JPH045652A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance resolution by incorporating a redox compound for releasing a development inhibitor in a silver halide emulsion layer or a hydrophilic colloidal layer formed on a support and a specified compound represented by a specified formula in the emulsion layer. CONSTITUTION:The photographic sensitive material has at least one silver halide emulsion layer on the support and the emulsion layer or another nonphotosensitive hydrophilic colloidal layer contains the redox compound capable of releasing the development inhibitor by being oxidized, and the emulsion layer contains the compound represented by formula I in which X is OR1; R1 is H or a group convertible into H by hydrolysis; each of R2 - R4 is H or a substitutable group; Y is a group for promoting adsorption to silver halide; L is a divalent bonding group; and (m) is 0 or 1, thus permitting the obtained photosensitive material to be high in contrast and wide in the tone reproduction range and used for forming a printing plate.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material which is particularly suitable for producing high-contrast images.

(Prior art) As one of the technologies for controlling the gradation of images of silver halide photographic light-sensitive materials, organic materials that generate development inhibitors imagewise or inversely imagewise during the development process have been gaining attention in recent years. has been developed. By applying these inhibitor-releasing compounds, improvements in the resolving power of photographic films, image quality due to the edge effect, and image reproducibility due to the interlayer effect in multilayer sensitive materials have been attempted.

In particular, in the field of photolithography, in order to deal with the variety and complexity of printed matter, there is a strong demand for photolithographic sensitive materials that can be easily and quickly developed and have good original reproducibility. JP 61-213847 and US 4,68
No. 4,604 discloses a silver halide sensitive material containing a redox compound that releases photographically useful groups.

However, when an inhibitor-releasing compound is used, the development speed becomes slow, and high-contrast sensitive materials for photolithography have the disadvantage that the high contrast fluctuates, making it impossible to take advantage of these characteristics.

(Object of the Invention) The first object of the present invention is to provide a silver halide photosensitive material with excellent resolution.

The second object is to provide a photosensitive material for plate making that has high contrast and a wide reproduction range of halftone gradation.

(Structure of the Invention) These objects of the present invention are to have at least one silver halide emulsion layer on a support, and to form a silver halide emulsion layer or other non-photosensitive hydrophilic colloid layer by oxidation. This was achieved by a silver halide photographic material containing a redox compound that releases a development inhibitor, and whose emulsion layer contains a compound represented by the following general formula (I).

It represents a linking group, and m represents 0 or 1.

Here, the group represented by R1 that can become a hydrogen atom by hydrolysis is, for example, COR? (R7 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted/R1 represents a hydrogen atom or a group that can become a hydrogen atom through hydrolysis, R, R, and R4 represent Each represents a hydrogen atom or a substitutable group, R, R, each represents a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, or a carbamoyl group, Y is an adsorption promoting group to silver halide, and L is 2
7 pieces of value! Represents multiple atoms necessary to form a heterocycle having a membered ring or a membered ring. ).

Examples of substitutable groups for R2, R3 and R4 include rogene atoms (fluorine, chlorine, bromine), alkyl groups (preferably those with 7 to 20 carbon atoms), aryl groups (preferably those with 1 to 20 carbon atoms). ), alkoxy group (preferably one with a carbon number of 1 to 20), acyloquino group (preferably one with a carbon number of t to 20), an alkylthio group (preferably one with a carbon number of 1 to 20), an arylthio group (preferably one with 7 to 20 carbon atoms), an asol group (preferably one with 2 to 20 carbon atoms), an acylamino group (preferably an alkanoylamino group with 1 to 20 carbon atoms, t-λO
benzoylamino group), nitro group, cyan group, oxycarminyl group (preferably alkoxycarbonyl group with carbon number/~20, aryloquine carbonyl group with carbon number 2~20), carboxy group, sulfo group, ureido Group (
Preferably an alkylureido group with carbon number/~20, an arylureido group with carbon number 2-λO), a sulfonamide group (preferably an alkylnulfonamide group with carbon number/~-0, an aryl group with carbon number t, 20) sulfonamide group),
A sulfamoyl group (preferably an alkylsulfamoyl group having a carbon number of /~ -0, an arylsulfamoyl group having a carbon number of 2 to 20), a carbamoyl group (preferably a carbon number /~
-〇 alkylcarbamoyl group, carbon number t to -〇 arylcarbamoyl group), acyloxy group (preferably carbon number/~20), amino group (unsubstituted amine, preferably carbon number/~20 alkyl group) Base, number of carbon atoms J
-20 aryl group substituted with a secondary or tertiary amino group), a carbonate group (preferably an alkyl carbonate group with carbon number/-20, an aryl carbonate group with carbon fiJ-JO), a sulfonyl group (preferably is the number of carbons/-
10 alkylsulfonyl groups, carbon Fz t -r
arylsulfonyl group), sulfinyl group (preferably carbon number/~).

R2, R3, and R4 may be the same or different, and R2, R
If any two of 3 and R4 are substituted on adjacent carbon atoms of the benzene ring, consecutively j to 7
A membered carbocyclic or heterocyclic ring may be formed, and these rings may be saturated or unsaturated.

Specific ring-forming compounds include cycloR/tane, nclohexane, nclohebutane, /crohante/, nclohexadiene, nclohebutadiene, indane, norbornane, norbornene, pyridine, etc., and these may further include substituents. It may have.

Further, the total carbon number of R2, R3, and R4 is preferably / to io.

R5 and R6 are hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted alkylsulfonyl groups, substituted or unsubstituted arylsulfonyl groups, substituted or unsubstituted alkylcarbonyl groups, LRs represents a substituted or unsubstituted arylcarbonyl group, a substituted or unsubstituted carbamoyl group
, R6 may be the same or different, or may be linked to form a nitrogen-containing heterocycle. (For example, morpholif group, Pi is lysino group, pyrrolidino group, imidazolyl group, Pi is radino group, etc.) Substituents for R5 and R6 include those listed as substitutable groups for R2, R3 and R4, and (-L - The latitude Y can be mentioned, and hydrogen atoms are more preferable as R5 and R6.

X is preferably substituted at the ortho or para position relative to the 10R1 group, and among those represented by X, 10R1 is more preferable, and R1 is more preferably a hydrogen atom.

Y is a group that promotes adsorption to silver halide, and L is a divalent linking group. m is O or /. Preferred examples of the adsorption-promoting group to silver halide represented by Y include a thioamide group, a mercapto group, a group having a disulfide bond, and a di- to t-membered nitrogen-containing heterocyclic group.

The thioamide adsorption promoting group represented by Y is a divalent group represented by 10-amino, and may be a part of a ring structure, or may be an acyclic thioamide group.

Useful thioamide adsorption promoting groups are described, for example, in U.S. Pat.
030, 9.2r, Dohiro, 03/, /λ7, Dogu,
O♂01207, sameμ, 2μ6,037, same, x
T.Y., J.

No. 77, No. 11.2tt, No. 073, and No. 1.27
J, jJg issue, and “Research Disclosure J”
Magazine number one! /Makigaku/! You can choose from those disclosed in Volume 176 A/7 A2A (/72/971).

Specific examples of acyclic thioamide groups include thiourido groups, thiourethane groups, dithiocarbamate groups, etc., and specific examples of cyclic thioamide groups include μm thiazoline-thione, ≠-imidacilline-λ-thione, etc. , 2-thiohydantoin, rhodanine, thiobarbic acid, tetrazoline-j-thione, /, λ,
q-triazoline-3-thione, i, 3. u-thiadiazoline-corchion, i, 3.4t-oxadiazolin-thione, benzimidacillin-2-thione, benzoxazoline-2-thione and (nzothiazoline-λ
-thione, etc., which may be further substituted.

The mercapto group of Y is an aliphatic mercapto group, an aromatic mercapto group, or a peta-ring mercapto group (if the carbon atom to which the -8H group is bonded is a nitrogen atom, it is a cyclic mercapto group that has a tautomeric relationship with this). sb is synonymous with the thioamide group, and specific examples of this group are the same as those listed above).

Examples of the negative to t-negative nitrogen-containing heterocyclic group represented by Y include j- to t-membered nitrogen-containing heterocycles consisting of a combination of nitrogen, oxygen, sulfur, and carbon. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine, and the like.

These may be further substituted with an appropriate substituent.

Examples of the substituents include those described as substituents for R2, R3, and R4.

Among those represented by Y, preferred are cyclic thioamide groups (i.e., mercapto-substituted nitrogen-containing heterocycles,
For example, 2-mercaptothiadiazole group, 3-mercapto-/, λ, cutriazole group, j-mercaptotetrazole group, -mercapto-i, 3. q-oxadiazole group, λ-mercapto oxazole group, etc.)
, or a nitrogen-containing heterocyclic group (eg, benzimidazole group, benzimidazole group, indazole group, etc.).

Two or more Y-(-L-% groups may be substituted, and may be the same or different.

The divalent linking group represented by L is C, N, S, 0
It is an atom or atomic group containing at least seven types of the following. Specifically, for example, alkylene group, alkenylene group, alkynylene group, 7'J-L'7 group, -0-1-S-1-N
It consists of H-1-N=, -CO-1-SO2- (these groups may have a substituent), etc., alone or in combination.

As a specific example, for example, -CONH--NHCON)(-1-8O2NH-1-
Examples include COO-1.

I-J −g) ■−ri I-B These may be further substituted with a suitable substituent.

Examples of the substituents include those described as substituents for R2, R3, and R4.

Preferred specific examples of the compound represented by the general formula (I) are shown next, but the scope of the present invention is not limited thereto.

I-/) ■-2) T-T (Jl-1 ■ 1-♂ r-ta) ■ -IO) -// ■-72 f-73) l-18) Below are the compounds of general formula (+) Typical synthesis methods will be explained using synthesis examples.

Synthesis example Synthesis of compound l-11 5-phenylbenztriazole carbonate 23.8
g (0.1 mol), 2-(4-aminophenyl)-ethylhydroquinone 25.2 g (0°11 mol), D
MAC100d was heated and stirred in an oil bath at 120"C (external temperature) for 5 hours under a nitrogen stream.

Next, DMAC was distilled off under reduced pressure and 200 ml of methanol was added, leaving a trace amount of black crystal by-product as an insoluble matter.

Insoluble materials were removed by suction filtration, methanol was distilled off under reduced pressure, and the resulting reaction mixture was isolated and purified using a silica gel column (chloroform/methanol-4/1). After washing with methanol, the target product 1-11 was isolated. Obtained. Yield 14.4 (38,
5%), melting point 256-7°C0 In addition, the compound represented by the general formula (1) is silver halide 1
It is preferable to contain 1X10-5 mol to 1×10-1 mol per mole, especially 1X10-' to 5X10
A preferable addition amount is in the range of -2 moles.

When these compounds of general formula (1) are incorporated into photographic light-sensitive materials, they may be contained in an aqueous solution if they are water-soluble, or as alcohols (e.g. methanol, ethanol), esters (e.g. ethyl acetate), or ketones if they are water-insoluble. It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as acetone (eg, acetone).

When added to a silver halide emulsion solution, it can be added at any time from the start of chemical ripening to coating, but it is preferable to add it after chemical ripening, especially when the coating is prepared for coating. It is preferable to add it to the liquid.

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, hydroxylamines, and reductones, and more preferably hydrazines.

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

General formula (R-1) R, -N-N-Gt (Time)t-PIG^I
At General formula (R-2) R, -Gt-Gt-N-N-CHzCH-(Time)
t-PIGA+ A3 A4 General formula (R-3) In these formulas, R3 is an aliphatic group or an aromatic group II
1111. G1 is -C- group, -C-C- group, S
NGz Rz11I Represents a C- group, -C- group, -5O- group, S02- group or -P- group. G2 is a single G, -R.

represents a bond, -〇-1-3- or -N-, and R
2 represents a hydrogen atom or R.

AI and A2 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 AA2 is a hydrogen atom. A is synonymous with A or -GHzC
H-(TiIIle) represents t-PIG.

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

Time represents a divalent linking group, L represents 0 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.

This alkyl group may have a substituent.

In general formulas (R-1), (R-2), and (Rf3), the aromatic group represented by R1 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group.

Examples include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, and an isoquinoline ring. Among these, 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, and a substituted amino group. , ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, rythio 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 has 7 to 30 carbon atoms), alkoxy group (preferably has 1 to 30 carbon atoms), substituted amino group (preferably has 1 to 30 carbon atoms)
~30 alkyl group substituted), acylamino group (preferably having 2 to 40 carbon atoms), sulfonamide group (preferably having 1 to 40 carbon atoms)
, ureido group (preferably having 1 to 40 carbon atoms)
, phosphoric acid amide group (preferably one having 1 to 40 carbon atoms)
etc.

General formulas (R-1), (R-2), (R-3) and Q
0 is -C- group, -S
An O□- group is preferred, and a -C- group is most preferred.

A+, At is preferably a hydrogen atom;

As hydrogen atom, -CHz-CH4Time Pt1
G is preferable.

In general formulas (R-1), (R-2), and (R-3), T
ime represents a divalent linking group and may have a timing 11 function.

The divalent linking group represented by Time represents a group that releases PUG from Ti+me-PIG 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. No. 4,310,612 (Japanese Unexamined Patent Publication No. 55-53,330) and U.S. Pat. No. 4,358. Those that release PUG by an intramolecular ring-closing reaction after ring opening as described in US Pat. No. 525, etc.; 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 Journal 21, 22B (December 1981)
), U.S. Patent No. 4,416,977
135.944), JP-A-58-209,736,
No. 5B-209,738, etc., which generates quinomonomethane or its analogs by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group and releases PUG: US patent Cylinder 4,420,5
No. 54 (Japanese Patent Publication No. 57136.640), Japanese Patent Application Publication No. 57-
No. 135.945, No. 57-188.035, No. 5B
-98728 and 5B-209,737, etc., which release PtJC from the 1-position of the enamine by electron transfer of the part having the 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. 5
2-90932), JP-A-59-93.442, JP-A-59-75475, JP-A-60-249148, JP-A-60-249149, etc. with the formation of aldehydes. Something that releases PUG; JP-A-51-1
No. 46,828, No. 57-179゜842, No. 59-
104,641 which releases PUG with decarboxylation of the carboxyl group, -0-COOCR, Re-P
It has the structure of IG (R-, Rh represent monovalent groups), and PUG with decarboxylation and subsequent generation of aldehydes.
Those that release PUG with the production of isocyanate as described in JP-A-60-7,429; Oxidized products of color developers as described in U.S. Pat. No. 4,438,193, etc. Examples include those that release PUG through a coupling reaction.

For specific examples of these divalent linking groups represented by Time, see JP-A No. 61-236,549 and Japanese Patent Application No. 63-Sho.
It is also described in detail in No. 98,803.

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

The development inhibitor represented by PUG or (Timeht P UG , E., Mees) and T.H. James (The Theory of the Photographic Process)
phicProcesses) J 3rd edition, 1966
Published by Macmillan, pp. 344-3
It is described on page 46.

The development inhibitor represented by PUG may be substituted. Examples of substituents include those listed as substituents for R3, and these groups may be further substituted.

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.

In addition, in general formulas (R-1), (R-2), and (R-3), R or (TimehtPUG) is a ballast commonly used in immobile photographic additives such as couplers. group or general formula (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 i 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 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-imidacylin-2-thousand, 2-thiohydantoin, rhodanine, thiobarbital acid, tetrazoline-5-thione, 1,2.4-) liazoline-3-thousand, 1,3.4 -Oxazoline-2
Cyclic thioamide groups, linear Thioamide group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (if the carbon atom to which the -3H group is bonded is a nitrogen atom, it is synonymous with a cyclic thioamide group that has a tautomeric relationship with this) ), 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.

NO! ■ 6H13 C, L go Nυ! In addition to the above-mentioned redox compounds, examples of redox compounds used in the present invention include those disclosed in JP-A No. 61-213゜847, No. 6
No. 2-260,153, Japanese Patent Application No. 1-1'02,393, No. 1-102.394, No. 1-102,395,
Those described in No. 1-114,455 can be used.

Examples of the synthesis method of the redox compound used in the present invention include JP-A-61-213,847 and JP-A-62-260.15.
No. 3, U.S. Patent No. 4,684.604, Patent Application No. 1983-
No. 98.803, U.S. Pat. No. 3,379,529, U.S. Pat. No. 3,620,746, U.S. Pat.
, No. 332,878, Tokukai Sho,! 19-129,536
No. 56153', 336, No. 56-153, 34
It is written in No. 2, etc.

The redox compound of the present invention is preferably 1X10-' to 5X10-2 mol per mole of silver halide, more preferably 1
It is used within the molar range of Xl0-' to lXl0-''.

The redox compound of the present invention can be used in a suitable water-miscible organic solvent, such as alcohols (methanol, ethanol, propatool, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethyl formamide, dimethyl sulfoxide, methyl cellosolve, etc. It can be used by melting it.

In addition, by the already well-known emulsification dispersion method, it is dissolved using an oil such as diethyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent 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 colloid mill, or an ultrasonic wave.

As the inhibitor-releasing redox compound, compounds having hydroquinones as a redox group can also be used. Examples of these compounds are listed in Kentoku 9849.9853.
9897, etc.

The redox compound of the present invention is added to a silver halide emulsion layer or other hydrophilic colloid layer.

The redox compound of the present invention and the compound of general formula (1) are:
They may be added to different layers or the same layer.

The silver halide photographic light-sensitive material of the present invention has type B having various layer configurations, but basically, (a) an inhibitor-releasing redox compound is combined with a silver halide emulsion layer in which the redox compound is released. (b) when the inhibitor acts functionally;
There are two cases in which the released inhibitor acts functionally on another silver halide emulsion layer (referred to as the "interlayer effect").

In case (b), it has multiple silver halide emulsion layers, the first emulsion layer or other hydrophilic colloid layer contains an inhibitor-releasing redox compound, and the second emulsion layer or other hydrophilic colloid layer contains an inhibitor-releasing redox compound. It is desirable that the layer contains a contrast enhancing compound.

If both are added to the hydrophilic colloid layer, the inhibitor-releasing compound is preferably added to the hydrophilic colloid layer in the vicinity of the first emulsion layer so as to maintain a close relationship with the respective emulsion layer. The contrast enhancing compound is preferably added to a layer near the second emulsion layer.

An intermediate layer of gelatin or other natural or synthetic polymer (polyvinyl acetate, polyvinyl alcohol, etc.) may be provided between the first emulsion layer and the second emulsion layer, and the thickness is 0.
．． The thickness is preferably 1 to 5.0μ, preferably 0.2 to 4μ.

As the high contrast compound, various known compounds can be used. Among these, hydrazine derivatives, tetrazolium salts, and polyoxyalkylene compounds are preferred, and hydrazine derivatives represented by the following general formula (n) are particularly preferred.

General formula (U) R, -N-N-G, -R2 A, A.

In the formula, R1 represents an aliphatic group or an aromatic group, R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, or a hydrazino group, and G1 represents a 10-group, -5O2 ○ 0 0 +1 1111 group, -8〇- group, -P- group, -C-C- group, thiocarbonyl group, or iminomethylene group, and AI and A2 are both hydrogen atoms, or one is a hydrogen atom and the other is a It represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In general formula (II), the aliphatic group represented by R8 preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
~20 straight chain, branched or cyclic alkyl groups. This alkyl group may have a substituent.

The aromatic group represented by R1 in general formula (II) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be fused with an aryl group.

Preferred as R1 is an aryl group, particularly preferably one containing a benzene ring.

The aliphatic group or aromatic 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, a ureido group, Urethane group, aryloxy group, sulfamoyl group, carbamoyl group,
Alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide Preferred substituents include alkyl groups (preferably those with 1 to 20 carbon atoms), aralkyl groups (preferably those with 7 to 30 carbon atoms), and alkoxy groups. Group (
(preferably those having 1 to 20 carbon atoms), substituted amine groups (preferably amino groups substituted with alkyl groups having 1 to 20 carbon atoms), acylamino groups (preferably those having 2 to 30 carbon atoms), sulfonamides. Group (preferably 1 to 1 carbon atoms)
30), a ureido group (preferably a carbon number of 1 to
30), a phosphoric acid amide group (preferably one having 1 to 30 carbon atoms), and the like.

The alkyl group represented by R2 in general formula (II) is preferably an alkyl group having 1 to 4 carbon atoms,
The aryl group is preferably a monocyclic or bicyclic aryl group (for example, one containing a benzene ring).

When G1 is a -C- group, preferred among the groups represented by R2 are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group,
3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (e.g., 0-hydroxybenzyl group, etc.), aryl group (e.g., phenyl group, 3°5-dichlorophenyl group, 0-methanesulfonamidophenyl group) , 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.),
Particularly preferred is a hydrogen atom.

R2 may be substituted, and the substituents listed for R1 can be used as substituents.

G in general formula (II) is most preferably a -C- group.

Also, R2 splits the G, -R2 part from the remaining molecule,
It may be one that causes a cyclization reaction to produce a cyclic structure containing an atom of the -Gl-R2 moiety, and examples thereof include those described in JP-A-6329751.

Hydrogen atoms are most preferred as A1 and A2.

R1 or R2 in the general formula (II) may have a ballast group or a polymer 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, and may be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. I can do it. Examples of the polymer include those described in JP-A-1-100530.

R1 or R2 in general formula (n) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc.
, No. 347, JP-A No. 59-195, 233, No. 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. 62-67.508,
Examples include the groups described in No. 62-67.501 and No. 62-67.510.

Specific examples of the compound represented by general formula (n) are shown below.

However, the present invention is not limited to the following compounds.

II-1 II-2 II-4 II-5 I[-6 I-8 ■-10 Sushi IItl ■ ■ ■ H ■ ■ ■-13 ■ ■ ■ ■ ■-25 ■-22 ■-26 I-1 ■ -24 In addition to the above-mentioned hydrazine derivatives used in the present invention, RESEARCHDISCLO3URE
Item23516 (November 1983 issue, P, 34
6) and the documents cited therein, as well as U.S. Pat.
No. 80.207, No. 4,269,929, No. 4.27
No. 6.364, No. 4,278,748, No. 4,385
, No. 108, No. 4,459,347, No. 4,560,
No. 638, 4. 478. No. 928, British Patent 2,
011,391B, JP-A-60-179734, JP-A No. 6
No. 2-270,948, No. 63-29,751, No. 6
No. 1-170゜733, No. 61-270,744, No. 62948, EP No. 217,310, or US 4
゜686.167, JP 62-178,246,
No. 63-32,538, No. 63-104゜047,
No. 63-121,838, No. 63129.337,
No. 63-223,744, No. 63-234,244, No. 63-234,245, No. 63-234,246
No. 63-294.552, No. 63-306, 43
No. 8, JP-A No. 1100.530, 1. 105.
No. 941, No. 1-105,943, JP-A-64-10
．． No. 233, Japanese Patent Application Publication No. 1-90,439, Patent Application No. 1983-
No. 105,682, No. 63-114,118, No. 63
-110,051, 63-114.119, 6
No. 3-116,239, No. 63-1.47,339,
No. 63-179,760, No. 63-229.163, Japanese Patent Application No. 1-18.377, No. 1-18,378,
1-18.379, 1-1.5,755, 1
-16.814, same] -40,792, same 1-42
．． 615, 1-42, 616, 123,6
93 and No. 1-126,284 can be used.

The amount of the hydrazine derivative added in the present invention is from 1X10-' mole to 5X10 mole per mole of silver halide.
-2 mol is preferable, and a particularly preferable addition amount is in the range of 1X10-5 mol to 2X10-2 mol.

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

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.
It is preferably 5μ or less. There are basically no restrictions on the particle size distribution, but monodisperse distribution is preferable. Monodisperse herein means that at least 95% of the particles by weight or number of particles are composed of particles having a size within ±40% of the average particle size.

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 be composed of uniform phases or may be composed 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. coexist in the silver halide grain formation or physical ripening process. You may let them.

The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as preventing irradiation. Filter dyes include dyes for further lowering photographic sensitivity, preferably ultraviolet absorbers that have a spectral absorption maximum in the intrinsic sensitivity range of silver halide, and dyes that are safe against safelight light when handled as bright-room sensitive materials. In order to increase the wavelength, a dye having substantial light absorption mainly in the region of 350 nm to 600 nm 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 further away from the silver halide emulsion layer with respect to the support. It is preferable to use it by fixing it.

It varies depending on the molar extinction coefficient of the dye, but usually 10-2 g.
/rrf to 1 g/rrf. Preferably it is 50 to 500 mg/po.

Specific examples of dyes are described in detail in Japanese Patent Application No. 61-209169, and some are listed below.

SO, KUCK O3Na The above dye is dissolved in a suitable solvent [e.g., water, alcohol (e.g., methanol, ethanol, propatool, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof] to produce the non-photosensitive dye of the present invention. It is added to the coating solution for the outer hydrophilic cloid layer.

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

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

The specific amount of dye used is generally 10-'g/rrf ~
Ig/rrr, especially 10-3g/bo to 0.5g/rrr
A preferred amount can be found within the range of .

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, graphs of gelatin and other macromolecules) polymers, proteins such as albumin and casein; hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethyl cellulose, cellulose sulfate esters, sodium alginate, lees
II derivatives such as J derivatives, single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Synthetic hydrophilic polymeric substances 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.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be chemically sensitized. Noble metal sensitization methods are known, and any of these methods may be used alone or in combination for chemical enhancement.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a total complex salt. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, palladium, and iridium. A specific example is U.S. Patent No. 2,448,06
No. 0, British Patent No. 618.061, etc.

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.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

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

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; ), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as benzentiosulfonic acid, pensensesulfinic acid, hensensulfonic acid amide, etc. Among these, preferred are benzotriazoles (eg 5-methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Further, these compounds may be included in the treatment liquid.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, etc.), aldehydes, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, activated vinyl compounds (1,3,5-triacryloyl-hexahydro-5- triazine, 1.3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2.
, 4-dichloro-6-hydroxy-5-triazine, etc.), mucohalogen acids, etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (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/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic surfactants such as alkyl esters such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, etc. Agents; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfonate Carboxy groups, such as alkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups; amino acids;
Ampholytic surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, and amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, complex compounds such as pyridinium, imidazolium, etc. Cationic surfactants such as ring quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

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. Additionally, a polymer latex such as polyalkyl acrylate may be included for dimensional stability.

Development accelerators or nucleating and infectious development accelerators suitable for use in the present invention include JP-A-53-77616 and JP-A-53-77616;
4-37732, 53-137°133, 60-1
In addition to the compounds disclosed in US Pat. No. 40,340, No. 60-14959, etc., various compounds containing N or S atoms are effective.

Next, specific examples are listed.

(C2Hs) 2NCH2CHCH20HOH n-CtHsN(C2HtOH)z S CH2UH2NLL:2Hsノ2 The optimum addition amount of these accelerators varies depending on the type of compound, but 1.
0X10~0.5g/m, preferably 5.0X10~
It is desirable to use it in the range of Z to 0.1 g/po. These promoters are dissolved in a suitable solvent (I) (alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution.

A plurality of types of these additives may be used in combination.

In order to obtain ultra-high contrast photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or U.S. Pat.
It is not necessary to use a highly alkaline developer with a pH close to 13 as described in No. 9,975, 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 high contrast negative image can be obtained using a developer having a pH of 10.5 to 12.3, particularly 11.0 to 12.0.

There are no particular limitations on the developing agents that can be used in the method of the present invention, such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone, 4゜4-dimethyl-1-phenyl- 3-pyrazolidone), aminophenols (e.g. N
-methyl-p-aminophenol) can be used alone or in combination.

In particular, the silver halide photosensitive 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 pyrazolidones or amine phenols. Preferably, in this developer, dihydroxobenzenes are used in an amount of 0.05 to 0.5 mol/l, and 3-pyrazolidones or aminophenols are used in an amount of 0.06 mol/l or less.

Further, as described in US Pat. No. 4,269,929, the development speed can be increased and the development time can be shortened by adding amines to the developer.

The developer also contains alkali metal sulfites, carbonates,
Contains pH buffering agents such as borates and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles). I can do it.

If necessary, water softeners, solubilizing agents, color toning agents, development accelerators, surfactants (especially preferably the above-mentioned polyalkylene oxides), antifoaming agents, hardeners, and silver stain prevention agents for films may be added. agents (for example, 2-mercaptobenzimidazole sulfonic acids, etc.).

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 fixing solution may contain a water-soluble aluminum salt or the like as a hardening agent.

The processing temperature in the method of the invention is usually from 18°C to 50°C.
Selected between ℃.

Although it is preferable to use an automatic processor for photographic processing, according to the method of the present invention, the total processing time from the time the photosensitive material is put into the automatic processor until it comes out can be set to 60 seconds to 120 seconds. , sufficiently ultra-high contrast negative gradation photographic characteristics can be obtained.

In the developing solution of the present invention, JP-A-56-2 is used as a silver stain preventive agent.
Compounds described in No. 4,347 can be used. Patent application 1986-109 as a solubilizing agent added to the developer.
Compounds described in No. 743 can be used. In addition, as a pH buffering agent for developing solutions, JP-A-60-93.4
Compounds described in No. 33 or Japanese Patent Application No. 18625/1986
9 can be used.

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

Example 1 (Preparation of photosensitive emulsion) Emulsion-A 4X10 per mole of silver was added to an aqueous gelatin solution kept at 50°C.
- In the presence of mol of potassium iridium(III) hexachloride and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide were simultaneously added for 60 minutes, and the pA
By keeping g at 7.8, the average particle size is 0.28
μ, average silver iodide content 0. A 3 mol % cubic monodisperse emulsion was prepared. This emulsion was desalted by the flocculation method, and then 40 g of inert ceratin per mole of silver was added and kept at 50°C as a sensitizing dye, 5,5'-dichloro-9-ethyl-3. ,3' bis(3-
sulfopropyl) oxacarbocyanine and a solution of 10@-1 mole of Kl per mole of silver, the mixture was allowed to stand for 15 minutes, and then the temperature was lowered.

Emulsion-B A silver nitrate aqueous solution was added to a gelatin aqueous solution with a pH of 4.0 kept at 50°C and 1.0% per mole of silver was added. 4X10-7 moles of ammonium rhodium(1) hexachloride and 4XlO-'
A mixed aqueous solution of sodium chloride and potassium bromide containing mol of potassium hexachloroiridium(III) acid was added simultaneously at a constant rate for 30 minutes to obtain an average particle size of 0.23μ.
A silver chlorobromide monodisperse emulsion CC1 (composition: 70 mol %) was prepared.

This emulsion was washed with water in a conventional manner to remove soluble salts, and then chemical sensitization was performed by adding sodium thiosulfate and potassium chloroaurate. Additionally, 0.0.
A potassium iodide solution corresponding to 1 mol % was added to convert the particle surface.

Furthermore, after this, the following compound was added as a sensitizing dye at 50 DEG C. at 2.7.times.10@-' mol/Ag mol, and after standing for 15 minutes, the temperature was lowered and stored.

(Preparation of coating sample) Support, undercoat layer made of vinylidene chloride copolymer (0,
Polyethylene terephthalate film (5μ) with
150μ) On the support, UL, ML,
It was applied so that it had a layer structure of OL and PC. The preparation method and coating amount of each layer are shown below.

(UL) After dissolving the emulsion-B together with seratin at 40°C,
5-methylbenztriazole, 85 mg/, 7.4-
Hydroxy-1,3,3a,7-chitrasaindene 12
Ag
3. 6 g/rri, 2.8 x 10 m01/vol of the hydrazine compound shown in Table 1, and 9 g/m of gelatin.

Compound (B) 1″5■/rr? Compound (c) C.H.

CH=CH+CH2÷ycON -CH, CHzSOa
NaCI(.

50■/- Compound (d) CH CH2= CH30tCH2CHC)I2SOzCH=
2.0 wt% (ML) of CH2 gelatin 10 g of gelatin 2. 0 wt % was added, water was added to give a final amount of 250 CIe, and the gelatin was coated at a concentration of 1.5 g/proof.

(OL) The above emulsion-A was dissolved at 40°C, and 3 mg/m of 5-methylbenztriazole, 4-hydroxy-1,
3,3a,7-thitrazaindene, compound of general formula (I) of the present invention shown in Table 1 4. 3X10-"mol/a, compound (a) 0.4■/a, (b) 1, 5■/a,
(c) Polyethyl acrylate was added in an amount of 30 wt % based on gelatin and compound (d) was added as a gelatin hardening agent in an amount of 2 wt % based on gelatin. A
It was applied so that the amount was 0.4 g/rrr.

(P C) A polymethyl methacrylate dispersion (average particle size 5.0μ) and the following surfactant were added to the gelatin solution to form gelatin 1. It was applied at a concentration of 5g/rrr and 0.3g/rl as polymethyl methacrylate.

Surfactant developer CH2C00C,H CHCOOC,H3Os Na 37■/1ri C,F,□SO,NCH2C00K CsHt 2. 5 mg/m (performance evaluation) These samples were exposed to tungsten light at 3200° through an optical wedge or an optical wedge and a contact screen (Fuji Film, 150L chain dot type), and then developed with the following developer at 348C for 30 seconds. , fixing, washing,
Dry.

As a fixer, Fuji Photo Film (manufactured by Kikisha, GR-F) was used.
l was used.

The results obtained are shown in Table 1.

The gradation (γ) is a characteristic curve with a density of 0° It is the slope of the straight line connecting the 0 points.

3 point and 3° The halftone gradation is expressed by the following formula.

*Done gradation = Exposure amount that gives a 95% dot area ratio (I!
The exposure amount (log
E5%) The halftone dot quality was visually evaluated on a five-level scale. The 5-level evaluation is
"5" indicates the best quality, and "1" indicates the worst quality. As halftone dot originals for plate making, "5" and "4" are practical, and "
3 is the practical limit level, and 2 and 1 are impractical quality levels.

From the results in Table 1, it can be seen that the samples of the present invention provide images with high T, wide halftone gradation, and good halftone quality.

Example 2 The compound of general formula (1) shown in Table 2 and a redox compound were added to Emulsion-A or Emulsion-B of Example 1, and 4-hydroxy-1,3,3a,7-chitrazaindene 12/
n(, 30 wt% polyethyl acrylate to gelatin and gelatin hardness (1 part 1,3-divinylsulfonyl-2-hydroxypropane to gelatin 2.
0 wt% was added, and the amount of silver was 3.8 g/n (and the amount of gelatin was 1°9 g/nf.) On top of this, a polymethyl methacrylate dispersion (average particle size 5.0 μ) was added to the gelatin solution. , add the following surfactant, add 1.5 g of gelatin
/nf, polymethyl methacrylate 0°3g/rtT.

(Evaluation of Photographic Performance) These samples were exposed to tungsten light at 3200' through an optical wedge, and then incubated at 38°C with the developer of Example 1.
The film was developed with various development times, fixed, washed with water, and dried. Table 2 shows the relationship between development time and gradation.The sample of the present invention has a gradation of 5 when developed for 20 seconds compared to the comparison sample.
Example 3 (Preparation of Photosensitive Emulsion B) 5.0% per mole of silver was added to an aqueous gelatin solution kept at 50°C.
X10-' moles of (N)lOzRhc j! After simultaneously mixing an aqueous silver nitrate solution and an aqueous sodium chloride solution in the presence of b, gelatin was added after removing soluble salts using 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.

(Coating of photosensitive emulsion layer) Hydrazine compound n-20 (9μ/rr
f), 5-methylbenzotriazole (5×10-'
mol/Ag mol), polyethyl acrylate latex (30 wt% to gelatin), and 13-divinylsulfonyl-2-propanol (2° Owt% to gelatin). The amount of silver coated was 3.5 g/po.

2nd layer gelatin (1.0 g/po) Prepared in the same manner as 3rd layer photosensitive emulsion B, except that the average grain size is 0.
．． 5-
Methylbenzotriazole (5 x 10-3 mol/Ag
mol), polyethyl acrylate latex (30
wt% vs. gelatin), 1.3-divinylsulfonyl-2
- Propatool (2wt% vs. gelatin). The following redox compound of the present invention (compound No. 3-9.3.4
X 10-'IIIot/n() and the compound of general formula (1) of the present invention shown in Table 3 were added.

Fourth layer (protective layer) 1.5 g/rrr of gelatin and 0.3 g of polymethyl methacrylate particles (average particle size 5.0 μ) as a matting agent
/rrf, and a protective layer containing the following surfactants, stabilizers, and ultraviolet absorbing dyes as coating aids was coated and dried.

Surfactant CHZCOOC6t (+3 CHCOOC6H13 Stabilizer This sample is used by Dainippon Screen Seimei-shiro 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.

Extracted character image quality 5 means that characters with a width of 30 μm are reproduced when a document as shown in Figure 1 is used and 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. -Emphatic character image quality 1
is an image quality that can only reproduce characters with a width of 150 μm or more when given the same appropriate exposure, and is considered poor character extraction quality, and is ranked between 5 and 1 with a sensory evaluation of 4 to 2. A value of 3 or higher is a practical level.

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

[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 paste-up base (opening) Line drawing original (black part indicates line drawing) (C) Transparent or semi-transparent pasting base (2) Halftone dot original (black part indicates halftone dot) () Photosensitive material for return (the shaded area indicates the photosensitive layer)

Claims (5)

[Claims] (1) It has at least one silver halide emulsion layer on a support, and the emulsion layer or other non-photosensitive hydrophilic colloid layer contains a redox compound that releases a development inhibitor when oxidized. , and furthermore, the emulsion layer has the following general formula (I
) A silver halide photographic material comprising a compound. General Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, , R_2, R_
3 and R_4 each represent a hydrogen atom or a substitutable group, and R_5 and R_6 each represent a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, or a carbamoyl group. In the formula, Y is a group promoting adsorption to silver halide, L is a divalent linking group, and m is 0 or 1. (2) having a first silver halide emulsion layer containing at least one type of silver halide emulsion on a support;
The other non-photosensitive hydrophilic colloid layer contains a hydrazine derivative, has a second silver halide emulsion layer, and is oxidized into the second emulsion layer or the other non-photosensitive hydrophilic colloid layer. The silver halide photographic light-sensitive material according to claim (I), which contains a redox compound capable of releasing a development inhibitor, and the second emulsion layer contains a compound of general formula (I). (3) Claims characterized in that the redox compound is a group selected from hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines, and reductones as a redox group (1) Silver halide photographic material. (4) The silver halide photosensitive material according to claim (1), wherein the redox compound has a hydrazine as a redox group. (5) Claim (1) characterized in that the redox compound has a hydroquinone as a redox group.
) silver halide photosensitive materials.