μ) support.

(1) Photoemulsion layer-A Using the photoemulsion formulation shown in Comparative Example 1, the silver content was 0.1%.
It was applied so as to be 4 g / m ² .

(2) Interlayer Gelatin 0.5 g / m ² Polyethyl acrylate latex 0.15 Redox compound of the present invention (shown in Table 2) (2) Interlayer Gelatin 0.5 g / m ² (4) Photosensitive emulsion layer-B Comparative Example-1 Was coated such that the silver amount was 3.4 g / m ² .

 The results are shown in Table 2.

The dot quality was visually evaluated on a 5-point scale. In the five-point evaluation, "5" indicates the best quality and "1" indicates the worst quality.
As plate making-like halftone dot masters, "5" and "4" are practically usable, "3" is a practically usable limit level, "2",
"1" is a quality that is impractical.

The results are shown in Table 2. The sample of the present invention has a high halftone quality and gives a halftone image with a wide halftone.

Example 4 5.0 × 10 5 per mol of silver was added to an aqueous solution of gelatin maintained at 50 ° C.
After simultaneously mixing an aqueous solution of silver nitrate and an aqueous solution of sodium chloride in the presence of ^-6 mol of (NH ₄ ) ₃ RhCl ₆ , gelatin is added after removing soluble salts by a method well known in the art, and then chemically added. 4-hydroxy- as a stabilizer without aging
6-Methyl-1,3,3a, 7-tetrazaindene was added.
This emulsion was a cubic monodisperse emulsion having an average size of 0.15 μm (Emulsion B). Further, the compounds of the present invention shown in Table 3 were added thereto, and 1,3-vinylsulfonyl-3- was used as a hardener. Propanol was added, and the mixture was coated on a polyester support so that the amount of Ag was 0.4 g / m ² . Gelatin was 0.3 g / m ² . After an intermediate layer of 0.5 g / m ² of gelatin was applied thereon, the next photosensitive layer was applied so that the silver amount was 3.4 g / m ² .

The following hydrazine compound was added to this emulsion. Further, a polyethyl acrylate latex was added at a solid content of 30 wt% based on gelatin, and 1,3-vinylsulfonyl-2-propanol was added as a hardening agent at 2.0 wt% based on gelatin.

On this, gelatin 0.5 g / m ² as a protective layer and polymethyl methacrylate particles (average particle size 2.5
μ) 0.3 g / m ² , and the following surfactant as a coating aid,
Apply a protective layer containing a stabilizer and a UV absorbing dye,
Dried.

Surfactant UV absorbing dye The sample was exposed through a document as shown in FIG. 1 through a light source printer P-607 manufactured by Dainippon Screen Co., Ltd., developed at 38 ° C. for 20 seconds, fixed, washed with water, dried, and then printed to obtain the image quality of blank characters. An evaluation was performed.

Character image quality of 5 means that a 30 μm wide character is reproduced when an appropriate exposure is performed so that a halftone dot area of 50% becomes a halftone dot area of 50% on a return photosensitive material using an original as shown in FIG. The image quality is very good and the image quality is very good. On the other hand, the extracted character image quality 1 is an image quality that can reproduce only characters having a width of 150 μm or more when the same appropriate exposure is given. Rank was set. Three or more is a practical level.

The results are shown in Table 3. The sample of the present invention is excellent in the character extraction image quality.

[Brief description of the drawings]

FIG. 1 shows a configuration at the time of exposure in the case where a character extraction image is formed by overlapping, and the reference numerals indicate the following. (B) Transparent or translucent paste base (b) Line drawing original (black part shows line drawing) (c) Transparent or translucent paste base (d) Halftone original (black part is halftone dot (E) Returning photosensitive material (note that the hatched portion indicates the photosensitive layer)

Claims (5)

(57) [Claims] A hydrophilic material different from at least one photosensitive silver halide emulsion layer containing a hydrazine derivative and a photosensitive silver halide layer containing a redox compound capable of releasing a development inhibitor when oxidized. A silver halide photographic material having a colloid layer. 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-
The silver halide photographic light-sensitive material according to claim 1, wherein the compound is at least one compound selected from the compounds represented by (1), (R-2) and (R-3). material. 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 - represents a. Time represents a divalent linking group, and t represents 0 or 1. PUG represents a development inhibitor. 5. The silver halide photographic material according to claim 1, wherein the redox compound is represented by the general formula (R-1).