JPH0367241A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material giving a fine line image or ensuring superior image quality such as suitability to grain enlargement or reduction by incorporating specified compds. into an emulsion layer or other hydrophilic colloidal layer. CONSTITUTION:At least one photosensitive silver halide emulsion layer is formed on a support and at least one kind of hydrazine deriv., at least one kind of compd. having a thioamido bond and a redox compd. releasing a development inhibitor on being oxdized are incorporated into the emulsion layer or other hydrophilic colloidal layer. The redox group of the redox compd. is preferably selected among hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines and reductones, especially hydrazines. A fine line image is obtd. or suitability to grain enlargement and reduction is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a iron halide photographic light-sensitive material, and particularly to an ultra-high contrast silver halide photographic light-sensitive material used for photolithography.

(Prior art) In the field of photoengraving, there is a wide variety of printed matter. j [To address these difficulties, there are demands for photographic materials with good original reproducibility, stable processing solutions, and easier replenishment.

Particularly in the line drawing process, manuscripts are created by pasting typesetting characters, handwritten characters, illustrations, halftone photographs, etc. Therefore, a document contains images of different densities and line widths, and there is a strong desire for a plate-making camera, a photosensitive material, or an image forming method that can finish these documents with good reproduction. On the other hand, enlarging (stretching) or reducing (shrinking) halftone photographs is widely used in plate making for catalogs and large bossks. The photograph will be taken at the point. When reduced, the number of lines per inch is larger than that of the original, and a thinner point is photographed. Therefore mP
In order to maintain full reproducibility, an image forming method having a wider latitude is required.

A halogen lamp or a xenon lamp is used as a light source for a plate-making camera. In order to obtain sensitivity to these light sources, photographic materials are usually orthosensitized. However, it has been discovered that ortho-sensitized photographic materials are more strongly affected by the chromatic aberration of lenses, and as a result, image quality tends to deteriorate. Moreover, this deterioration is more noticeable for xenon lamp light sources.

As a system that meets the demands of a wide range of latitudes, lithium-type silver halide photosensitive materials are made from silver chlorobromide (containing at least 50% tin chloride), but the effective concentration of sulfite ions is extremely low (usually 0.1 mol). A known method is to obtain a line or halftone image with high contrast and high blackening density, in which image areas and non-image areas are clearly distinguished, by processing with a hydroquinone developer. However, due to the low concentration of sulfite in the developing solution, this method is extremely unstable to air oxidation, and various efforts and innovations have been made to keep the solution activity stable. Currently, the process is extremely slow, reducing work efficiency.

For this reason, the above development method (lith development system)
There is a need for an image forming system that eliminates the instability of image formation caused by the method, develops with a processing solution that has good storage stability, and obtains ultra-high contrast photographic characteristics.One example of this is US Pat. No. 4,166. No. 742, No. 4,168,977, No. 4,221,857, No. 4,224,401, No. 4
, 243°739, 4,272.606, 4,
31). As seen in No. 781, a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound was added was prepared at a pH of 1), 0 to 12.3, and sulfite preservative was added to 0.
．． Processed with a developer containing 15 mol/2 or more and having good storage stability, super 1iJ with r exceeding 10! A system for forming negative images of m was proposed. This new image forming system can only use silver chlorobromide, which has a high silver chloride content, in contrast to conventional ultra-high contrast image forming.
It has the characteristic that silver iodobromide and silver chloroiodobromide can also be used.

The above image system has sharp halftone dot quality, processing stability,
Although the system exhibits excellent performance in terms of speed and original reproducibility, there is a need for a system that is more stable and has improved original reproducibility in order to cope with the diversity of printed materials in recent years.

Examples of systems using hydrazine containing a redox compound that releases a development inhibitor upon oxidation are disclosed in JP-A-61-213847 and JP-A-64-72140. On the other hand, examples containing thioamide compounds are disclosed in JP-A-53-137133, JP-A-61-47943, and JP-A-62-278692.

(Problems to be Solved by the Present Invention) The first object of the present invention is to provide a silver halide photographic light-sensitive material which has excellent image quality such as suitability for line drawing, eye stretching, and eye shrinkage.

A second object of the present invention is to provide a silver halide photographic material in which sensitivity, T, and Dmax do not decrease much even when the pH decreases or the bromide ion concentration increases due to processing of a large amount of film. It is.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, in which the emulsion layer or other hydrophilic colloids are added. This was achieved by a silver halide photographic material characterized in that the layer contains at least one of a hydrazine derivative, a compound having a thioamide bond, and a redox compound that releases a development inhibitor when oxidized.

The redox compound of the present invention that can release a development inhibitor when oxidized will be explained.

The redox group of the redox compound is preferably hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylaquines, or reductones, and more preferably hydrazines. .

The hydrazines used as the redox compound that releases a development inhibitor upon oxidation of the present invention are preferably represented by the following general formulas (R-1), (R-2), and (R-3): It is expressed as A compound represented by general formula (R-1) is particularly preferred.

General formula (R-1) A+ At General formula (R-2) A, Ih 4 General formula (R-3) O In these formulas, R' is an aliphatic group or aromatic group○ 1 or -P- group , G8 is just a bond, G, -
R.

10--3- or -N-, R2 is water t Represents an elementary atom or R.

A+ and Ax 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 A1) 80 is a hydrogen atom. Ax is synonymous with A or -C
HzCH+Ti+ie) represents t-PUG.

4 A4 represents a nitro group, a cyano group, a carboxyl group, a sulfo group, or -G, -G, -R.

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

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

In general formulas (R-1), (R-2), (R-3),
The aliphatic group represented by R is preferably one having 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

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

In general formulas (R-1), (R-2), (R-3), R
The aromatic group represented by 8 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, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Examples include isoquinoline ring, benzimidazole ring, thiazole ring, and benzothiazole ring, among which those containing a benzene ring are preferred.

Preferred R1 for samurai is an aryl group.

The aryl group or unsaturated heterocyclic group of R1 may be substituted, and typical substituents include 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,
Examples include carbonamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, etc. Preferred substituents include linear, branched or cyclic alkyl group (preferably one having 1 to 20 carbon atoms), aralkyl group (preferably is a monocyclic or bicyclic alkyl moiety having 1 to 20 carbon atoms),
Alkoxy group (preferably one having 1 to 30 carbon atoms), substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 30 carbon atoms), acylamino group (preferably one 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. be.

For general formulas (R-1), (R-2), and (R-3), -C- group and -SO□- group are preferable, and -C- group is most preferable.

AI and Ax are hydrogen atoms, alkylsulfonyl groups having 20 or less carbon atoms, and arylsulfonyl groups (preferably phenylsulfonyl groups or)\met, where the sum of the substituent constants is -
(phenylsulfonyl group substituted so that 0.5 or more), acyl TE (preferably benzoyl group, or) \met having 20 or less carbon atoms, substituted so that the sum of the substituent constants of \met is -0.5 or more benzoyl groups, or direct, branched or cyclic unsubstituted and substituted aliphatic acyl groups (
Examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group. )) is preferred.

As AI and Ax, a hydrogen atom is most preferable.

A is a hydrogen atom, -CHt-CH-+Timeh
c PUG4 is most preferred.

In general formulas (R-1), (R-2), and (R-3), T
ime represents a divalent linking group, and timing mi! ff
t represents O or 1, which may have a function.

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

As the divalent linking group represented by Time, for example, U.S. Pat.
U.S. Pat. Those that release PUG by an intramolecular ring-closing reaction after ring cleavage as described in US Pat. No. 4,330.617, US Pat.
No. 4,483,919, JP 59-121.328
U.S. Patent No. 4,40, which releases PUG with the production of an acid anhydride through an intramolecular ring-closing reaction of the carboxyl group of a succinic acid monoester or its analog described in US Patent No. 4,40.
No. 9,323, No. 4,421.845, Research Disclosure Magazine NCL 21.228 (December 1981), U.S. Patent No. 4,416,977 (Japanese Patent Application Laid-open No. 5
No. 7-135,944), JP-A-58-209゜736
No. 58-209.738, etc., quinomonomethane or its analogues are produced by electron transfer via a double bond conjugated with an oxy group or a heterocyclic oxy group, and PUG is released. U.S. Patent No. 4,420
, No. 554 (Japanese Unexamined Patent Publication No. 57-136,640), Unexamined Japanese Patent Application No. 57-135.945, No. 57-188,035,
No. 58-98,728 and No. 5B-209,737
A nitrogen-containing heterocycle which releases PUG from the 7-position of the enamine by electron transfer of the moiety having an enamine structure in the nitrogen-containing heterocycle described in JP-A No. 57-56,837; PUG is formed by an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated with an atom.
Those that emit
No., JP-A-59-75475, JP-A-60-2491
48, JP-A-60-249149, etc., which release PUG with the production of aldehydes; JP-A-Sho. 5
1-146,828, 57-179,842, and 59-104,641 which release PUG with decarboxylation of carboxyl groups; -0-COOCR
-Rh-PLIG (R,, R5 represents a monovalent group,
), which releases PUG with decarboxylation and subsequent generation of aldehyde surfaces; JP-A-60-7,42
PUG is released with the formation of incyanate as described in No. 9;
Examples include those that release UG.

Time of general formulas (R-1), (R-2), (R-3)
The divalent group represented by is preferably represented by the following general formula (T-
1) is represented by the general formula (T-6>. In these, ** represents the site where Time binds to PUG, and book represents the other binding site.

General Formula (T-1) In the formula, W represents an oxygen atom, a sulfur atom or a -N-13 group, and R8 and R1) represent a hydrogen atom or a substituent. R1) represents a substituent, L is 1 or 2
When e 1 is 2, two -W-C-IK represent the same or different, R8 and R
When I2 represents a substituent and R1, representative examples are R14 group, R, CO- group, R14SO2- group, R1, respectively.
, , NC0- group or IS R+ -N SOz- group, etc. 8 where R1
4I5 represents an aliphatic group, aromatic group or heterocyclic group, R15
represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom.

R1, RI! Each of R1 and R1 represents a divalent group, and the case where they are linked to form a cyclic structure is also included.

Specific examples of the group represented by general formula (T'-1) include the following groups.

$-0-C1l-rate book c+ttcFi.

0-CHz-N-CH2-*Umbrella general formula (T-2) *-Nu-Link-E-** In the formula, Nu represents a nucleophilic group, and an oxygen atom or a sulfur atom is an example of a nucleophilic species. , and E represents an electrophilic group, which is a group that can cleave the bond with this seal by receiving a nucleophilic attack from Nu, and Li
nk represents a linking group that sterically relates Nu and E so that they can undergo an intramolecular nucleophilic W exchange reaction, and has the general formula (
Specific examples of the group represented by T-2) are as follows.

Shil'+3 +13 O l Book-MCHffi ÷ completed N-C-Kining General formula (T-3) During the ceremony, 1 R1)・ RIK and t are (T-1) It has the same meaning as explained above.

specifically Examples include the following groups.

1)-〇General formula (T-4) General formula (T-5) *-0-C-** Book-5-C-1)1 General formula (T-6) In the formula, W and R1 are general This has the same meaning as explained in formula (T-1). Specific examples of the group represented by general formula (T-6) include the following groups.

Also, as Time, general formula (T-1) ~ - general formula T=
A group formed by combining two or more groups represented by 6) is also useful. Preferred specific examples thereof are shown below: *, *
The term "umbrella" has the same meaning as in general formulas (T-1) to -general formula T-6).

Umbrella-〇-CL C2H.

/ tHs Hon-〇-CHz CtHs H3 C[13 Ning-0-C-O←CH2u-rN C-”ne
CJs For specific examples of these divalent linking groups represented by Time, see JP-A No. 6], -236,549, JP-A No. 6
It is also described in detail in Japanese Patent Application No. 4-88451, Japanese Patent Application No. 63-98.803, etc.

PUG represents (Tjme)-z PUG or a group having a development inhibiting effect as PUG.

P U G or (T im e +-t P U
The development inhibitor represented by G is a known development inhibitor that has a -tero atom and is bonded via a hetero atom,
These include, for example, C.E.C.E.

1Mess) and Chi James (τ, l
! .

James) The Theory of Photography 7 Process
photographicProcesses) J3rd
ed., published by Macmillan in 1966, pages 344 to 346. Specifically, mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, mercaptopyrimidines, mercaptobenzimidazoles, mercaptobenzthiazoles, mercaptobenzoxazoles, mercaptothiadiazoles, benztriazole□, benzimidazoles, indazoles, Examples include adenines, guanines, tetrazoles, tetraazaindenes, triazaindenes, and mercaptoarenes.

The development inhibitor represented by PUG may be substituted. Examples of substituents include the following:
These groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups,
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, aryloxycarbonyl basis,
Acyl group, alkoxycarbonyl group, acyloxy group,
These include a carbonamide group, a sulfonamide group, a carboxyl group, a sulfoxy group, a phosphono group, a phosphinico group, a phosphoamide group, and the like.

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

Main development 1) W1 agents are shown below.

(2) 1-(4-hydroxyphenyl)-5-mercaptotetrazole (3) 1-(4-aminoethyl)-5-mercaptotetrazole (4) 1-(4-carboxyphenyl)-5-mercaptotetrazole ( 5) 1-(4-chlorophenyl)-5-mercaptotetrazole (6) 1-(4-methylphenyl)-5-mercaptotetrazole (7) 1-(2,4-jethoxyethyl)-5-mercaptotetrazole ( 8) 1-(4-sulfamoylphenyl)-5-mercaptotetrazole (9) 1-(3-carboxyphenyl)-5-mercaptotetrazole Gω 1-(3,5-dicarboxyphenyl)-5-mercaptotetrazole (II)1. -(4-methoxyphenyl)-5-mercaptotetrazole 02) 1-(2-methoxyphenyl>-5-mercaptotetrazole Q$ 1-(4-(2-hydroxyethoxy>phenyl)-5-mercaptotetrazole Q41 1- (2,4
-dichlorophenyl)-5-mercaptotetrazole (151)-(4-dimethylaminophenyl)-5-mercaptotetrazole 1) 61)-(4-nitrophenyl)-5-mercaptotetrazole 01.4-bis(5-mercapto -1-tetrazolyl)
Benzene 0FfJL-(α-naphthyl)-5-mercaptotetrazole Qll-(4-sulfophenyl)-5-mercaptotetrazole ■ 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-valmityl-5-mercaptotetrazole (29) 1-carboxyethyl-5-mercaptotetrazole (30) 1- (2 , 2-jethoxyethyl)-5-mercaptotetrazole (31) L-(2-aminoethyl)-5-mercaptotetrazole hydrochloride (32) 1-(2-diethylaminoethyl>-5 = mercaptotetrazole (33) 2 -(5-mercapto-1-tetrazolyl)ethyltrimethylammonium chloride (34) 1-
(3-phenoxycarbonylphenyl)-5-mercaptotetrazole (35) 1-(3-maleigodophenyl)-6-mercaptotetrazole 2 Mercaptodo azole 6 (1) 4-phenyl-3-mercaptotetrazole (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-dimethylaminoethyl)-3-mercaptotriazole (7) 4-(α-naphthyl)-3-mercaptotriazole (8) 4-(4-sulfophenyl)-3-mercaptotriazole (9) 4- (3-nitrophenyl)-3-mercaptotriazole (2) 1,5-diphenyl-2-mercaptoy and dazole (31)-(4-carboxyphenyl)-2-mercaptoimidazole (4) 1-(4 -hexylcarbamoyl)-2-mercaptoimidazole (5) 1-(3-nitrophenyl)-2-mercaptoimidazole (6) l-(4-sulfophenyl)-2-mercaptoimidazolkapi Uracilmethylthiouracil ethylthiouracil probylthiouracil nonylthiouracylaminothiouracil hydroxythiouracil mercap Bendai 8 - Lu (1) 2-mercaptobenzimidazole (2) 5-carboxy-2-mercaptobenzimidazole (3) 5- Amino-2-mercaptobenzimidazole (4) 5-nitro-2-mercaptobenzimidazole (5) 5-chloro-2-mercaptobenzimidazole (6) 5-methoxy-2-mercaptobenzimidazole (7) 2-mercaptobenzimidazole 7 Toiadazole (8) 2-mercapto-5-sulfobenzimidazole (9) 1-(2-hydroxyethyl)-2-mercaptobenzimidazole Ill 5-caproamido-2-mercaptobenzimidazole (105-(2-ethylhexane) 2-mercabutobenzimidazole merca diazole' (1) 5-methylthio-2-mercapto-1,3゜4-
Thiadiazole (2) 5-ethylthio-2-mercapto-193゜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 Luca Benzol (1) 2-mercaptobenzthiazole (215-nitro-2-mercaptobenzthiazole (3) 5-carboxy-2-mercaptobenzthiazole (4) 5-sulfo-2-mercaptobenzthiazole 8 Mercapto Benzoxazole - (1) 2-Merkabutopenzoxazole (2) 5-nitro-2-mercaptobenzoxazole (3) 5-carboxy-2-mercaptobenzoxazole (4) 5-sulfo-2-mercaptobenzoxazole 9 Benzo 1 Azole 6 (1) 5,6-dimethylbenzotriazole (2) 5-
Butylbenzotriazole (3) 5-methylbenzotriazole (415-chlorobenzotriazole (5) 5-bromobenzotriazole (6) 5.6-dichlorobenzotriazole (7) 4,
6-dichlorobenzotriazole (8) 5-nitrobenzotriazole (9) 4-nitro 6-chloro-benzotriazole α0) 4.5.6-Dolichlorobenzotriazole 01] 5-carboxybenzotriazole 02) 5-sulfonate Benzotriazole Na salt 1) 3) 5-methoxycarbonylbenzoto I77zole 5-aminobenzotriazole 5-butoxybenzotriazole 5-ureidobenzotriazole benzotriazole 5-phenoxycarbonylbenzotriazole (19) 5-(2,3-dichloro Propyloxycarbonyl) benzotriazole Penzimidazole Benzimidazole 5-Chlorobenzimitasol 5-Nitrobenzimitasol 5-n-Butylbenzimidazole 5-Methylbenzimidazole 4-Chloropenzimitasol 5.6-Simethylbenz Imidazole 5-nitro-2-()lifluoromethyl)benzimidazole inzole 6 (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-nitrointasol (9) 3
-Carboxy-5-nitroindacy-root-zole 1 (1) 5-(4-nitrophenyl)tetrazole (2)
5-phenyltetrazole (315-(3-carboxyphenyl)-tetran-
13 Tetozyne-1 (1) 4-hydroxy-6-methyl-5-nitro-1,
3,3a,7-thitraazaindene (2) 4-mercaptol 6-methyl-5-nitro-1,3,3a,7-
Citraazaindenmercabutoar 0) 4-Nitrothiophenol (2) Thiophenol (3) 2-carboxythiophenol Also in general formulas (R-1), (R-2), (R-3) , R, or -+Time←tPUG contains a ballast group commonly used in immobile photographic additives such as couplers, and general formulas (R-1), (R-2), (R-3).
) may be incorporated with a group that promotes adsorption of the compound represented by () to silver halide.

The ballast group has the general formula (R-1), (R-2), (R-3
) is an organic group that provides a sufficient molecular weight to substantially prevent the compound represented by the formula from diffusing into other layers or into the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, and an amide group. group, a ureido group, a urethane group, a sulfonamide group, etc. The ballast group is preferably a ballast group having a substituted benzene ring, particularly a ballast group having a benzene ring substituted with a branched alkyl group.

Specifically, the adsorption promoting group to silver halide is 4-
Thiazoline-2-thione, 4-imidacyline-2-thione, 2-thiohydantoin, rhodanine, thiobarbital acid, tetrazoline-5-thione, 1,2.4-) liazoline-3-thione, 1,3.4- Oxazoline-2
- cyclic thioamide groups, linear thioamide groups such as -thione, benzimidacillin-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3-imidacillin-2-thione, Aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (if the carbon atom to which the -5H group is bonded is a nitrogen atom, it has the same meaning as a cyclic thioamide group that has a tautomeric relationship with this group, and Specific examples of the group are the same as those listed above), a group having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole,
Nitrogen, such as oxazole, oxazoline, thiadiazole, oxathiazole, triazine, azaindene,
Examples include a 5- to 6-membered nitrogen-containing heterocyclic group consisting of a combination of oxygen, sulfur, and carbon, and a quaternary heterocyclic salt such as benzimidazolinium.

These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent for R1.

Specific examples of compounds used in the present invention are listed below, but the present invention is not limited thereto.

■-1゜ ■−4° ■ ■ ■−3° ■ 6゜ ■ 7゜ n-s.

9゜■ ■ 12゜C2L (n) 1)-20゜1)-2 1゜NO! ll-25゜n-26゜ll-27゜I[-22゜I[-23゜1[-24゜n-28゜n-29゜n-30゜NLI customer! ! -38゜It-39゜+1-40゜ll-42゜O2 I[-43゜■-44゜ll-45゜If-49゜[[-50゜5O)Na [[-46゜ff-47゜-48゜■ 1 ■ 2 ■ 3 ll-54 ■ 5 ■-59 ■-60 ■-61 (:J+5 Chll'! ■-56 ■-57 ■-58 ■ 3 ■-64 \ Cl Go ■-65 ■ 8 ■-69 ■-70 1)-7 1 ■-72 In addition to the above-mentioned redox compounds used in the present invention, for example, JP-A-61-213847 and JP-A No. 61-213847;
No. 2-260,153, Japanese Patent Application No. 1) No. 02.393, No. 1-102,394, No. 1-102,395, No. 1
-1) Those described in No. 4,455 can be used.

The method for synthesizing the redox compound used in the present invention is, for example, JP-A No. 61213,847, No. 62260.153, U.S. Pat.
, 803, U.S. Patent No. 3,379,529, 3,
No. 620.746, 4, 31). No. 634, 4,3
No. 32.878, JP-A-49-129,536, No. 5
It is described in No. 6-153,336, No. 56-153.342, etc.

The redox compound of the present invention is used in an amount of 1X10 to 5 X I O-'' mol, more preferably 1X10-' to I X I O-'' mol per mole of silver halide.

The redox compounds of the present invention have suitable water miscibility. Solvents, such as alcohols (metamel, ethanol,
propanol, alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve, etc.

In addition, by the well-known emulsification dispersion method, it is dissolved using oils such as dibutyl phthalate, tricresyl phosphate, glycerin triacetate or diethyl phthalate, and auxiliary solvents such as ethyl acetate or cyclohexanone, and then mechanically emulsified and dispersed. You can also create and use things.

Alternatively, by a method known as solid dispersion method,
The powder of the redox compound can also be dispersed in water using a ball mill, a colloidal gel, or ultrasonic waves.

The hydrazine derivative used in the present invention has the following general formula N
) are preferred.

General formula (1) In the formula, R represents an aliphatic group or an aromatic group, and R1 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryoloxy group, an amino group, a carbamoyl group, or an oxycarbonyl group. represents G.

represents a carbonyl group, a sulfonyl group, a sulfoxy group, a 1-P- group, or an iminomethylene group, and t B+ and Bz 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.

In general formula (1), the aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. The branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms, and the alkyl group may be an aryl group,
It may have a substituent such as an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

The aromatic group represented by R in the general formula (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 ring group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Examples include isoquinoline ring, benzimidazole ring, thiazole ring, and benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R3 is an aryl group.

The aryl group or unsaturated heterocyclic group of R may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, and 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, alkyloxy Carbonyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group or carboxyl group, phosphoric acid adando group, diacylamino group,
Imide group, etc., and preferred substituents include linear, branched or cyclic alkyl groups (preferably 1 carbon number
~20 carbon atoms), aralkyl groups (preferably monocyclic or bicyclic alkyl moieties having 1 to 3 carbon atoms), alkoxy groups (preferably carbon atoms of 1 to 20 carbon atoms), substituted amino groups (preferably amino group substituted with an alkyl group having 1 to 20 carbon atoms), acylamino group (preferably 2 carbon atoms)
-30), sulfonamide group (preferably has 1 to 30 carbon atoms), ureido group (preferably has 1 to 30 carbon atoms), phosphoric acid adando group (preferably has 1 to 30 carbon atoms), ~30).

The alkyl group represented by R1 in general formula (1) is preferably an alkyl group having 1 to 4 carbon atoms,
It may have a substituent such as a halogen atom, cyano group, carboxy group, sulfo group, alkoxy group, phenyl group, or sulfonyl group.

The aryl group is preferably a monocyclic or bicyclic 7-aryl group, and includes, for example, a benzene ring. This aryl group is, for example, a halogen atom, an alkyl group, a cyano group,
It may be monosubstituted with 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, such as a halogen atom, an aryl group, etc. !
may have been replaced.

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

The amino group includes an unsubstituted amino group and a carbon number of 1 to 10.
An alkylamino group or an arylamino group is 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 or an aryloxycarbonyl group having 1 to 10 carbon atoms, 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, when C is a carbonyl group, preferred are 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 (e.g., 0
-hydroxybenzyl group), aryl group (e.g.
phenyl group, 3,5-dichlorophenyl group, 0-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, etc., and a hydrogen atom is particularly preferred.

In addition, when G1 is a sulfonyl group, Rt is an alkyl group (for example, methyl group), an aralkyl group (for example, 0
-hydroxyphenylmethyl group), aryl group (e.g. phenyl group) or substituted amino group (e.g.
Dimethylalcohol groups, etc.) are preferred.

When G is a sulfoxy group, preferred R2 is a cyanobenzyl group, a methylthiobenzyl group, a methoxy group,
An ethoxy group, a butoxy group, a phenoxy group, and a phenyl group are preferred, and a phenoxy group is particularly preferred.

When G is an N-substituted or unsubstituted iminomethylene group,
Preferred R2 is a methyl group, an ethyl group a, or an unsubstituted phenyl group.

As the substituent for R1, the substituents listed for R can be used.

-I'9 G in formula (1) is most preferably a carbonyl group.

Also, Rt splits the C+-Rt part from the remaining molecule, and -
It may be one that causes a cyclization reaction to produce a cyclic structure containing atoms of G, -R, moieties, and specifically, one that can be represented by general formula (a). .

General formula (a) -Rs -z In the formula, Zl attacks G nucleophilically, and G +
Rs is a group that can split the Z 1 moiety from the remaining molecules, R3 is R2 with one hydrogen atom removed, and zl
makes a nucleophilic attack on G1, G,,R,.

A cyclic structure can be generated with Zl.

More specifically, Z easily undergoes a nucleophilic reaction with 61 when the hydrazine compound of the general formula (+) generates the next reaction intermediate by oxidation etc., resulting in R, -N-N-C, -R3- ZI R, -N-N group can be split from G, specifically OH, SH or! ``NHR4CR, is a hydrogen atom,
Alkyl group, aryl group, -COR, or -3Ot
(RS represents a hydrogen atom, alkyl group, aryl group, heterocyclic group, etc.), G such as C00N, etc.
, may be a functional group that directly reacts with (where O
) I, SH, NHR4゜-COOH may be temporarily protected so that these groups are generated by hydrolysis with alkali etc.) Hydrogen atom, alkyl group, alkenyl group, aryl group or heterocyclic group It may be a functional group that can react with G by reacting with a nucleophile such as a hydroxyl ion or a sulfite ion, such as (representing G).

Furthermore, the ring formed by G+, R3, and ZI is preferably a 5- or 6-membered ring.

Among those represented by general formula (a), preferred are those represented by general formulas (b) and (C).

General formula (b) In the formula, R>'""R1' is a hydrogen atom, an alkyl group,
(preferably those with 1 to 12 carbon atoms), alkenyl groups (
B may be the same or different, and B may have a substituent. These are atoms necessary to complete a membered ring or a 6-membered ring, m and n are 0 or 1, and (n+m) is 1 or 2.

Examples of the 5- or 6-membered ring formed by B include a cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring, and a quinoline ring.

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

General formula (c) In the formula, Re' and Re2 represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, etc., and may be the same or different.

R and 3 represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

p represents O or 1, and q represents 1-4.

Re' s Re '' and R% may be bonded to each other to form a ring as long as Z can make an intramolecular nucleophilic attack on G.

Re'sRc'' is preferably a hydrogen atom, a halogen atom, or an alkyl group, and Rc3 is preferably an alkyl group or an aryl group.

q preferably represents 1 to 3; when q is l, P represents 1 or 2; when q is 2, p represents 0 or 1; when q is 3, p represents O or 1; when q is 2, p represents 0 or 1; or CR when 3
,' Rc! may be the same or different.

Zl has the same meaning as in general formula (a).

AI, At is a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms, and an arylsulfonyl group (preferably a phenylsulfonyl group or a sum of Hammett's substituent constants -
0.5 or more), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more) A benzoyl group, or a linear, branched, or cyclic unsubstituted or substituted aliphatic acyl group (substituents include, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group,
Examples include sulfonic acid groups. )) B, , B is most preferably a hydrogen atom.

R2 or Rt in the general formula ([) may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein.

The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
It can be selected from alkylphenoxy groups, etc.

R1 or R2 in the general formula (1) may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Examples of such adsorption groups include a thiourea group, a heterocyclic thioamide group, and a mercapto group. U.S. Pat. No. 4,385.108, U.S. Pat. No. 4,459, for ring groups, triazole groups, etc.
, No. 347, JP-A No. 59-195, 233, No. 59-
200゜No. 231, No. 59-201.045, No. 59
-201.046, 59-201,047, 5
9-201.048, 59-201.049, JP-A-61-170,733, JP-A-61-270,744
No. 62-948, patent application No. 62-67.508,
Examples include the groups described in Nos. 62-67.501 and 62-67,510.

Specific examples of the compound represented by the -JG formula ([) are shown below, however, the present invention is not limited to the following compounds.

! -1) I-2) ■-3) ■-4) Js I-6) 1-12) r-15) ! -16) ■-7) l-8) 1-9) CHzC1'! tcIhsH 1-1)) [-17) 1-1.8) N■-N 1-20) <i N■口NI 22) ■ 23) xHs 1-26> 1-31) 1-33) r -34) 1-27) 1-28) 1-30) 1-35) 1-36> r-37) r-38) Shit IIs Shi II Tomi υn 1-39) 1-40) [-41) T -42) I-47) 1-48) 1-49) 1-50) H M Cj! 1-43) r-44) 1-45) 1-46) r-51) r-52) 1-53) r-54) In addition to the above, hydrazine derivatives used in the present invention include RESEARCHDISCLO5uRE.
I te+m23516 (January 1983), P.
346) and the references cited therein, as well as U.S. Pat.
No. 080.207, No. 4,269.929, No. 4.
No. 276.364, No. 4,278,748, No. 4,3
85.108, 4,459,347, 4,56
No. 0,638, No. 4,478.928, British Patent No. 2,
01), 391B, JP-A No. 60-179734, No. 6
2-270,948, 63-29.751, JP 61-170,733, JP 61-270,744, JP 62-948, EP 217,310, Japanese Patent Application 1983
No. 1-175,234, No. 61-251,482,
No. 61-268, 249, No. 61-276゜283,
〃62-67528, 〃62-67゜509, #6
No. 2-67.510, No. 62-58.513, 162
-130,819, l162-143,467,
62-166.1) No. 7, or tJs4,686,1
No. 67, JP-A-62-178,246, JP-A-63-
No. 234,244, No. 63-23.4.245, No. 6
No. 3-234.246, No. 63-294.552, No. 63-306.438, Patent Application No. 62-168゜1) 7
No., -62-247,478, l63-105.68
No. 2, 163-1) 4.1) No. 8, 163-1) 0.0
No. 51, -63-1) 4, 1) No. 9, 163-1) 6.
No. 239, No. 163-147.339, jI63-17
No. 9.760, No. 163-229,163, Patent Application No. 1-
No. 18,377, #1-18,378, 1)-18,
No. 379, 1)-15.755, #1-16,814
No., No.-1-40,792, 1) No.-42,615,〃
1-42,616 can be used here.

In the present invention, when the hydrazine derivative represented by the general formula (1) is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer, but it is preferably contained in a non-photosensitive hydrophilic colloid layer (for example, a protective layer). , intermediate layer, filter layer, Haley silane prevention layer, etc.).Specifically, if the compound used is water-soluble, it may be contained in an aqueous solution, or if it is poorly water-soluble, it may be contained in alcohols or esters. It can be added to a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as a ketone.When added to a silver halide emulsion layer, it can be added at any time from the start of chemical ripening to before coating. However, it is preferable to add it between the end of chemical ripening and before coating, and it is particularly preferable to add it to the coating liquid prepared for coating.

In the present invention, the hydrazine derivative represented by the general formula (1) is preferably contained in an amount of 1×10 4 mol to 1
It is preferable to contain 0-' to 4×10-' moles.

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

In the formula, RI3 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic residue, Q represents a simple bond, a sulfur atom or selenium atom as a divalent group, an oxygen atom as a divalent group, a disulfide group (-3- 3-)NR,,,R,,N-
C-3-5- or NR1, C5 is represented by 1, provided that R8 has the same meaning as R1.

R1 and R2 each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, or an amino group.

A 5- or 6-membered heterocycle may be formed between Ro and R14, Ro and R,t, or R1 and RI3, provided that Ro
When a 5- or 6-membered heterocycle is formed between and R1ff, neither R1) nor Rra contains a hydrogen atom.

The alkyl groups represented by R1), R12, R1 and Rra have 1 to 20 carbon atoms, including substituted ones, and include, for example, a halogen atom (for example, a chlorine atom).
, cyano group, carboxy group, hydroxy group, carbon number 2~
6 acyloxy group (e.g. acetoxy group), alkoxycarbonyl group having 2 to 22 carbon atoms (e.g. ethoxycarbonyl group, butoxycarbonyl group, aryl group (monocyclic or bicyclic), which may be substituted, even R phenyl Examples of advantageous alkyl groups include the following: methyl, tolyl, p-sulfophenyl, etc.
Ethyl group, propyl a (n- or hi-), butyl group (n-1i- or t-), amyl (which 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, carboxymethyl group, 2-carboxyethyl group, 2-hydroxyethyl group, 2-acetoxyethyl group, acetoxyethyl group,
Ethoxycarbonylmethyl group, butoxycarbonylmethyl group, 2-methoxycarbonylethyl group, benzyl group,
O-nitrobenzyl group, p-sulfur benzyl group.

The aryl group represented by Ro, Rat, R13 and R14 is monocyclic or 21t, preferably monocyclic.
Examples of substituents include alkyl groups having 1 to 20 carbon atoms (such as methyl groups,
ethyl group, nonyl group), alkoxy group having 1 to 20 carbon atoms (e.g. methoxy group, ethquine group), hydroxy group,
Examples include halogen atoms (for example, chlorine atoms and bromine atoms), carboxy groups, and sulfo groups. Specific examples of aryl groups are:
phenyl group, p-)lyl group, p-methoxyphenyl group,
p-hydroxyphenyl group, p-chlorophenyl 5.2
．． s-dichlorophenyl group, p-carboxyphenyl f
=, o-carboxyphenyl, 1.4-sulfophenyl group, 2.4-disulfophenyl group, 2.5-disulfophenyl group, 3-sulfophenyl group, 3,5-disulfophenyl group, etc. .

The heterocyclic residue of R8, R1□, R1ff or R8 is preferably a 5- to 7-membered residue, such as pyrrolidine, pyrrole, tetrahydrofuran, furan, tetrahydrothiophene, thiophene, thiazole, thiasiapurine, oxazole, oxazoline, imidazole. ,
Examples include imidacilline, triazole, tetrazole, thiadiazole, oxadiazole, benzothiazole, benzoxazole, benzimidazole, morpholine, pyridine, quinoline, quinoxaline, azepine, and the like. These may be substituted with the groups mentioned as substituents for R+ to R.

R1ff and Ro or R1 and R1! 5 formed by
Examples of the membered or six-membered ring include a piperidine ring, a perazine ring, a virol ring, a pyrazole ring, an imidazole ring, and a triazole ring, and preferred are a piperidine ring, a virol ring, a piperazine ring, and a morpholine ring.

The 5- or 6-membered heterocycle formed between Ro and R is, for example, a rhodanine ring, a thiazoline ring, a thiazolidine ring, a selenazoline ring, an oxazoline ring, an oxazolidine ring, an imidacilline ring, an imidazolidine ring, a birapurine ring,
Pyrazolidine ring, l.

3.4-thiadiazoline ring, 1.3.4-oxadiazoline ring, L, 3.4-1-riazoline ring, tetrazoline ring, thiohydantoin ring, dihydropyridine ring, dihydrobiridine ring, dihydrotriazine ring, etc. . Of course, these heteroFiJs include those in which a 5- to 7-membered carbocycle or heterocycle is condensed. Namely, for the thiazole ring, benzothiapurine nucleus, naphthothiazoline nucleus, dihydronaphthothiazoline nucleus, tetrahydrobenzothiazoline nucleus, etc.; for the selenazole ring, benzoselenazoline nucleus, etc.; for the oxazoline ring, benzoxazoline nucleus, naphthoxazoline nucleus, etc.; imidacillin Benzimidacilline nucleus, dihydroimidazolopyrimidine nucleus, etc. for the ring; dihydrotriazolobiridine nucleus, dihydrotriazolopyrimidine nucleus, etc. for the triazoline ring; dihydropyrazolopyridine nucleus, di- and dropyrazolopyrimidine nucleus between the pyrazoline ring etc.; A dihydropyrazolopyrimidine nucleus, a dihydropyrrolopyrimidine nucleus, a dihydrotriazolopyrimidine nucleus, etc. are included between the dihydropyrimidine ring.

The carbon atoms of these heterocyclic nuclei can have various substituents. For example, an alkyl group having 1 to 20 carbon atoms (for example, 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 1&), alkylthio groups having 1 to 20 carbon atoms (e.g. methylthio group, ethylthio group, butylthio group), hydroxy group, mercapto group, Amino groups (including unsubstituted as well as substituted amino groups, such as dimethylamino group, methylamino group,
Alkyl-substituted amino groups such as diethylamino group, butylamino group, benzylamino group; aryl-substituted amino group such as anilino group, diphenylamino group; acetylamino group, capryloylamino group, benzoylamino group, methylsulfonylamino group, benzenesulfonylamino group,
P-) Acylamino groups such as luenesulfonylamino groups; thioamide groups such as acetylthioamide groups and propionylthioamide groups), aryl groups (e.g. phenyl groups, naphthyl groups, tolyl groups), alkenyl groups having 2 to 20 carbon atoms (e.g. allyl group, methallyl group), aralkyl group having 1 to 4 carbon atoms in the alkyl moiety (e.g. benzyl group, phenethyl group), halogen atom (e.g. chlorine, bromine), cyano group, carboxy group, sulfo group, carbamoyl group (substituted For example, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group,
ethylcarbamoyl group, phenylcarbamoyl group), thiocarbamoyl group (including substituted ones, such as thiocarbamoyl group, methylthiocarbamoyl group, dimethylthiocarbamoyl group, ethylthiocarbamoyl group,
phenylthiocarbamoyl group), alkoxycarbonyl group having 2 to 22 carbon atoms (e.g. methoxycarbonyl group,
ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), C2-C22 furkylcarbonyl group (for example, acetyl group, capryloyl group), oxygen atom, etc.

The alkyl group may further include a carboxy group, a sulfo group, an alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group), an acyloxy group (e.g. acetoxy group), an aryl group (e.g. phenyl group, an optionally substituted e.g. nitrophenyl group). ) etc. may be substituted.

On the substitutable nitrogen atom in the heterocyclic chain, R1□
can have substituents as shown for.

When Q represents N R, the alkyl group represented by R14 has 1 to 20 carbon atoms and includes substituted ones. Examples of substituents for alkyl groups include halogen atoms, cyano groups, carboxy groups, sulfo groups, sulfato groups, phosphor groups, carbamoyl groups, aminosulfonyl groups, hydroxy groups, and alkoxy groups having 1 to 20 carbon atoms (for example, methoxy groups, ethoxy group, propoxy group,
Butoxy group: Also includes substituted groups, such as hydroxy group, alkoxy group having 1 to 6 carbon atoms (e.g. methoxy group, ethoxy group, propoxy group), acyloxy group having 2 to 8 carbon atoms (e.g. acetoxy group, propionic group) oxy group), sulfo group, sulfoalkoxy group having 1 to 6 carbon atoms (for example, 2-sulfoethoxy group, 3-sulfopropoxy group), acyloxy group having 2 to 22 carbon atoms (for example, acetoxy group, 10 pionoxy &), alkenyl group having 2 to 22 carbon atoms (e.g. vinyl group), alkoxycarbonyl group having 2 to 22 carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group,
butoxycarbonyl group, dodecyloxycarbonyl group)
, aryl group (monocyclic or bicyclic, optionally having a substituent, e.g. phenyl group, p-sulfophenyl group), heterocyclic residue (e.g. thiazole ring residue, oxazole ring residue, imidazole ring residue) group, thiadiazole ring residue, oxadiazole ring residue, triazole ring residue, tetrazole ring residue, pyrimidine ring residue, etc.

), etc.

Specific examples of the alkyl group represented by R1□ are as follows: methyl group, ethyl group, propyl group (n- or i
-), butyl group (n-1sec-1= 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-sulfoethyl group, 3-sulfobutyl group,
4-sulfobutyl group, 2-sulfatoethyl group, 2-phenylethyl 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, methoxycarbonylmethyl 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.

A more preferable compound among the compounds represented by -Tsuriyoshi (III) is shown by -Tsuriyoshi (I[Ia) below.

(I[[a) ,...Ql.

c-n-R,.

Q' represents an atomic group required to complete a 5- or 6-membered heterocycle, and R14 has the same meaning as in general formula (III). However, R14 does not generate hydrogen atoms,
In the atomic group represented by Q', the atoms adjacent to the thioketo group are never bonded to a hydrogen atom.

A specific example of a heterocycle completed with Q is R3, and RIf
The same as shown for the heterocycle formed by f.

The heterocycle completed by Ql has a divalent substituent, such as an oxo group (-0), a thioxo group (-5), an ethylidene group (CH, CH-), a WtI3 ethylidene group (for example, a benzoxazolilidene ethylidene group, thiazolinylidene ethylidene group, pyridylidene ethylidene group, quinolylidene ethylidene group), heterocyclic divalent residues (for example, benzoxazolilidene group, benzthiazolylidene group thiazolinylidene group, pyridylidene group, quinolylidene group) etc.).

Compounds represented by the general formula (Iff) are, for example, Japanese Patent Publication No. 48-34, 169 (Compound-Nllll to 8,
31.32), Pharmaceutical Journal, 1365-1369 (1
954) (Compound Example-N1)9), Beinste
inxm, 394, It/121 (Compound examples - 菟12 and 13), Japanese Patent Publication No. 47-18008 (Compound examples - NCJ
, l 9 ), Japanese Patent Publication No. 4B-34168 (Compound Example - Toru 25), etc.

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

[[[-1m-2 l-3 1) [-4 -5 1)-6 CH.

CH8 1)-7 1[1-8 Hx isoc5H++ 1)1-9 ■-10 Hs ■-1) ■-12 ■-13 gHs ll-14 ll-20 ■-21 ■-22 ■-23 ■-15 1[1-16 1[[-17 CtH,OH 1)[-19 ■-24 ■-27 ■-28 ■-29 S -30 ■-32 ■ 3 ■ 4 In the present invention, -FG formula (I[ The compound represented by I) is preferably contained in the silver halide emulsion layer, but is also included in other non-photosensitive hydrophilic colloid layers (e.g. protective layer,
(intermediate layer, filter layer, antihalation layer, etc.).Specifically, if the compound used is water-soluble, it may be contained in an aqueous solution, or if it is poorly water-soluble, it may be contained in alcohols, esters, ketones, etc. It is best to add it to a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as a water-miscible organic solvent.If it is added to a silver halide emulsion layer, it can be added at any time from the start of chemical reaction to before coating. However, it is preferable to add it between the end of chemical ripening and before coating.
In particular, 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 determined by 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 fog. It is desirable to select the optimum amount depending on the type of inhibitory compound, etc., and testing methods for selection are well known to those skilled in the art. or lXl
0-'' moles, especially in the range of 10-'' to 5×10-'' moles.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver iodochlorobromide, etc., but iodobromide is preferable.The content of silver iodide is It is preferably 10 mol% or less, particularly 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, 0.7μ or less), particularly 0.7μ or less.
．． There is basically no limit to the zero particle size distribution, which is preferably 5 μm or less, but it is preferably monodisperse. Monodisperse herein means that at least 95% of the particles by weight or number of particles is composed of particles having a size within 140% of the average particle size.

Silver halide grains in photographic emulsions are cubic, octahedral, 14
It may have regular crystal bodies such as a hedron or a rhombic dodecahedron, and particularly preferred are a cube and a dodecahedron. Also spherical, plate-shaped, aspect ratio 3
~20 irregularities such as plate-like
r) crystals, or a composite form of these crystal forms.

The interior and surface layers of the silver halide grains may have a uniform phase or may consist of different phases.

Two or more silver halide emulsions formed separately may be used in combination.

In the silver halide emulsion used in the present invention, cadmium salt, ginate, lead salt, thallium di salt, rhodium salt or its complex salt, iridium salt or its complex salt, etc. are added to the silver halide emulsion in the process of forming silver halide grains or during physical ripening. They may coexist.

Silver halides particularly suitable for use in the present invention are prepared in the presence of 10-3 to 10-' mole of iridium salt or complex salt thereof per mole of silver, and have a silver iodide content on the grain surface of The silver iodide content is higher than that of silver iodide. When an emulsion containing such silver haloiodide is used, photographic characteristics with higher sensitivity and higher gamma can be obtained.

In the above, it is desirable to add the iridium salt in the above amount before the completion of physical ripening in the silver halide emulsion manufacturing process and during grain formation.

The iridium salt used here is a water-soluble iridium salt or an iridium complex salt, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridate (II[), potassium hexachloroiridium (IV) a, ammonium hexachloroiridium (Iff) a and so on.

The emulsion of the present invention does not need to be chemically sensitized, but may be chemically sensitized. Examples of chemical sensitization methods include sulfur sensitization, reduction sensitization, gold sensitization, etc. The methods can be used alone or in combination. A preferred chemical sensitization method is sulfur sensitization.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used. Specific examples are U.S. Patent Nos. 1.574.944 and 2.
, No. 278,947, No. 2,410,689, No. 2,
No. 728,668, No. 3,501.313, No. 3,6
No. 56,955. Preferred sulfur compounds are thiosulfates and thiourea compounds, and the PAg during chemical sensitization is preferably 8.3 or less, more preferably in the range of 7.3 to 8.0.

Furthermore, Mo1sar, Klein Gelatine
, Proc, Symp, 2nd+301~309
(1970) et al. also give good results using a combination of polyvinylpyrrolidone and thiosulfate.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. There is no problem in containing complex salts of noble metals other than metals, such as platinum, palladium, and iridium.
No. 0, British Patent No. 618.061, etc.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in U.S. Pat.
, 518,698, 2゜983.609, 2,98
No. 3,610 and No. 2°694.637.

The silver halide emulsion in the light-sensitive material used in the present invention is
One type may be used alone, or two or more types (for example, those with different average particle sizes, those with different halogen compositions, those with different crystal habits, and those with different chemical sensitization conditions) may be used in combination.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol, Various synthetic hydrophilic polymers such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc.+4j! /J quality can be used.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

In the present invention, JP-A No. 55-52050, page 45~
It is also possible to add a sensitizing dye (for example, cyanine dye, merocyanine dye, etc.) having an absorption maximum in the visible region as described on page 53. This allows spectral sensitization to be performed on the longer wavelength side than the inherent sensitivity region of silver halide.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

Useful sensitizing dyes, supersensitizing dye combinations and supersensitizing substances include Research Discro salts, aliphatic or aromatic quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
and cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocycles.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more and described in Japanese Patent Publication No. 5B-9412.

Further, in order to prevent static electricity, it is preferable to use a fluorine-containing surfactant described in JP-A-60-80849.

The photographic light-sensitive material of the present invention contains hydroquinone derivatives (so-called DIR-
hydroquinone).

Specific examples thereof include U.S. Pat. No. 3,379,529, U.S. Pat. No. 3,620.746, and U.S. Pat.
No. 4, U.S. Patent No. 4,332,878, Japanese Unexamined Patent Publication No. 49-1
29,536, JP 54-67.419, JP 56-153,336, JP 56-153,342
No., JP-A No. 59-278,853, JP-A No. 59-9043
Examples include compounds described in No. 5, No. 59-90436, and No. 59-138808.

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

The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example, a polymer containing as a monomer component alkyl (meth)acrylate, alkoxy acrylic (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. is used. 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 organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acrylic acid. Polymers or copolymers having acid monomers such as , maleic acid, phthalic acid as repeating units may be mentioned. Regarding these compounds, see JP-A-61-223834 and JP-A No. 61-223834.
-228437, 62-25745, and 62
The record of specification No.-55642 can be referred to. Among these compounds, particularly preferred is ascorbic acid as a low-molecular compound, and as a high-molecular compound, an acid monomer such as acrylic acid and a crosslinking monomer having two or more unsaturated groups such as divinylbenzene are particularly preferred. It is a copolymer water-dispersible latex.

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

In order to obtain ultra-high contrast and high-sensitivity photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or US Pat.
It is not necessary to use a highly alkaline developer having a pH close to 13 as described in No. 419,975, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains 0.15 mol/1 or more of sulfite ion as a preservative, and has a pH of
A sufficiently ultra-high contrast negative image can be obtained using a developer having a pH of 10.5 to 12.3, particularly pH 1) and 0 to 12.0.

There is no particular restriction on the developing agent used in the developer used in the present invention, but it is preferable that it contains dihydroxybenzenes, since it is easy to obtain a good quality award. A combination of -3-pyrazolidones or a combination of dihydroxybenzenes and P-aminophenols may also be used.

The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Examples include dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, and hydroquinone is particularly preferred.

As the developing agent for 1-phenyl-3-pyrazolidone or its derivative used in the present invention, l-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-4-pyrazolidone, 1-phenyl-4-methyl-4 -Hydroxymethyl-3-virapritone, ■-phenyl-44-diroxymethyl-3-pyrazolidone, 1-phenyl-5-
Methyl-3-virapritone, 1-P-aminophenyl-
4,4-dimethyl-3-pyrazolidone, ip tolyl-
Examples include 4,4-dimethyl-3-pyrazolidone.

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

The developing agent is preferably used in an amount of usually 0.05 mol/l to 0.8 mol/l. When using the former, set it to 0.
05 mol/l to 0°5 mol/l, the latter 0.06 mol/l
It is preferable to use it in an amount equal to or less than i.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium hexaethite, potassium metabisulfite, formalde and sodium metabisulfite. The amount of sulfite is preferably 0,715 mol/i or more, particularly 0.5 mol/1 or more, and the upper limit is preferably 2.5 mol/l.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
The pH of the developer, including the H moderation agent and buffering agent, is 10.5 to 1.
It is set between 2 and 3.

Additives used in addition to the above ingredients include compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, and methyl cellosolve. , organic solvents such as hequinlene glycol, ethanol, and methanol; antifoggants such as indazole compounds such as i-phenyl-5-mercaptotetrazole and 5-nitroindazole; and penttriazole compounds such as 5-methylbenztriazole; It may also contain a black pepper inhibitor, and if necessary, a color toning agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, and JP-A-56-10
It may also contain the azuno compound described in No. 6244.

The developing solution of the present invention contains a silver stain preventive agent.
, No. 347 can be used. Patent application 1986-109, 1974 as a solubilizing agent added to the developer.
Compounds described in No. 3 can be used. Furthermore, as a pH 17i additive for use in developing solutions, JP-A-60-93,4
Compounds described in No. 33 or Japanese Patent Application No. 61-28708
Compounds described in this issue can be used.

As the fixing agent, those having commonly used compositions can be used. In addition to thiosulfates and thiocyanates, there are other fixing agents that are known to be effective as fixing agents. R sulfur compounds can be used.

The fixing solution may contain water-soluble aluminum (e.g. aluminum sulfate, light bread, etc.) as a hardening agent, where the amount of water-soluble aluminum salt is usually 0.4 to 2.0.
g-AN/l. A trivalent iron compound can also be used as an oxidizing agent in the form of a complex with ethylenediaminetetraacetic acid.

The processing temperature is usually selected between 18°C and so'c, more preferably between 25°C and 43°C.

(Example) Next, the formulation of the developing solution described below will be specifically explained based on Examples of the present invention.

Using.

(Developer formulation) Hydroquinone N, methyl P, aminophenol 1/2 sulfate, sodium hydroxide, potassium hydroxide, 5-sulfosalicylic acid, boric acid, potassium sulfite, ethylenediamine, tetraacetic acid, disodium chloride, potassium bromide, 5-methylbenzotriazole, n, butyl, diethanol a Add hot water and add 45.0g 8g 8g 8g 8g 8g 8g 1, Og 6, Og 0.6g 0゜18゜55゜45゜25゜1) 0゜15.0g f (pH song 1)゜6) Example-l Particle size 0.1 using controlled double jet method.
25μ cubic monodisperse silver iodobromide emulsion (varying number 0.15
, silver iodide 0.5 mol %, uniform iodine distribution) was prepared. This silver iodobromide emulsion contains 3 TrCl, h 4
10-'-T: JL//A g -1-/L/ was added.

This emulsion was desalted by the flochieration method, and then kept at 50'C, and the following compound (a) was added as a sensitizing dye to 1 mol of silver - 5 x 10-' mol, 104 per 1 mol of silver.
A molar potassium iodide solution was added and the mixture was allowed to stand for 15 minutes, and then the temperature was lowered.

4-hydroxy-6methyl-1 was added to this emulsion as a stabilizer.
．． 3,3a,? - Tetrazaindene, 5-methylbenztriazole, the following compound (b) (a) (b) (c) Add ethylene glycol to 15 tng/ni, and dissolve the solid content of polyethyl acrylate dispersion against gelatin. 1,3-divinyl-sulfonyl-2-propanol was added as a hardening film at a ratio of 30 wt%, and the film was coated on a polyethylene terephthalate film. It was applied at a weight of 3.6 g/bo. On top of this, 1.2 g/m of gelatin was added as a protective layer.
40mg of amorphous 5jOx matting agent with a particle size of approximately 3μ
/rd, methanol silica O, Ig/m, polyacrylamide 100■/E, hydroquinone 200■/rrr
A silicone oil and a fluorosurfactant (b) represented by the following structural formula as a coating aid were added at a rate of 5 cm/h, respectively.

As a hydrazine compound (1-19) (IXIO''S mol 1 mol Ag) (1-5) (5X10-' mol 1 mol A
g) was added thereto, and a layer containing poly with an average molecular weight of 1) 600 and sodium dodecylbenzenesulfonate was simultaneously coated to prepare samples as shown in Table 1.

The bank layer was applied using the following recipe.

[Back layer prescription]

Gelatin 4g/Bomanoto agent Polymethyl methacrylate (particle size 3.0-4.0
μ) 10■/Boratex Polyethyl acrylate 2g/Bosurfactant Sodium p-dodecylbenzenesulfonate 40■/Bofluorine surfactant dye (a) CH3-C-CCH-C--C-CI (ffl Dye (b) Gelatin hardening agent 5 / Bo CH Awa cHsoz Dye Dye (a), Material dye (a) Dye (b) Dye (c) CH.

CON　H-’ 1)0IIIg/rrr Mixture of [b] and (c) 50■/bo 100mg/bo 50ff1g/po Dye [C] The evaluation was conducted using the following test method.

(Photographic characteristics) Photographic characteristics 1 was obtained using a developer with the above prescription using an FC-660F automatic processor (manufactured by Fuji Photo Film Co., Ltd.) at 38
This is the result of C30' processing.

Photographic property 2 is 100% black Fujiris Ortho Film G
A-100 complete size (50.8CIllX61cm)
These are the results of processing in the same manner as in Photographic Properties 1 using a developer after processing 150 sheets.

〔image quality〕

1. Evaluation of image quality (1) Creation of manuscript Monochrome scanner 5CA manufactured by Fuji Photo Film Co., Ltd.
NART30 and special sensitive material 5F-1o.

Using this method, we created a transparent image of a person consisting of halftone dots and a step wedge in which the halftone percentage was changed stepwise. At this time, the number of screen lines was 150 lines/inch.

(2) Photography by Dainippon Screen ■ The original was set on a plate-making camera C-440 so that the magnification was equal to 1:1, and then the evaluation sample was exposed to light by irradiating it with a Xe lamp.

At this time, exposure was performed so that 95% of the step wedge of the original was exposed to 5%. Note that the filter of the present invention was installed between the original and the light source.

(3) As in evaluation (2), the exposure amount is 1! The halftone percentage of the small dot side (highlight part) was combined, and the sample was evaluated on a five-point scale (5 to 1) in descending order of the gradation reproducibility (difficulty of halftone dots being crushed) in the shadow area. Ta.

2. Evaluation of 6-picture image quality Grade 7 Mincho typeface with reflection density in the range of 0.5 to 1.2.
This is the result of a manuscript consisting of Gothic phototypesetting letters taken with a Dainippon Screen camera (DSC351) and then developed (38"C30') under the same conditions as the photographic characteristics.Evaluation is in 5 stages. ``5'' is the best.
"1" represents the worst quality, "5" or "4" is usable, "3" is poor but barely practical, and "2" or "rl" is impractical.

Procedural amendment 1990 2pm close month end/day

Claims (5)

[Claims] (1) In a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, the emulsion layer or other hydrophilic colloid layer contains a hydrazine derivative, a compound having a thioamide bond, and an oxidized silver halide emulsion layer. 1. A silver halide photographic light-sensitive material, each containing at least one redox compound that releases a development inhibitor by releasing a development inhibitor. (2) Claim No. (1) characterized in that the redox compound has hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines, and reductones as redox groups. The silver halide photographic material described in Section 1. (3) Claim (1) characterized in that the redox compound has a hydrazine as a redox group.
The silver halide photographic material described in Section 1. (4) The redox compound has the following general formula (R-1), (R
The silver halide photographic material according to claim (1), which is at least one compound selected from the compounds represented by -2) and (R-3). General formula (R-1) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (R-2) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (R-3) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ In these formulas, R_1 represents an aliphatic group or an aromatic group ▲ Numerical formulas, chemical formulas, tables, etc. are available. G_1 is -C- group, -C-C- group, ▲numerical formula,
Chemical formulas, tables, etc. are available ▼ -SO- group, -SO_2 group or ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ Represents. G_2
represents a simple bond, -O-, -S-, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, 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 has the same meaning as A_1 or represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 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 stands for development inhibitor. (5) The silver halide photographic material according to claim (1), wherein the redox compound is represented by the following general formula (R-1). General formula (R-1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A_1 and A_2 are both hydrogen atoms, or one is a hydrogen atom and the other is a sulfinic acid residue, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R_0 represents an alkyl group, alkenyl group, aryl group, alkoxy group or aryloxy group, l represents 1 or 2), Time represents a divalent linking group, and t represents 0 or 1
represents. PUG stands for development inhibitor. G_1 is carbonyl group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, sulfonyl group, sulfoxy group, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ (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. )