JPH03294844A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material of a super- high contrast adequate for a photoengraving process by forming a silver halide emulsion of monodisperse particles consisting of >=50 mol% silver chloride and <=20 dispersion coefft. CONSTITUTION:The silver halide emulsion is the monodisperse particles consisting of >=50 mol% silver chloride and <=20 dispersion coefft. The hydrazine deriv. to be incorporated into photosensitive silver halide emulsion layers is preferably the compd. expressed by formula I. In the formula I, R1 denotes an aliphat. group or arom. group; R2 denotes a hydrogen atom, alkyl group, hydrazino group, etc.; G1 denotes a -SO2- group, -SO- group, carbonyl group or iminomethylene group, etc. Both of A1 and A2 denote a hydrogen atom or either thereof denotes the hydrogen atom and the other denotes a substd. or unsubstd. alkylsulfonyl group or substd. or unsubstd. aryl sulfonyl group or substd. or unsubstd. acyl group. The photosensitive material which is excellent in image quality, such as line images or suitability for dot expanding and contracting, is obtd. in this way.

Description

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

(Prior Art) In the field of photoengraving, 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) net photographs is widely used in the making of catalogs and large posters.
In plate making that uses enlarged halftone dots, the number of lines becomes coarser, resulting in blurred dots. When reduced, the number of lines per inch is larger than that of the original, and a thinner point is photographed. Therefore, in order to maintain halftone reproducibility, an image forming method having a wider latitude is required.

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

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

For this reason, the above development method (lith development system)
There is a need for an image forming system that eliminates the instability of image formation caused by the process, develops with a processing solution that has good storage stability, and obtains ultra-high contrast photographic characteristics, and one example of this is U.S. Pat. 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
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 sulfite preservative of 0.00.
A system has been proposed for forming ultra-high contrast negative images with γ of more than 10 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 the system exhibits excellent performance in terms of speed and original reproducibility, there is a need for a system that is more stable and has improved original reproducibility in order to cope with the diversity of printed materials in recent years.

Examples of systems using hydrazine containing a redox compound that releases a development inhibitor upon oxidation are disclosed in JP-A-61-213847 and JP-A-64-72140.

On the other hand, an example using silver chlorobromide is disclosed in JP-A No. 60-83028.
It is disclosed in 60-112034, 62-235947, and 63-103232.

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

A second object of the present invention is to provide a silver halide photographic material in which sensitivity, γ, and D maX are less likely to decrease even when the pH decreases or the bromide ion concentration increases due to processing of a large amount of film. That's true.

(Means for Solving the Problems) The above object of the present invention is to provide a light-sensitive silver halide emulsion layer containing at least one hydrazine derivative on a support, and an oxidized silver halide emulsion layer or other hydrophilic colloid layer. SS is characterized by containing at least one redox compound that releases a development inhibitor by
In the rosin silver photographic light-sensitive material, the silver halide emulsion consists of 50 mol% or more of silver chloride and has a dispersion coefficient of 20%.
This was achieved by using a negative-working silver norogenide photographic light-sensitive material characterized by the following monodispersed grains.

The hydrazine derivative used in the present invention has the following general formula (
Preference is given to compounds represented by I).

General formula (I) R, -N-N-G, -R2 A2 In the formula, R1 represents an aliphatic group or an aromatic group, and R2 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, represents an amino group or a hydrazino group, G1 represents a -C- group, a -8022 carbonyl group or an iminomethylene group, and AI, A
Both 2 represent a hydrogen atom, or one of them 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 (I), the aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. This alkyl group may have a substituent.

The aromatic group represented by R in general formula (I) 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 group, carboxyl group, phosphoric acid amide group, diacylamino group, imide O 111 group, R2-NHCN-C- group, etc. Preferred substituents include an alkyl group (preferably a carbon number 1 group).
~20 carbon atoms), aralkyl groups (preferably 7~20 carbon atoms),
30), alkoxy group (preferably 1 to 2 carbon atoms)
0), substituted amino groups (preferably 1 to 20 carbon atoms), substituted amino groups (preferably 1-20 carbon atoms)
(an amino group substituted with an alkyl group), 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 (preferably one having 1 carbon number) 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 (1) is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, one containing a benzene ring). .

1 When G1 is a 10-group, preferable groups 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-hydroquinbenzyl group, etc.), aryl group (e.g., phenyl group, 3゜5-dichlorophenyl group, 0-methanesulfonamidophenyl group, etc.) group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.),
Particularly preferred is a hydrogen atom.

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

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

Also, R2 splits the GI-R2 part from the remaining molecules,
It may be one that causes a cyclization reaction to produce a cyclic structure containing an atom of the G1 Rt moiety, and examples thereof include those described in JP-A No. 63-29751.

A hydrogen atom is most preferable as A, A2.

R1 or R2 in the general formula (1) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. A 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,
It can be selected from phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group, etc. Examples of the polymer include those described in JP-A No. 1-100530.

R1 or R2 in general formula (I) 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
No. 201.046, No. 59-201,047, No. 59
-201,048, 59-201,049, JP-A-61-170,733, JP-A-61270.744,
Patent Application No. 62-948, Patent Application No. 62-67.508, No. 6
Examples thereof include groups described in No. 2-67.501 and No. 62-67.510.

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

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

-1 -4 -6 -3 [7 2Hi -8 1-9 ■-10 ■ 5 ■-12 ■-13 -14 ■-18 ■ 0 ■-25 ■-26 ■-24 Hydrazine derivative used in the present invention In addition to the above, RESEARCHDISCLO3URE
Item23516 (November 1983 issue, P, 3
46) and the documents cited therein, as well as U.S. Pat.
No. 76.364, No. 4,278,748, No. 4,38
No. 5,108, No. 4,459,347, No. 4,560
, No. 638, 4. No. 478.928, 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. 62-948, EP No. 217,310, or US4
゜686.167, JP 62-178,246,
No. 63-32,538, No. 63-104゜047,
No. 63-121,838, No. 63-129.337, No. 63-223,744, No. 63-234,244
No. 63-234,245, No. 63-234,24
No. 6, No. 63-294.552, No. 63-306, 4
No. 38, JP-A-1-100,530, JP-A No. 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
3-116,239, 63-147,339, 63-179,760, 63-22'9,163, Japanese Patent Application No. 1-18.377, 1-18,378 ,
1-18.379, 1-15,755, 1-
No. 16.814, No. 1-40,792, No. 1-42.
No. 615, No. 1-42, 616, No. 1-123.69
No. 3, 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-' mol to 2X10-' mol.

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 which 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) R1-N-N-G+ -(Time)t-PUGA
, A.

General formula (R-2) A1 As A+ General formula (R-3) In these formulas, R1 represents an aliphatic group or an aromatic group, -G
t R1 1 group, -0- group, 180- group, -5O2- 1 group or -P- group. Gt is just a knot G2
Rt represents a compound, -O--S- or -N-, and R12 represents a hydrogen atom or R1.

A1 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. A8 is synonymous with A or -CH2C
H(Time) represents -PUGA4.

A represents a nitro group, a cyano group, a carboxyl group, a sulfo group or -GI Gt R3.

Time represents a divalent linking group, and t represents 0 or 1. PUG stands for 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 R1 preferably has 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), (R-3),
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.

For example, among the benzene ring, naphthalene ring, pyridine ring, quinoline ring, isoquinoline ring, etc., those containing a benzene ring are preferred.

Particularly preferred as R1 is an aryl group.

The aryl group or unsaturated heterocyclic group of R1 may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, Ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group,
Acyl group, alkoxycarbonyl group, acyloxy group,
Examples include carbonamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, etc. Preferred substituents include linear, branched or cyclic alkyl group (preferably one having 1 to 20 carbon atoms), aralkyl group (preferably is one having 7 to 3 carbon atoms), an alkoxy group (preferably one having 1 to 3 carbon atoms), a substituted amine group (preferably one having 1 to 3 carbon atoms)
~30 alkyl group substituted), acylamino group (preferably having 2 to 40 carbon atoms), sulfonamide group (preferably having 1 to 40 carbon atoms)
, a ureido group (preferably one having 1 to 40 carbon atoms,
Examples include phosphoric acid amide groups (preferably those having 1 to 40 carbon atoms).

The general formulas (R-1), (R-2), and (R-3) are most preferred.

A is preferably a hydrogen atom, and A is preferably a hydrogen atom.

is a hydrogen atom, CH2CHf T +m e-+
-TP[JGA.

is preferred.

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

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

As the divalent linking group represented by Time, for example, U.S. Pat.
U.S. Pat. No. 4,310,612 (JP-A-55-53,330) and U.S. Pat. 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 Magazine Nα21,228 (1981
February), U.S. Patent No. 4,416,977 (Japanese Unexamined Patent Publication No. 57
-135.944), JP-A No. 58-209.736, JP-A No. 58-209,738, etc., quinomonomethane is produced by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group. , or an analog thereof to release PUG: U.S. Pat. No. 4,420,
No. 554 (Japanese Patent Publication No. 57-136,640), Japanese Patent Application Publication No. 5
No. 7-135゜945, No. 57-188,035, No. 58-98.728, No. 5B-209,737, etc., by electron transfer of the moiety having an enamine structure of the nitrogen-containing heterocycle. One that releases PUG from the γ-position of Those that release PUG; U.S. Patent No. 4,146,396 (JP 52-90932), JP 59-93,442, JP 59-75475, JP 60-24914
8, JP-A-60-249149, etc., which releases PUG with the production of aldehydes: JP-A-51
-146,828, 57-179.842, 5
9-104,641 which releases PUG with decarboxylation of the carboxyl group, -0-COOCR,R
b -Puc (R, , R, represents a -valent group) structure, which releases PUG with decarboxylation and subsequent generation of aldehydes; JP-A-60-7,429 Examples include those that release PUG with the production of isocyanate as described in U.S. Pat. Can be done.

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

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

E, ni0Mess) and Chi H James (T
``The Theory of the Photographic Process'' by James H.
f Photographic Process
s) J 3rd edition, 1966 Macmillan
1lan) Publishing, pp. 344-346.

The development inhibitor represented by PUG may be substituted. Examples of substituents include those listed as substituents for R1, 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 the general formulas (R-1), (R-2), and (R-3), R1 or WT time + TPUG contains a ballast group commonly used in immobile photographic additives such as couplers, and 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
) is an organic group that provides a sufficient molecular weight to substantially prevent the compound represented by the formula from diffusing into other layers or into the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, and an amide group. group, a ureido group, a urethane group, a sulfonamide group, etc. The ballast group is preferably a ballast group having a substituted benzene ring, particularly a ballast group having a benzene ring substituted with a branched alkyl group.

Specifically, the adsorption promoting group to silver halide is 4-
Thiazoline-2-thione, 4-imidacyline-2-thione, 2-thiohydantoin, rhodanine, thiobarbital acid, tetrazoline-5-thione, 1. 2. 4-
Triazoline-3-thione, 1. 3. 4-oxazoline-2-thione, benzimidacillin-2-thione,
Benzoxazoline-2-thione, benzothiazoline-
Cyclic thioamide group, linear thioamide group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (of the carbon atom to which the -3H group is bonded) such as 2-thione, thiotriazine, When the neighbor is a nitrogen atom, it has the same meaning as a cyclic thioamide group which has a tautomeric relationship with this, and the specific examples of this group are the same as those listed above.), a group having a disulfide bond, a benzo triazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, oxazole, oxazoline, thiadiazole,
Examples include 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 heterocyclic quaternary salts such as benzimidazolinium. .

These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent for R4.

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

\ # ; 303- = \ In addition to the above-mentioned redox compounds used in the present invention, for example, JP-A-61-213゜847 and JP-A No. 61-213゜847,
No. 2-260,153, Patent Application No. 1-102,393,
Those described in No. 1-102,394, No. 1-102,395, and No. 1-114,455 can be used.

The method for synthesizing the redox compound used in the present invention is, for example, JP-A-61-213,847, JP-A No. 62260.153.
No. 4, U.S. Pat. 684. No. 604, patent application 1986
-98,803, U.S. Patent No. 3,379,529,
3,620,746, 4,377.634, 4.332.878, JP 49-129,536, 56-153.336, 56-153,342
It is written in the number 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 range of Xl0-5 to lXl0-2 mol.

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 dissolving it in

In addition, by the well-known emulsification and dispersion method, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or diethyl phthalate can be dissolved using 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.

The halogen composition of the monodispersed silver halide emulsion used in the present invention has a silver chloride content of 50 mol% or more, silver chlorobromide,
It consists of either silver iodochloride or silver iodochlorobromide. The silver iodide content is 3 mol% or less, more preferably 0.5 mol% or less.

Various methods known in the field of silver halide photographic materials can be used to prepare the monodisperse silver halide emulsion used in the present invention. For example, P. Glafkide (P, Gla)
fkides) [Chimie et Physique Photography (Chimie et Physique Ph
otograhique) J (Paul Monte1, 1967), G.
Written by F. Duffin [
Photographic Emulsion Chemistry (P
photographicEmulsion Chemi
The Focal Press (The Focal Press)
cal Press), 1966), V.L.
Zelikman (V, L, Zelikman et
a1) [Making and Coating Photographic Emulsion (Making and Coating Photographic Emulsion)
CoatingPhotographic Emu
lsion) J (The Focal Press (Th)
e Focal Press (1964)).

In the present invention, a monodispersed emulsion has a coefficient of variation of 20% or less;
Particularly preferred is a silver halide emulsion having a grain size distribution of 15% or less.

Here, the coefficient of variation is Defined as

The average grain size of grains in a monodisperse silver halide emulsion is 0.
．． 5 μm or less, particularly preferably 0.1 μm to 0.1 μm.
It is 4 μm.

As a method of reacting the water-soluble silver salt (silver nitrate aqueous solution) and the water-soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. As one type of simultaneous mixing method, the pA in the liquid phase in which silver halide is produced is
A method of keeping g constant, ie, a controlled double jet method, can also be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetrasubstituted thiourea.

More preferred are tetrasubstituted thiourea compounds, which are disclosed in JP-A No. 5
It is described in No. 3-82408 and No. 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-dimethyl-2-imidazolidinethione.

The controlled double jet method and the grain formation method using a silver halide solvent can easily produce a silver halide emulsion with a regular crystal shape and a narrow grain size distribution, and are suitable for producing the emulsion used in the present invention. It is an effective method.

The monodisperse emulsion preferably has a regular crystal shape such as a cube, an octahedron, or a tetradecahedron, and a cubic shape is particularly preferred.

The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

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 may coexist in the silver halide grain formation or physical ripening process. good.

In the present invention, the silver halide emulsion which is particularly suitable as a light-sensitive material for line drawing and halftone dot creation is
It is an emulsion prepared in the presence of 0-'' to 10-s mol of iridium salt or a complex salt thereof.

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

The iridium salt used here is a water-soluble iridium salt or an iridium complex salt, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridate (DI), potassium hexachloroiridate (IV),
Examples include ammonium hexachloroiridate (III).

It is preferable to chemically sensitize the monodispersed emulsion of the present invention, and known methods such as sulfur sensitization, reduction sensitization, gold sensitization, etc. can be used, and these methods can be used alone or in combination. A preferred chemical sensitization method is total sulfur sensitization.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used. Specific examples are U.S. Patent Nos. 1,574,944 and 2.
, No. 278,947, No. 2,410,689, No. 2,
No. 728,668, No. 3,501,313, No. 3.
656. It is described in No. 955. Preferred sulfur compounds are thiosulfates and thiourea compounds, and the pAg during chemical sensitization is preferably 8.3 or less, more preferably in the range of 7.3 to 8.0.

Furthermore, Mo1sar, Klein Gelatin
e, Proc, Syme.

2nd, 301-309 (1970) et al., which uses polyvinylpyrrolidone and thiosulfate in combination, also gives good results.

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.

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

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

In the present invention, JP-A No. 55-52050, page 45~
It is also possible to add aggravating dyes (for example, cyanine dyes, merocyanine dyes, etc.) having an absorption maximum in the visible range as described on page 53. As a result, spectral deterioration can be achieved on the longer wavelength side than the specific sensitivity region of silver halide.

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

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

Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are disclosed in Research Disclosure (Res.
176 Volume 1
7643 (published in December 1978), page 23, item 3.

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, promohenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitro benzotriazoles, etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1°3.3a, 7 A number of compounds known as antifoggants or stabilizers can be added, such as tetrazaindenes (frequently), pentaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Among these, preferred are hensitriazoles (e.g., 5-methyl-benzotriazole) and nitroindazoles (e.g., 5-nitroindazole), and these compounds may also be included in the treatment solution. JP-A-62-3
A compound that releases an inhibitor during development as described in No. 0243 may be included as a stabilizer or for the purpose of preventing black spots.

The photographic material of the present invention may contain developing agents such as hydroquinone derivatives and phenidone derivatives for various purposes such as stabilizers and accelerators.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer.
For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes, (formaldehyde, glucuraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, activated vinyl compounds (1,
3,5 triacryloyl-hexahydro-3-triazine, l,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-5-) riazine, etc.), mucohalogen Acids (such as mucochloric acid), 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 carboxylic acids, and amine oxides; complexes such as alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, and imidazolium. Cationic surfactants such as ring quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in Japanese Patent Publication No. 58-9412.

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

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

Specific examples thereof include U.S. Pat. No. 3,379,529, U.S. Pat. No. 3,620,746, and U.S. Pat.
No. 4, U.S. Patent No. 4,332,878, Japanese Unexamined Patent Publication No. 49-1
29.536, JP 54-67.419, JP 56-153,336, JP 56-153,342
No., JP-A-59278.853, JP-A No. 59-90435
No. 59-90436, No. 59-138808, and the like.

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

The light-sensitive material used in the present invention may contain a dispersion of water or a poorly soluble synthetic polymer for the purpose of dimensional stability. For example, a polymer containing as a monomer component alkyl (meth)acrylate, alkoxy acrylic (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. is used. be able to.

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention preferably contain a compound having an acid group. Examples of the compound having an acid group include organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acrylic acid. Polymers or dipolymers having acid monomers such as , maleic acid, phthalic acid as repeating units may be mentioned. Regarding these compounds, see JP-A-64-223834 and JP-A-64-61.
No. 228437, No. 62-25745, and No. 62-
The record of specification No. 55642 can be referred to.

Among these compounds, particularly preferred are ascorbic acid as a low molecular compound, and acid monomers such as acrylic acid and crosslinkable monomers having two or more unsaturated groups such as divinylbenzene as high molecular compounds. It is a water-dispersible latex of a copolymer consisting of -.

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

In order to obtain ultra-high contrast and high sensitivity photographic properties using the halogenated SMI"E optical material of the present invention, it is necessary to use a conventional infectious developer or a high alkaline developer with a pH close to 13 described in U.S. Pat. No. 2,419,975. It is not necessary to use a liquid, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains 0.15 mol/1 or more of sulfite ion as a preservative, and has a pH of
A sufficiently ultra-high contrast negative image can be obtained with a developer having p) of 10.5 to 12.3, particularly p) of 111.0 to 12.0.

There is no particular restriction on the developing agent used in the developer used in the present invention, but it is preferable that it contains dihydroxybenzenes, since it is easy to obtain good halftone dot quality, and dihydroxybenzenes and 1-phenyl- A combination of 3-pyrazolidones or a combination of dihydroxybenzenes and p-aminephenols may also be used.

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

The developing agent for 1-phenyl-3-pyrazolidone or its derivative used in the present invention is 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-4-pyrazolidone, l-phenyl-4-Jf)Ii -4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-
Dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-P-aminophenyl-44-dimethyl-3-pyrazolidone, 1-P-tolyl-4,4-dimethyl-3-pyrazolidone, etc. There is.

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

The developing agent is usually preferably used in an amount of 0.05 mol/l to 0.8 mol/l. In addition, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols, the former is 0.
0.05 mol/1 to 0.5 mol/l, the latter 0.06 mol/l
It is preferable to use it in an amount of 1 or less.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The amount of sulfite is preferably 0.15 mol/1 or more, particularly 0.5 mol/1 or more, and the upper limit is preferably 2.5 mol/l.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
The pH of the developer solution, including H2FM moderator and buffering agent, is 10.5.
It is set between 12.3 and 12.3.

Additives used in addition to the above ingredients include compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, and methyl cellosolve. , hexylene glycol, ethanol, methanol, etc. Solvent: 1-
Antifoggants such as indazole compounds such as phenyl-5-mercaptotetrazole and 5-nitroindazole, and penttriazole compounds such as 5-methylbenztriazole, or black pepper.
Inhibitor: May also contain a color toner, a surfactant, an antifoaming agent, a water softener, a film hardening agent, and JP-A-56-
It may also contain the amino compounds described in No. 106244.

The developing solution of the present invention contains a silver stain preventive agent.
．． The compound described in No. 347 can be used as a solubilizing agent added to the developer, which is disclosed in Japanese Patent Application No. 109/1974.
Compounds described in No. 3 can be used. In addition, as a pHv and buffer agent used in developing solutions, JP-A-60-93, 43
The compound described in No. 3 or the compound described in Japanese Patent Application No. 61-28708 can be used.

As the fixing agent, those having commonly used compositions can be used. As the fixing agent, in addition to periosulfate and thiocyanate, organic sulfur compounds known to be effective as fixing agents can be used.

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

The processing temperature is usually selected between 1 day and 50°C, more preferably between 25°C and 43°C.

(Examples) Next, the present invention will be described in more detail based on Examples.

Using.

(Developer prescription) hydroquinone N・Methyl P・Aminophe Nol 1/2 sulfate Sodium hydroxide potassium hydroxide 5-sulfosalicylic acid Boric acid potassium sulfite Ethylenediaminetetraacetic acid di sodium salt potassium bromide 5-methylbenzotriazole n-butyl jetanol min add water For the developer, use the recipe listed below. 45.0g 8g 8g 8g 8g 8g 8g 1.0g 6.0g 0.6g 0° 18° 55° 45° 25° 110° 15.0g 11I.

(pH-11.6) (Example 1) (Preparation of emulsion according to the invention) Emulsion A: 0.13 M aqueous silver nitrate solution and (NH,), RhCI corresponding to 1X10-7 mol per mol of silver.

A halogen salt aqueous solution containing 0.04M potassium bromide and 0.09M sodium chloride was added to an aqueous gelatin solution containing sodium chloride at 45°C for 12 hours with stirring.
Added by double jet method for 1 minute, average particle size 0
．． Nucleation was performed by obtaining silver chlorobromide grains of 15 μm and a silver chloride content of 70 mol %. Then 0.8 in the same way
7M silver nitrate aqueous solution, 0.26M potassium bromide,
A halogen salt aqueous solution containing 0.65M sodium chloride was added over 20 minutes by a double jet method.

After that, conversion was performed by adding 1X10-'' mol of Kl solution, washing with water by flocculation method according to a conventional method, adding 40 g of gelatin, pH 6.5, pAg 7.
．． 5, and further added 5 μ of sodium lithiosulfate and 8 μ of chloroauric acid per mole of silver, heated at 60° C. for 60 minutes, and subjected to chemical sensitization treatment, and as a stabilizer, 3.
3a, ? - Added 150 μ of tetrazaindene. The obtained particles were cubic silver chlorobromide particles with an average particle size of 0.27 μm and a silver chloride content of 70 mol%. (Coefficient of variation 15%).

Emulsion B: 0.13 M aqueous silver nitrate solution and (NH4)iRhCl m corresponding to 1X10-' mol per mol of silver.
A halogen salt aqueous solution containing 0.04M potassium bromide and 0.09M sodium chloride was added to an aqueous gelatin solution containing sodium chloride and l,3-dimethyl-2-imidazolidinethione at 38°C for 12 hours with stirring.
Added by double jet method for 1 minute, average particle size 0
．． Nucleation was performed by obtaining 15 μm 1 silver chlorobromide grains with a silver chloride content of 70 mol %. Then 0.8 in the same way
7M silver nitrate aqueous solution, 0.26M potassium bromide,
A halogen salt aqueous solution containing 0.65M sodium chloride was added over 20 minutes by a double jet method.

After that, convert 1×10-” mol of KI solution, wash with water by flocculation method according to the conventional method, add 40 g of gelatin, pH 6.5, pAg 7.
．． 5, and further added 5 μ of sodium lithiosulfate and 8 μ of chloroauric acid per mole of silver, heated at 60° C. for 60 minutes, chemically sensitized, and added 1.5 μ as a stabilizer. 3. 3
a.? - Added 150 μ of tetrazaindene. The resulting grains had an average grain size of 0.27 μm and a silver chloride content of 7.
It was 0 mol% silver chlorobromide cubic particles. (coefficient of variation 1
0%).

Emulsion C Same as Emulsion B, but using 1,8- as silver halide solvent instead of 1,3-dimethyl-2-imidazolidinethione.
Emulsion C was prepared in exactly the same manner except that dihydroxy-3,6-cythiaoctane was used. (Variation coefficient 12%
) Emulsion D: 0.13 M aqueous silver nitrate solution with (NH,), RhCI corresponding to 1X10-7 moles per mole of silver.

-, a halogen salt aqueous solution containing 0.052M potassium bromide and 0.078M sodium chloride, and 1. Silver chlorobromide particles with an average particle size of 0.15 μm and a silver chloride content of 60 mol% were added to an aqueous gelatin solution containing 3-dimethyl-2-imidazolidinethione at 45° C. for 12 minutes with stirring using a double jet method. Nucleation was performed by obtaining Then 0 in the same way
．． A halogen salt aqueous solution containing an 87M silver nitrate aqueous solution, 0.34M potassium bromide, and 0.52M sodium chloride was added over 20 minutes by a double jet method.

After that, conversion was performed by adding 1X10-'' mol of Kl solution, washing with water by flocculation method according to a conventional method, adding 40 g of gelatin, pH 6.5, pAg 7.
．． 5, and further added 5 μ of sodium lithiosulfate and 8 μ of chloroauric acid per mole of silver, heated at 60° C. for 60 minutes, chemically sensitized, and added 1.5 μ as a stabilizer. 3. 3
a. 150 mg of 7-chitrazaindene was added. The obtained particles were cubic silver chlorobromide particles with an average particle size of 0.27 μm and a silver chloride content of 60 mol%. (Coefficient of variation lO%).

(Preparation of comparative emulsion) Emulsion E: 0.13M silver nitrate aqueous solution and (NH4)JhCA'- corresponding to 1X10-' mol per 1 mol of silver.
A halogen salt aqueous solution containing 0.078M potassium bromide and 0.052M sodium chloride was added to an aqueous gelatin solution containing sodium chloride at 45°C with stirring.
The material was added by a double jet method for 12 minutes to obtain silver chlorobromide particles having an average particle size of 0.15 μm and a silver chloride content of 70 mol %, thereby performing extraction forming. Then 0 in the same way
．． A halogen salt aqueous solution containing an 87M silver nitrate aqueous solution, 0.522M potassium bromide, and 0.348M sodium chloride was added over 20 minutes by a double jet method.

After that, conversion was performed by adding 1X10-'' mol of Kl solution, washing with water by flocculation method according to a conventional method, adding 40 g of gelatin, pH 6.5, pAg 7.
．． 5, and further added 5 μ of sodium thiosulfate and 8 μ of chloroauric acid per mole of silver, heated at 60° C. for 60 minutes, chemically sensitized, and added 1.5 μ as a stabilizer. 3. 3
a. 150 μ of 7-chitrazaindene was added. The resulting grains had an average grain size of 0.27 μm 1 silver chloride content 4
It was 0 mol% silver chlorobromide cubic particles. (coefficient of variation 1
1%).

(Emulsion F) Emulsion F was prepared in exactly the same manner as Emulsion A except that the stirring was changed and the degree of supersaturation during grain formation was changed. (Coefficient of variation 30%) (Emulsion G) Emulsion G was prepared in exactly the same manner as in emulsion preparation, except that the degree of supersaturation during grain formation was changed by changing the stirring. (Coefficient of variation 25%) [Emulsion] Add 1 mol of silver nitrate aqueous solution and 1.2X10-' mol of (NH4) per 1 mol of silver in the presence of ammonia to an aqueous gelatin solution kept at 50°C.
Potassium iodide and potassium bromide aqueous solutions containing 3RhCA fi were added at the same time for 60 minutes, and the pAg was adjusted to 7.8 during that time.
A cubic monodisperse emulsion with an average grain size of 0.25 μm and an average silver iodide content of 1 mol % was prepared by maintaining the pH at
= 6.0 pAg = 8.5, added 5 ■ of sodium thiosulfate and 6 ■ of chloroauric acid, heated at 60°C for 60 minutes, subjected to chemical sensitization treatment, and added I, 3.3a, as a stabilizer.
150 μ of 7-chitrazaindene was added. (Variation coefficient 9
%) Emulsions A to H are summarized in Table 1.

(Table 1) These emulsions were divided to give sensitizing dyes of 1X10-'' moles of 5-(3-(4-sulfobutyl)-5-chloro-2-oxazolidylidene)-1- per mole of silver. Hydroxyethyl-3-(2-pyridyl)-2-thiohydantoin was added, and further 2XIO-' moles of 1-phenyl-5-mercaptotetrazole and 5X10-' moles of a short-wave cyanine dye represented by the following structural formula (a) were added. ,(b)
A water-soluble latex (200 μ/I) and a dispersion of polyethyl acrylate (200 μ/I) represented by hydrazine compound was added as shown in Table 2.

(a) (b) CH.

-fic-CH2 CH.

(Preparation of redox compound-containing layer emulsion) Emulsion A: 1.0
An aqueous halogen salt solution containing 0.3 M potassium bromide and 0.74 M sodium chloride, containing 3XlO-' mol of (NH4)3RhCA per mole of silver, and 1 ．． 3-dimethyl-
The mixture was added to an aqueous gelatin solution containing 2-imidazolidinethione by a double jet method at 45° C. for 30 minutes with stirring to obtain silver chlorobromide particles having an average particle size of 0.28 μm and a silver chloride content of 70 mol%. After that, wash with water by the flocculation method according to the usual method, and use 40 g of gelatin.
was added to adjust the pH to 6.5 and pAg to 7.5, and further added 5 μ of sodium thiosulfate and 8 μ of chloroauric acid per mole of silver.
was added, heated at 60°C for 60 minutes, subjected to chemical sensitization treatment, and 1,3°3a,7-chitrazaindene 1 was added as a stabilizer.
50 ■ was added.

The obtained grains were cubic silver chlorobromide grains with an average grain size of 0.28 μm and a silver chloride content of 70 mol %.

(Coefficient of variation lO%).

This emulsion was divided into lX per mole of silver as a sensitizing dye.
10-' moles of 5-[:3-(4-sulfobutyl)-
5-Chloro-2-oxazolidylidene]1-hydroxyethyl-3-(2-pyridyl)=2-thiohydantoin was added and an additional 2X10-' moles of 1-phenyl-5-
A dispersion of mercaptotetrazole and polyethyl acrylate was prepared at 50 mg/rrr, 2-bis(vinylsulfonylacetamido)ethane was prepared at 40 mg/rrr, and a redox compound represented by the general formula (II) of the present invention was prepared as shown in Table 2.
It was added as follows.

A hydrazine-containing layer was added to the bottom layer (Ag 3.6 g/g, Seratin 2 g/rrr), and an intermediate layer (gelatin 0, 5
g/rd) via a layer containing a redox compound (Ag0
．． 4g/rd, gelatin 0. 5g/rrr) and on top of this as a protective layer gelatin 1.0g/d, an amorphous Si0g matting agent with a particle size of about 3.5μ 40μ/rrr
, methanol silica 0.1g/rrr, polyacrylamide 100mm/rrr, hydroquinone 200mm/rr, silicone oil, and as a coating aid fluorine surfactant C, F, , So, NCH, C00K C shown by the following structural formula. >Ht and a layer containing sodium dodecylbenzenesulfonate were simultaneously applied to prepare samples as shown in Table 1.

The back layer and back layer protective layer were coated using the following formulations.

[Back layer prescription]

Gelatin 3 g/rd latex Polyethyl acrylate 2 g/% Surfactant Sodium p-dodecylbenzenesulfonate 40/M Gelatin hardener 110/d Dye Mixture of dyes [a], [b], and [c] Dye (all 50■/I dye (b)
:] 100■/d dye (c)
50■/Resistance [Back protective layer] Gelatin 0.8g/Polymethyl methacrylate resistant fine particles (average particle size 4.5μ) 30■/Idihexyl α-sulfosacnate sodium salt 15■/M dodecylbenzenesulfonic acid sodium salt 15■ /d Fluorine surfactant 5■/Resistance to C, F,, So,
N-CH,C00K C,H.

sodium acetate dye [a] 40■/endurance Dye (b) SO* K So, K So, K So, to dye (c) Figure 1 shows an outline of the layer structure.

The evaluation is based on the following test method.

(Photographic characteristics) Photographic characteristics 1 was obtained using a developer with the above prescription at 34° using an FG-660F automatic processor (manufactured by Fuji Photo Film Co., Ltd.).
This is the result of 030' processing.

GR-F1 was used as the fixer.

Photographic property 2 is 100% black Fujiris Ortho Film G
A-100 large size (50.8cm x 61cm) 1
These are the results of processing in the same manner as in Photographic Characteristics 1 using a developer after processing 50 sheets.

Here, the sensitivity is a relative value of the reciprocal of the exposure amount that gives a density of 1.5 when developed at 34.degree. C. for 30 seconds, and the value of sample 1 is set to 100.

Here γ is 3. 0-0. 3 OI K os　K Defined by

〔image quality〕

log (exposure amount that gives a density of 0.3) 1. Evaluation of image quality (1) Creation of manuscript Monochrome Scanner 5CA manufactured by Fuji Photo Film Co., Ltd.
Using NART30 and special photosensitive material 5F-100, a transparent image of a person consisting of halftone dots and a step wedge in which the halftone percentage was changed in stages were created. At this time, the number of screen lines was 150 lines/inch.

(2) Photographed by Dainippon Screen (Xe
The evaluation sample was exposed to light by irradiating it with a lamp.

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

(3) Adjust the exposure amount as in evaluation (2) to the small dot side (highlight area)
A five-grade evaluation (from 5 to 1) was performed in descending order of the gradation reproducibility (difficulty of halftone dot collapse) in the shadow areas of the samples, which combined the halftone dot percentages.

2. Evaluation of line drawing image quality: Reflection density is 0.5 to 1. A manuscript consisting of 7th grade Mincho typeface and Gothic typeface typesetting characters in the range 2 was photographed with a Dainippon Screen camera (DSC351) and then developed (34'C30') under the same conditions as the photographic characteristics. This is the result of doing this. Evaluation is performed on a five-point scale, with "5" representing the best quality and "l" representing the worst quality. “5” or “4” is practical, “3” is poor quality, but it is barely practical and “2”
Or "1" is not practical.

As is clear from Table 3, the sample of the present invention■■■■■■■00
0 means that the fluctuation due to processing is small and the image quality is good.

In particular, the emulsion ■■■@■O prepared using thiourea shows better performance with smaller processing fluctuations.

(Example 2) (Preparation of emulsion I of the invention) Emulsion A: A 0.13 M aqueous silver nitrate solution and a solution of Nl(4)3Rhc 1 corresponding to 10-7 mol of silver per 1 mol of silver.
- and 2 X 10-7 mol (DKs I r C1s
The content is 0. .

A halogen salt aqueous solution containing 4M potassium bromide and 0.09M sodium chloride was double jetted into a gelatin aqueous solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione at 38°C for 12 minutes with stirring. Nucleation was carried out by adding silver chlorobromide grains with an average grain size of 0.15 μm and a silver chloride content of 70 mol %. Subsequently, a halogen salt aqueous solution containing 0.87M silver nitrate aqueous solution, 0.26M potassium bromide, and 0.65M sodium chloride was similarly added over 20 minutes by the double jet method. After that, wash with water by the flocculation method according to the usual method, and use 40 g of gelatin.
was added to adjust the pH to 6.5 and pAg to 7.5, and then added 5 mg of sodium lithiosulfate and 8 g of chloroauric acid per mole of silver.
(1) was added, heated at 60°C for 60 minutes, chemically sensitized, and used as a stabilizer (1). 3. 3a, 150 μ of 7-chitrazaindene was added. The obtained particles were cubic silver chlorobromide particles with an average particle size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%).

Example 1 was prepared by dividing emulsion B and emulsion I used in Example 1).
Sample 31 as shown in Table 4 with exactly the same additives and layer configuration as
-45 were produced.

The photographic performance of these samples was evaluated in the same manner as in Example 1. The results are shown in Table 5.

As is clear from Table 5, all the samples show good results, but the sample containing an iridium compound particularly gives good photographic performance.

4,

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of the layer structure of the sensitive material in Example-1.

Claims (1)

[Scope of Claims] 1) A photosensitive silver halide emulsion layer containing at least one hydrazine derivative on a support, which releases a development inhibitor upon oxidation into the emulsion layer or other hydrophilic colloid layer. In a silver halide photographic light-sensitive material containing at least one redox compound, the silver halide emulsion consists of 50 mol% or more of silver chloride and has a dispersion coefficient of 2.
A negative-working silver halide photographic material characterized by having monodisperse particles of 0% or less. 2) The silver halide photographic material according to claim 1, wherein the silver halide emulsion is grain-formed in the presence of a tetrasubstituted thiourea compound. 3) The silver halide photographic material according to claim 1, wherein the silver halide emulsion is grain-formed in the coexistence of an iridium complex salt. 4) The redox compound according to claim 1, wherein the redox compound has hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines, and reductones as redox groups. Silver halide photographic material. 5) The silver halide photographic material according to claim 1, wherein the redox compound has a hydrazine as a redox group.