JPH0339952A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a contrasty image with a developing soln. having high stability by forming a photosensitive silver halide emulsion layer contg. a hydrazine deriv. and a hydrophilic colloidal layer contg. a redox compd. capable of releasing a development inhibitor when oxidized. CONSTITUTION:At least one photosensitive silver halide emulsion layer contg. a hydrazine deriv. and a hydrophilic colloidal layer contg. a redox compd. capable of releasing a development inhibitor when oxidized and different from a photosensitive silver halide emulsion layer are formed. The redox group of the redox compd. is preferably selected among hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines and reductones, especially hydrazines. An image can be made contrasty by development with a processing soln. having satisfactory shelf stability.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material and a method for forming an ultra-high contrast negative image using the same, and in particular to a silver halide photograph used in a photolithography process. The present invention relates to ultra-high contrast negative type photographic materials suitable for photosensitive materials.

(Prior Art) In the field of photoengraving, in order to deal with the diversity and complexity of printed matter, there are demands for photosensitive materials with good original reproducibility, stable processing solutions, and easy 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 posters. The point will be photographed. When reduced, the number of lines/ink is larger than that of the original, resulting in a photograph of a thinner point. Therefore m1
In order to maintain the reproducibility of ii., 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 found that ortho-sensitized photographic materials are more strongly affected by the chromatic aberration of the lens, 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 for a wide latitude, we use a lithium-type silver halide photosensitive material made of silver chlorobromide (silver chloride content of at least 50%), with an extremely low effective concentration of sulfite ions (total, 1 mol/min). I!, hereafter)
A method is known in which a line image or a halftone dot image with high contrast and high blackening density, in which image areas and non-image areas are clearly distinguished, is obtained 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. is extremely slow,
The current situation was that work efficiency was decreasing.

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-gradation photographic characteristics, and one example of this is US Pat. No. 4,166. No. 742, No. 4,168,977, No. 4
, No. 221,857, No. 4,224,401, No. 4,
No. 243゜739, No. 4,272,606, No. 4,3
As seen in No. 11.781, a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound has been added is prepared at a pH of 11.0 to 12.3 and a sulfite preservative of 0.00.
A system has been proposed in which a super-tone negative image with T of more than 10 is formed by processing with a developer containing 15 mol/1 or more and having good storage stability. This new image forming system has the feature that it can also use silver iodobromide and silver chloroiodobromide, whereas conventional ultra-high contrast image formation could only use silver chlorobromide, which has a high silver chloride content. There is.

The above image system has sharp halftone dot quality, processing stability,
Although it shows excellent performance in terms of speed and original reproducibility, a system with further improved original reproducibility is desired in order to deal with the variety of printed matter in recent years.

JP 61-213847 and US 4,684.6
No. 04 discloses a photosensitive material containing a redox compound that releases a photographically useful group upon oxidation, and attempts are made to widen the gradation reproduction range. However, in ultra-high contrast processing systems using hydrazine derivatives, these redox compounds have the disadvantage of inhibiting high contrast, and their properties cannot be utilized.

(Objective of the Invention) Therefore, the first object of the present invention is to provide a photosensitive material for plate making that can produce high-contrast images using a highly stable developer.

The second object is to provide a photosensitive material for plate making with a wide halftone gradation. Thirdly, it is an object of the present invention to provide a photosensitive material for plate making which is a high-contrast photosensitive material using a hydrazine nucleating agent and has a wide halftone gradation.

(Structure of the Invention) These objects of the present invention are to provide at least one photosensitive silver halide emulsion layer containing a hydrazine derivative and a photosensitive silver halide emulsion layer containing a redox compound capable of releasing a development inhibitor upon oxidation. It was coupled with a silver halide photographic light-sensitive 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 when oxidized will be explained.

The redox group of the redox compound is preferably hydroquinones, catechols, naphthohydroquinones, aminophenols, birapritons, hydrazines, hydroxylamines, and 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) I At General formula (R-2) 1 A.

4 General formula (R-3) 0 In these formulas, 1 represents an aliphatic group or aromatic group 1 or -P- group, G3 is a simple bond, Gt
R* represents -O--S- or -N-, and R8 represents a hydrogen atom or R1.

A + , A z are hydrogen atoms, alkylsulfonyl groups,
In general formula (R-1), which represents an arylsulfonyl group or an acyl group and may be substituted, at least one of AI%At is a hydrogen atom. A has the same meaning as A, or represents -GHzCH-+Time)z-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, O represents O or l, and PUG represents a developing printing agent.

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 straight, 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 carbonate group.

In general formulas (R-1), (R-2), (R-3), R
The aromatic group represented by 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 7-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.

Particularly preferred as R1 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, a W-substituted amino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, i-halogen group, 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 straight, 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), azilamino group (preferably one 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 acid amide group (preferably having 1 to 40 carbon atoms), etc. .

For general formulas (R-1), (R-2), and (R-3), -0- group and -SO,- group are preferable, and -C- group is most preferable.

At, At is a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms, and an arylsulfonyl group (preferably a phenylsulfonyl group or) \ phenylsulfonyl substituted such that the sum of the substituent constants of Met is -0.5 or more group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or) a benzoyl group substituted such that the sum of the substituent constants of Met is -0.5 or more, or a linear, branched, or cyclic group 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.

At, a hydrogen atom is most preferred as At.

A is a hydrogen atom, -CHz-CH-eTi+
-1PUG4 is most preferred.

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

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 opening 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 an analogue thereof;
No. 9,323, No. 4,421.845, Research Disclosure Magazine No. 21,228 (December 1981)
), U.S. Patent No. 4,416,977
135,944), JP-A-58-209゜736,
58-209,738, etc., which generates quinomonomethane or its analogues by electron transfer via a double bond conjugated with an oloxy group or a heterocyclic oxy group and releases PUG; U.S. Patent No. 4,420,5
No. 54 (Japanese Patent Publication No. 57-136.640), JP-A-57
- ■ No. 35.945, No. 57-188,035, No. 5
8-98,728 and 58-209,737, etc., which release PUG from the γ-position of the enamine by electron transfer of the moiety having an enamine structure of the nitrogen-containing heterocycle; JP-A-57-56 , 837, which releases PUG through an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated with the nitrogen atom of a nitrogen-containing heterocycle; US Pat. No. 4,146,396 ( JP-A-52-90932), JP-A-59-93,442,
JP-A-59-75475, JP-A-60-249148
JP-A-60-249149, etc., which release PUG with the production of aldehydes; JP-A-51-
No. 146,828, No. 57-179,842, No. 59
-0-COOCR,R which releases PUG with decarboxylation of the carboxyl group as described in No. 104.641; -0-COOCR,R
, -PUG (R, , R5 represents a monovalent group), and releases PUG with decarboxylation and subsequent generation of aldehydes; disclosed in JP-A-60-7,429 Examples include those that release PUG with the production of incyanate as described; those that release PUG through a coupling reaction with an oxidized color developer described in U.S. Pat. No. 4,438,193, etc. .

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 general formula (T-6). In these, ** represents the site where Time binds to PUG.

* indicates the other bonding site according to the general formula (T-1), where W represents an oxygen atom, a sulfur atom, or a -N-R+Z group, Ro and R72 represent a hydrogen atom or a substituent, and RIf represents a substituent. where t is 1 or RI
or 2. When t is 2, two -W-C-R4 represent the same or different *When RII and RIz represent a substituent, and typical examples of RIz are R0 group, R,, CO- group, respectively. , R, , SO Tomi-group, R
,,NC〇- group or ISR,,NSO,- group, etc. are mentioned. Here R1
41 represents an aliphatic group, an aromatic group, or a heterocyclic group, and RI5
represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom.

Each of Ro, Ro and R1ff represents a divalent group, and cases in which they are linked to form a cyclic structure are also included.

Specific examples of the group represented by general formula (T-1) include the following groups.

This-〇-CI(-rate CHzCI(z rate-0-C)lz-N-CL-" rich general formula (T-2) *-Nu-Link-E-** In the formula, Nu is a nucleophilic group, 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 the mark ** upon receiving a nucleophilic attack from Nu.
nk represents a linking group that sterically relates Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction, and is represented by the general formula (
Specific examples of the group represented by T-2) are as follows.

General Formula (T-3) In the formula, W, R++, R4 and L have the same meanings as explained for (T-1), and specifically include the following groups.

■uz General formula (T-4) General formula (T-5) General formula (T-6) In the formulas, W and Ro have the same meanings as explained in the general formula (T-1). Specific examples of the group represented by general formula (T-6) include the following groups.

Book-〇-C-Umbrella-5-C-** 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: *, *
* has the same meaning as in general formulas (T-1) to -general formula T-6).

Umbrella-04Hz Js / C! Is Ning-0-C111 C Tomi US CzHs CH.

OCHx 1 Umbrella-0-C-N+C11t U-r-N-C-Mari rate 11 C.O.

(1, CH2O II I I+ $-0-C-0←CHt+-rN C-*Cold C
zHs For specific examples of these divalent linking groups represented by Time, see JP-A-61-236,549 and JP-A-64.
-88451, Japanese Patent Application No. 63-98.803, etc. are also described in detail.

PUG represents (Time)-, PtJC; or a group having a development inhibiting effect as PUG.

The development inhibitor represented by PUG or (Ttme)-t PUG is a known development inhibitor that has a heteroatom and is bonded via the heteroatom, and these are described, for example, by C.E.C. C,E.

K, Mess) and Chi H James (↑, H
The Theory of the Photography Process (1 James)
Photographic Processes) J 3rd edition, 1966 Macmillan (MacIII fa)
n) Published by Sha, pages 344 to 346, etc.

Specifically, mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, mercaptopyrimidines, mercaptobenzthiazoles, mercaptobenzthiazoles, mercaptobenzoxazoles, mercaptothiadiazoles, benztriazoles, 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,
Azylacameno 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, aryl oxycarbonyl group,
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.

The main development inhibitors are shown below.

(2) 1-(4-hydroxyphenyl)-5-mercaptotetrazole (3) 1-(4-aminoethyl)-5-mercaptotetrazole (4) 1-(4-carboxyphenyl)-5-mercaptotetrazole ( 5) L-(4-chlorophenyl)-5-mercaptotetrazole (6) L-(4-methylphenyl)-5-mercaptotetrazole (7) 1-(2,4-dihydroxyphenyl)-5-mercaptotetrazole (8 ) 1-(4-sulfamoylphenyl)-5-mercaptotetrazole (9) I-(3-carboxyphenyl)-5-mercaptotetrazole (to) 1-(3,5-dicarboxyphenyl) = 5-
Mercaptotetrazole (IDI-(4-methoxyphenyl)-5-mercaptotetrazole QZI-(2-methoxyphenyl)-5-mercaptotetrazole Qm 1-(4-(2-hydroxyethoxy)phenyl)-5-mercaptotetrazole a4 L -(2,4
-dikuoo7znyl)-5-mercaptotetrazole Q511-(4-diethylaminoethyl)-5-mercaptotetrazole 0611-(4-nitrophenyl)-5-mercaptotetrazole 07) 1,4-bis(5-mercapto-1- Tetrazolyl)benzene (lfl) 1-(α-naphthyl)-5-mercaptotetrazole 09) 1-(4-sulfophenyl)-5-mercaptotetrazole eel-(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-mercaptotetrazo-
(27) 1-cyclohexyl-5-mercaptotetrazole (28) 1-pal-thi-5-mercaptotetrazole (29) 1-carboxyethyl-5-mercaptotetrazole (30) 1-(2,2-jethoxyethyl)- 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-(3
-phenoxycarbonylphenyl)-5-mercaptotetrazole (35) 1-(3-maleinimidophenyl)-6-mercaptotetrazole mercapto 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-mercaptoimidazole (3) 1-(4-carboxyphenyl)-2-mercaptoimidazole (4) to 1-(4- xylcarbamoyl)-2-mercaptoimidazole (5) 1-(3-nitrophenyl)-2-mercaptoimidazole (6) 1-(4-sulfophenyl)-2-mercaptoimidazole Ethylthiouracilprobylthiouracilnonylthiouracylaminothiouracilhydroxythiouracillukatobenziξ zole (1) 2-mercaptobenzimidazole (2) 5-carboxy-2-mercaptobenzimidazole (3) 5-mercapto Benzimidazole (4) 5-nitro-2-mercaptobenzimidazole (5) 5-chloro-2-mercaptobenzimidazole (6) 5-methoxy-12-mercaptobenzimidazole (7) 2-mercaptonaphthoimidazole (8) 2 −
Mercapto-5-sulfobenzimidazole (9) 1-(2-hydroxyethyl)-2-mercaptobenzimidazole aω 5-caproamido-2-mercaptobenzimidazole 0115-(2-ethylhexanoylamino)-2-mercaptobenzimidazole Mercatothiadiazole theory (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 Luca benzthiazole 6 (1) 2-mercaptobenzthiazole (2) 5-
Nitro-2-mercaptobenzthiazole (3) 5-carboxy-2-mercaptobenzthiazole 5-sulfo-2-mercaptobenzthiazo (4) 1-mercaptobenzoxazole- (1) 2-mercaptobenzoxazole (2) 5 -Nitro-2-mercaptobenzoxazole (3) 5-carboxy-2-mercaptobenzoxazole (4) 5-sulfo-2-mercaptobenzoxazole benzo i azole μ (115,6-dimethylbenzotriazole (2) 5-
Butylbenzotriazole (3) 5-methylbenzotriazole (4) 5-chlorobenzotriazole (5) 5-butylbenzotriazole f6) 5.6-dichlorobenzotriazole (7) 4,
6-dichlorobenzotriazole (8) 5-nitrobenzotriazole (9) 4-2)rJ-6-chloro-benzotriazole Ql 4,5.6-)lichlorobenzotriazole aos-s lupoxybenzotriazole 21 5 -Sulfobenzotriazole Naaos 5-methoxycarbonylbenzotriazole 7' -l 5-aminobenzotriazole 5-butoxybenzotriazole 5-ureidobenzotriazole benzotriazole 5-phenoxycarbonylbenzotriazole (1!D5-(2,3-dichloropropyl (oxycarbonyl) benzotriazole O benzyl ≧ Benzimidazole 5-chlorobenzimidazole 5-nitrobenzimitazole 5-n-butylbenzitazol 5-methylbenzimidazole 4-chlorobenzimidazole 5.6-dimethylbenzimidazole 5 -Nitro-2-()rifluoromethyl)benzimidazole inzole (I) 5-nitroindazole (2) 6-nitroindazole (3) 5-aminoindazole (4) 6-aminoindazole (5) Indazole ( 6) 3-nitroindazole (7) 5-nitro-3-chlorointasole (81
3-70 rho 5-nitrointasol (9) 3-carboxy-5-nitroindazole 2-tosol (1) 5-(4-nitrophenyl)tetrazole (2)
5-phenyltetrazole (3) 5-(3-carboxyphenyl)-tetrazole 1 --Zaine-(1) 4-hydroxy-6-methyl-5-nitro 1
3,3a,7-thitraazaindene (2) 4-mercapto-6-methyl-5-nitrol, 3,3a,7-thitraazaindene (1) 4-nitrothiophenol (2 ) Thiophenol (3) 2-carboxythiophenol Also, in the general formulas (R-1), (R-2), and (R-3), R or (Time)-t PUG contains a coupler, etc. Ballast z, which is commonly used in immobile photographic additives, and general formulas (R-1), (R-2), (R-
A group that promotes adsorption of the compound represented by 3) to silver halide may be incorporated.

The ballast group has the general formula (R-1), (R-2), (R-3
) has a molecular weight sufficient to substantially prevent the compound represented by the formula from diffusing into other layers or into the processing solution.
It is a group consisting of a combination of one or more of an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, an amide group, a ureido group, a urethane group, a sulfuramide 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 halogenated radiation 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-oxaprine-2-thione, benzimidacillin-2-thione, benzoxazoline-2-thousone, benzothiazoline-2
-thione, thiotriazine, 1,3-imidacillin-2
- Cyclic thione group such as thione, dehydrated thioamide group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (if the carbon atom to which the -3H group is bonded is adjacent to a nitrogen atom, it is interchangeable with this group) Synonymous with the cyclic thioamide group related to the mutant, and specific examples of this group are the same as those listed above), group having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benzimidazole , imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, oxazole, oxazoline, thiadiazole,
5- or 6-membered nitrogen-containing heterocyclic groups consisting of a combination of nitrogen, oxygen, sulfur, and carbon such as oxathiazole, triazine, and azaindene, and cyclic quaternary salts such as benzimidasilinium. Can be mentioned.

These may be further substituted with a suitable substituent.

Examples of direct substituents include those described as substituents for R1.

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

CJt (n) 17° 1 day.

NO electric 21° O NO! 22゜ 26° 27° 9 30° 3 days 39° 40° 42° Of 43° 44° 45° SO co Na 46° 47° 4 days.

N.L.I.

49゜50゜1 2 3 4 55 6 7 8 9 0 1 C411 CJ+s 2 3 4 N-base N 5 66 8 9 O O1 The layer containing the redox compound of the present invention is a photosensitive emulsion containing a hydrazine nucleating agent. 0 provided on the upper or lower layer of the layer
The layer containing the redox compound of the present invention may further contain photosensitive or non-photosensitive silver halide emulsion grains.
An intermediate layer containing gelatin or a base polymer (polyvinyl acetate, polyvinyl alcohol, etc.) may be provided between the layer containing the redox compound of the present invention and the photosensitive emulsion layer containing the hydrazine nucleating agent.

The hydrazine nucleating agent used in the present invention has the following -FI
A compound represented by Q formula (1) is preferred.

General formula (1) In the formula, R+ represents an aliphatic group or an aromatic group, and R8
is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group,
GI represents a carbamoyl group, sulfonyl group, sulfoxy group, 1-P- group, or iminomethylene group, and 2 A, , A are both hydrogen atoms. Alternatively, one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, 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 3 carbon atoms, particularly 1 to 3 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 therein, 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 R1 in 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.

Examples include benzene ring, napucrene 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 7-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, a substituted 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,
Preferred substituents include an acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoamide group, a diacylamino group, and an Ikudo group. Preferred substituents include a straight chain, branched or cyclic alkyl group (preferably a carbon 1 to 20>, aralkyl group (preferably a monocyclic or bicyclic alkyl group with 1 to 3 carbon atoms), alkoxy group (preferably one with 1 to 20 carbon atoms), substituted amino group (preferably one with 1 to 20 carbon atoms), (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably one having 2 to 30 carbon atoms), a sulfonamide group (preferably one having 1 to 30 carbon atoms), a ureido group group (preferably having 1 to 30 carbon atoms), a phosphoric acid amide group (preferably having 1 to 30 carbon atoms), and the like.

The alkyl group represented by Rz 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 aryl group, such as one containing a benzene ring. This aryl group is, for example, a halogen atom, an alkyl group, a cyano group,
It may be substituted with a carboxyl group, a sulfo group, a sulfonyl group, etc.

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

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

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 R2, preferred is G.

is a carbonyl group, a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 6,3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, a phenylsulfonylmethyl group), an aralkyl group (
(eg, IJ, O- and troxybenzyl groups, etc.), aryl groups (eg, phenyl group, 3,5-dichlorophenyl group, O-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, etc.), Particularly preferred is a hydrogen atom.

In addition, in the case of G or a sulfonyl group, R2 is an alkyl group (e.g., methyl group, etc.), an aralkyl group (e.g., 0
-hydroxyphenylmethyl group), aryl group (e.g. phenyl group) or substituted amino group (e.g.
(dimethylamiki group, etc.) are preferred.

When G1 is a sulfoxy group, R2 is preferably a cyamibenzyl 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, or a substituted or unsubstituted phenyl group.

As the substituent for R2, the substituents listed for R can be applied.

-m G in formula (1) is most preferably a carbonyl group.

Also, R□ splits the G, -R, part from the remaining molecule,
It may be one that causes a cyclization reaction to produce a cyclic structure containing an atom of the GI R2 moiety, and specifically, one that can be represented by general formula (a).

General formula (a) -Rs-Z+ In the formula, Zl attacks G1 nucleophilically and GI -R1
- A group that can split the L moiety from the remaining molecules, R1 is one hydrogen atom away from Rz, ZI makes a nucleophilic attack on G, and a cyclic structure can be generated with GI and R3Zl It is.

More specifically, Zl easily undergoes a nucleophilic reaction with 61 when a hydrazine compound of the general formula (H) is oxidized to produce the following reaction intermediate: R+-N-N-GI-Rs-
Z+ R+ -N-N is a group that can be split from 01, specifically ○H, SH or NHR, (R is a hydrogen atom,
Alkyl group, aryl group, -CORa, or -So!
(R5 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.)
, may be a functional group that directly reacts with (where O
H, SH, NHR.

-COOH represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group (which may be temporarily protected so as to generate these groups by hydrolysis of alkyl, etc.). It may be a functional group that can react with G by reacting with a nucleophile such as an acid ion or a sulfite ion.

Furthermore, the ring formed by G, , R, and Z is preferably 5- or 6-membered.

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

General formula (b) In the formula, R1 to R, a are hydrogen atoms, alkyl groups (preferably those having 1 to 12 carbon atoms), alkenyl groups (preferably those having 2 to 12 carbon atoms), oryl groups (preferably those having 6 to 12 carbon atoms), and may be the same or different. B is an atom necessary to complete a 5-membered ring or a 6-membered ring which may have a substituent, m%n is 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.

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

General formula (c) c +N+-T+CR,'R,''4421 In the formula, RcI,
R♂ represents a hydrogen atom, an alkylalkenyl group, an aryl group, or a halogen atom, and may be the same or different.

RC3 represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

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

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

Rct, Rct preferably represents a hydrogen atom, a halogen atom,
or an alkyl group, and R,3 is preferably an alkyl group or an aryl group.

q preferably represents 1 to 3; when q is 1, p represents 1 or 2; when q is 2, p represents O or l; when q is 3, P represents O or 1; when q is 2 or CR when 3
c′ R,” may be the same or different.

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

At, At is a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms, 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. ) As AI and At, a hydrogen atom is most preferable.

R1 or R5 in general formula (1) 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.

R3 or R 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 heterothioamide group, and a mercapto group. U.S. Pat. No. 4.385.108, Mo. 4.459, etc.
, No. 347, JP-A-59-195,233, Do-59-
200゜231, 59-201,045, 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, . Examples include groups described in No. 108, No. 62-67.501, and No. 62-67.510.

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

1-L) I-2) ■-3) ■-4) xHs I-6)! -7) HI-8) [-9) Book C) lICHOCH,SH! -10) 1-11) 1-12) 1-15) S)1 1-16) 1-17) 1-1.8) N=■N r-20) SH -N r-22) ○ 1- 23) ○ Js 1-26)! -27) [-28)! -30) 1-31) 1-32) 1-33) r-34) ! -35) 1-36) 1-37) ! -38) 1-40) [-41) r-42) N 2 1-43) r-44) , 1-45) 1-46) 1-47) 1-48) 1-49) [-50) 1-51) 1-52) 1-53) r-54) In addition to the above-mentioned hydrazine derivatives used in the present invention, RESEARCII DISCLO3UR
E I tem23516 (November 1983 issue, p.
, 346) and the documents cited therein, as well as U.S. Pat.
．． No. 276.364, No. 4,278,748, No. 4,
No. 385,108, No. 4,459,347, No. 4,5
No. 60,638, No. 4,478,928, British Patent 2
．． OLL, 391B, JP 60-179734, JP 62-270 948, JP 63-29,751, JP 61-170.733, JP 61-270,744
No. 62-948, EP 217,310, Patent Application No. 175.234/1982, No. 61-251,482,
No. 61-268.249, No. 61-276゜283, No. 62-67528, No. 62-67゜509, No. 62-67.510, No. 62-58.513, No. 6
No. 2-130,819, No. 62-143,467, No. 62-166.117, or US No. 4,686,16
No. 7, JP-A No. 62-178, 246, JP-A No. 63-234
, No. 244, No. 63-234.245, No. 63-23
4゜246, 63-294,552, 63-3
No. 06.438, Patent Application No. 166.117 of 1982, No. 6
No. 2-247.478, No. 63-105゜682, No. 63-114.118, No. 63-110.051,
No. 63-114,119, No. 63-116,239, No. 63-147,339, No. 63-179,760
No. 63-229.163, patent application No. 1-18, 37
No. 7, No. 1-18,378, No. 1-18.379,
1-15.755, 1-16,814, 1-
No. 40,792, No. 1-42,615, No. 1-42,
Those described in No. 616 can be used.

In the present invention, when a hydrazine derivative is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer, but other non-photosensitive hydrophilic colloid layers (such as a protective layer, an intermediate layer, a filter layer, 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 water such as alcohols, esters, ketones, etc. It may be added to the hydrophilic colloid solution as a solution of a miscible solvent.If added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating. V#! It is preferable to add it after a certain period of time and before coating, especially in the liquid 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 antifogging compound, etc. Accordingly, it is desirable to select an optimal amount, and test methods for its selection are well known to those skilled in the art. Usually and preferably from 10-& mol to 1X10-' mol per mole of silver halide, In particular, it is used in a range of 10" to 4 x 10" 2 moles.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide, and silver iodochlorobromide.

The average grain size of the silver halide used in the present invention is preferably fine (for example, 0.7 μm or less), particularly 0.7 μm or less.
There is basically no limit to the particle size distribution, which is preferably 5 μ or less, but monodisperse is preferable. Monodisperse here means at least 95% of the weight or number of particles is ±40% of the average particle size. This means that the particle group having a size within the range of tJI is applied.

Silver halide grains in photographic emulsions may have regular crystals such as cubic or octahedral, or irregular crystals such as spherical or plate-like.
ular) 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, sulfite, lead salt, thallium salt, rhodium salt or its complex salt, iridium salt or its complex salt, etc. are allowed to coexist in the silver halide grain formation or physical ripening process. Good too.

The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye as a filter dye or for irradiation prevention or other purposes. A dye to further lower the sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity range of /%Q silver genide, or a dye to increase safety against safelight when handled as a light-sensitive material. , mainly J J OnmwA 00
A dye with substantial optical absorption in the nm region is used.

These dyes are added to the emulsion layer depending on the purpose, or they are added together with a mordant to the upper part of the silver halide emulsion layer, that is, to the non-light-sensitive hydrophilic colloid layer which is far from the silver halide emulsion layer with respect to the support. It is preferable to use it by fixing it.

Although it depends on the molar extinction coefficient of the dye, it is usually l0-21/
It is added in the range of m2~/97m2. Preferably JOnri~! θOIII is 7m2.

Specific examples of dyes can be found in the patent application published in 1977/-CoO? / J No. 5' contains detailed information, but some of them are listed below.

5 (J3K S (J3K Q 3K O3K S (J 3N a SIJ 3N a Solvent] and added to the coating solution for a non-photosensitive hydrophilic colloid layer of the present invention.

Two or more of these dyes can also be used in combination.

The dyes of the invention are used in amounts necessary to permit bright room handling.

The specific amount of dye used is generally 10 S'/m2
~/? /m % 4'? niio y7m -o
.

, ry/m2.

Gelatin is advantageously used as the binder or Vi protective colloid for 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, hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethyl cellulose and cellulose sulfate esters, glue derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl biloride/, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of imidazole, polyvinylpyrazole, and the like.

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.

The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but may be chemically sensitized. As methods for chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization, and noble metal sensitization methods are known, and any of these methods can be used alone or in combination for chemical sensitization. Good too.

Among the negative metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. No problem may be contained in complex salts of noble metals other than pure metals, such as platinum, palladium, and iridium. A specific example is U.S. Patent Co., ψψr, ot
o Spider It is described in British Patent No. 67r, OtI, etc.

As a sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, a-danines, etc. can be used as an irises reduction sensitizer that can be used with gold. For example, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

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

The photosensitive material of the present invention can contain various gold compounds for the purpose of preventing fogging during the production process, storage, or photographic processing of the photosensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazole salts, nitroindazoles, chlorobe/zimigzoles, p-amobenzimidazoles, mercaptothiazoles, mercaptothiazoles/zodeazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobencitriazoles. , etc.; mercaptopyrimidines; mercagutotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindefs (particularly q-hydroxym-converted (/, 3.3a A number of compounds known as anti-capri agents or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.;

Among these, preferred are benzotriazoles (e.g. !-methyl-benzotriazole) and nitroindazoles (e.g. !-nitroindazole).
It is. Further, these compounds may be included in the treatment liquid.

In the photographic light-sensitive material of the present invention, an inorganic 1. Or organic Ut! The membrane agent may contain gold. For example, aluminum salts (chromium alum, etc.), aldehydes, geltal aldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, activated vinyl compounds (lI3.j-triacryloyl-hexahydro-S −)! J azine, /, 3-vinylsulfonyl-2-glopanol, etc.), active halogen compounds (j, goudichlor-2-hydroxy-5-)
riazine, etc.), mucohalogen acids, etc. can be used alone or in combination.

The photographic emulsion layer tube or other hydrophilic colloid layer of the photosensitive material prepared using the photosensitive material of the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g.,
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polyglopylene/glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, Non-ionic materials such as alkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyalcohols, alkyl esters of sugars, etc. surfactants; alkyl carboxylates, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene/sulfonates, alkyl sulfates, alkyl phosphate esters, N-acyl-N-alkyl taurines, Acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants containing; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amide/oxides; alkylamine salts, aliphatic or aromatic Cationic surfactants such as ψ-class ammonium salts, heterocyclic V, 4-class ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

In particular, the surfactant that is most preferably used in the present invention is Tokukosho! - Polyalkylene/oxides having a molecular weight of too much or more described in Tag No. 72 publication. Further, for dimensional stability, a polymer latex such as polyalkyl acrylate can be completely contained.

Development accelerators or nucleating and contagious development accelerators suitable for use in the present invention include JP-A-33-77474, Ibid.
Goo37732. same! J-/37°/33, 40-/
In addition to the compounds disclosed in 4tO, Jg θ, 0-/4473, etc., various compounds containing N or 5IJK metal particles are effective.

Next, specific examples are listed.

The optimum amount of these accelerators to be added differs depending on the type of compound; These accelerators are dissolved in a suitable solvent (H2(J) alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellenlube, etc.) and added to the coating solution.

All of these additives may be used in combination.

In order to obtain ultra-high contrast photographic characteristics using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developing solution or US Pat. ψ/
It is not necessary to use a highly alkaline developer close to p )l /3 as described in No. 9', 777, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention has a sulfite ion θ, /! as a preservative. Contains mol/e or more, pH
10, j~/u, J, especially pHt/, 0-/, 2
．． A sufficiently ultra-high contrast negative image can be obtained using a developer of 0.

The developing agents that can be used in the method of the present invention include special f&
II is not limited to, for example, dihydroxybenzenes (e.g. hydroquinone), J-pyrazo! 7) '7el (e.g. /-phenyl-3-pyrazolidone, ri.

l-dimethyl-7-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), etc. can be used alone or in combination.

In particular, the silver halide Zhiguang material of the present invention contains dihydroxybenzenes as a main developing agent and 3-3 as an auxiliary developing agent.
Suitable for processing with developers containing silazolidones or aminophenols. Preferably, in this developer, dihydroxybenzenes are used in combination in an amount of 0.0j-0.1 mol/113-pyrazolidones or aminophenols in a range of 0.06 mol/l or less.

Further, as described in US Pat. No. 722P, the development speed can be increased and the development time can be shortened by adding amines to the developer.

In addition, the developer contains alkali metal sulfites, charcoal salts,
p' H buffering agents such as borates and phosphates, development inhibitors such as bromides, iodides, and organic antifoggants (preferably nido-a indazoles or benzotriazoles); Antifoggants and the like can be included. If necessary, water softeners, solubilizing agents, color toning agents, development accelerators, surfactants (especially preferably the aforementioned polyalkylene oxides), antifoaming agents, hardeners, and film silver stain preventive agents may be added. (For example, Komel Kabutobe/zimidazole sulfone @ etc.) May contain gold.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixer may contain a water-soluble aluminum salt or the like as a hard IFJ agent.

The processing temperature used in the method of the present invention is usually from tr''c to jo.
Selected between 6c.

Although it is preferable to use an automatic processor for photographic processing, the method of the present invention requires a total processing time 't (yo seconds to iao seconds) from the time the photosensitive material is put into the automatic processor until it comes out
Even when the setting is set to seconds, sufficient ultra-high contrast negative gradation photographic characteristics can be obtained.

The developing solution of the present invention contains JP-A Shojt-j as a silver stain preventive agent.
ψ, the compound described in No. 34c7 can be used.

Patent application 1986-/θ5 as a dissolution aid added to the developer
', No. 74'j can be used.

Furthermore, as a pH buffering agent used in the developer, JP-A-Shoto O-
5'j, 1. The compound described in LJ J or +
Compounds described in Ej Species Showa Gj-IB'l- can be used.

The present invention will be described in detail below with reference to Examples.

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

Comparative Example 1 (Preparation of photosensitive emulsion) Gelatin water kept at 50°C? Yong 7F! i, 7 mol of iridium hexachloride (I [[)
In the presence of potash and ammonia, an aqueous solution of silver nitrate, potassium iodide, and potassium bromide was simultaneously added for 60 minutes, and the PAg was maintained at 7.8 during that time. Content 0.3 mol%
A cubic monodisperse emulsion was prepared. This emulsion was desalted by the flocculesitane method, and then 40 g of inert gelatin per mole of silver was added and kept at 50°C to use 5.5'-dichloro-o-9-ethyl as a sensitizing dye. -3,3'
- Bis(3-sulfoprobyl) oxacarbocyanine and 10-3 moles of K per mole of
After allowing the mixture to stand for 5 minutes, the temperature was lowered.

(Coating of photosensitive emulsion layer) This emulsion was redissolved, and the following hydrazine derivative was added at 40°C, and 0.02 mol/A of methylhydroquinone was added.
gmol, Js? , lX10-' mol/Ag mol and 5-methylbenztriazole, 4-hydroxy-
1,3,3a,7-chitrazaindene, the following compounds (a) and (b), 30 wt% polyethyl acrylate based on gelatin, and the following compound (as a gelatin hardening agent)
Undercoat J made of vinylidene chloride copolymer with the addition of c)
It was coated onto a polyethylene terephthalate film (150μ) having W (0.5μ) so that the amount of silver was 3.4g/r4.

(B) tHs 3.5 mg/Bo (B) (C) H CH! YOCH30tC)ItCHCHzSO□C)ICH2For gelatin 2. OwtX (Coating of protective layer) On top of this, as a protective layer, gelatin 1.5g/rrf and polymethyl methacrylate particles (average particle size 2.5μ) 0.
3g/rrr, Ag (1 fine particle (
0.08μ) was coated using the following surfactant so that the Ag amount was 0.3g/bo.

Comparative Examples 2 to 4 Redox compound 6.14 was added to the light-sensitive emulsion layer of Comparative Example 1. ．．
21 for each 2. 0 X I Q-'a+ol/T
The rest was the same as Comparative Example 1 except that Tr was added.

Example 1 1.5 gelatin was added between the light-sensitive emulsion layer of Comparative Example 1 and the support.
g/rrr and redox compound 2 of the present invention shown in Table 1
, OX 10''a+ol/n (0 layer of gelatin was provided).

These samples were exposed to an optical wedge and contact screen (Fuji Film,
After exposure through a 150L chain dot type), the film was developed with the following developer at 34°C 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 gradation is expressed by the following formula.

*Exposure amount that gives a halftone dot area ratio of 1m-95% (j!
ogE95%) -5% exposure amount (1
4ogE5%) The sample of the present invention had significantly wider halftone gradation than the comparative example. In contrast to Comparative Examples 2 to 4, where G is 10 or less, the contrast is significantly impaired, the samples of the present invention maintain high contrast.

In addition, the shape of the halftone dots in the sample of Comparative Example 1 is irregular with conspicuous unevenness, and the samples of Comparative Examples 2 to 4 have low optical density and are in a blurry state, whereas in the present invention The example sample had a smooth shape and halftone dots with high optical density.

current image liquid table Example 2 Using a layer with the following composition as the gelatin 0 layer of Example 1, The rest was carried out in the same manner as in Example 1.

As a result of exposure and development processing in the same manner as in Example 1, the halftone dots were of good quality and the halftone gradation was further widened to 1.40.

Example 3 The following layers were applied in sequence onto a polyester film (150μ) support:

(1) Light-sensitive emulsion layer-A Using the light-sensitive emulsion formulation shown in Comparative Example 1, the amount of silver was 0.
It was coated at a concentration of 4 g/rrf.

(2) Intermediate layer gelatin 0.5 g/nl Polyethyl acrylate latex 0.155 Redox compound of the present invention (shown in Table 2) (3) Intermediate layer gelatin 0.5 g/nl (4
) Photosensitive emulsion layer-B The photosensitive emulsion layer of Comparative Example-1 was coated so that the amount of silver was 3.4 g/rrf.

The results are shown in Table 2.

The quality of the surface soil spots was visually evaluated in five stages. The 5-level evaluation is
"5" indicates the best quality and "1" indicates the worst quality.As a plate-making halftone original plate, "5" and "4" are practical, and "
3" is a practical limit level, and 12J, rli is an impractical quality.

The results are shown in Table 2. The samples of the present invention have high halftone dot quality and give halftone images with wide halftone gradations.

Example 4 5.0 per mole of silver in an aqueous gelatin solution maintained at 50'C.
X10-' moles of (N)In) JhCj! After simultaneous mixing of an aqueous silver nitrate solution and an aqueous sodium chloride solution in the presence of h, gelatin is added after removing soluble salts by methods well known in the art, and 2- Methyl-4-hydroxy-1,3,3a,
7-Chitrazaindene was added. This emulsion was a cubic monodisperse emulsion with an average size of 0.15 microns.

(Emulsion B) The following hydrazine compound was added to this emulsion.
5■/bo The compound of the present invention shown in Table 3 was further added, and 1,3-vinylsulfonyl-2-propanol was added as a hardening agent, so that the amount of Ag was 0.14 g/rrf on the polyester support. Coated. Gelatin was 0.3 g/rrr. On top of this, an intermediate layer containing gelatin of 0.5 g/rrf was coated, and then the next photosensitive layer was coated so that the amount of silver was 3.4 g/rrf.

The following hydrazine compound was added to emulsion B, and the solid content of polyethyl acrylate latex was 30 wt to gelatin.
% added and 1,3-vinylsulfonyl-2 as a hardening agent.
-Propanol 2. Owt% vs. gelatin added.

On top of this, 1.5 g/rd of gelatin was added as a protective layer, 0°3 g/rrr of polymethyl methacrylate particles (average particle size 2.5μ) was added as a matting agent, and the following surfactants and stabilizers were added as coating aids: and a protective layer containing ultraviolet absorbing dye was applied and dried.

surfactant CHiCOOCaH+5 t CHCOOCJ+s 0sNa 37■/bo C@F+tSO1NCIIgGOOK c.i.

5■/rrl Stabilizer Thioctic acid 1■/V Ultraviolet absorbing dye This sample is used by Dainippon Screen ■Meisho Printer P
-607, image exposure was carried out through the original as shown in FIG. 1, and the image was developed at 38° C. for 20 seconds, fixed, washed with water, and dried. After that, the cutout character image quality was evaluated.

A double character stroke 1t5 is a character with a width of 30 μm that is reproduced when a manuscript like the one shown in Figure 1 is exposed appropriately so that 50% of the halftone dot area becomes 50% of the halftone dot area on the photosensitive material for return. In terms of image quality, the image quality is very good. On the other hand, the character drawing parable 1 refers to the image quality that can only reproduce characters of 150 μm or larger when given the same appropriate exposure, and is poor character quality, with a sensory evaluation of 4 to 2 between 5 and 1. A rank was established. A value of 3 or higher is a practical level.

The results are shown in Table 3. The samples of the present invention have excellent cut-out character image quality.

table

[Brief explanation of drawings]

FIG. 1 shows the configuration at the time of exposure when forming a cut-out character image by overlapping and repeating, and each reference numeral indicates the following. (b) Transparent or semi-transparent pasting base (b) Line drawing original (black areas indicate line drawings) (c) Transparent or semi-transparent pasting base (d) Halftone dot original (black areas indicate halftone dots) (shown) (e) Photosensitive material for turning (the shaded area indicates the photosensitive layer)

Claims (5)

[Claims] (1) At least one photosensitive silver halide emulsion layer containing a hydrazine derivative and a hydrophilic colloid layer different from the photosensitive silver halide layer containing a redox compound capable of releasing a development inhibitor upon oxidation. A silver halide photographic material comprising: (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. G_1 has ▲mathematical formulas, chemical formulas, tables, etc.▼group, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. There are tables, etc. ▼ Represents a group. G
_2 represents a simple bond, -O-, -S-, or ▲a numerical formula, chemical formula, table, 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 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. ▼ (In the formula, R_0 represents an alkyl group, alkenyl group, aryl group, alkoxy group, or aryloxy group, and l represents 1 or 2.) Time represents a divalent linking group, and t represents 0. or 1
PUG represents a 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. )