JP2704449B2 - Silver halide photographic material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a super-high contrast silver halide photographic light-sensitive material used for photolithography.

(Prior Art) In the field of photoengraving, there is a demand for a photographic photosensitive material having good original reproducibility, a stable processing solution, or a simple replenishment in order to cope with the variety and complexity of printed matter.

Particularly in the line drawing photographing process, the manuscript is made by pasting typesetting characters, handwritten characters, illustrations, halftone pictures, and the like. Therefore, images having different densities and line widths are mixed in an original, and a plate-making camera, a photographic photosensitive material, or an image forming method for finishing these originals with good reproducibility is strongly desired. On the other hand, in plate making of catalogs and large posters, enlargement (enlargement) or reduction (shrinking) of a halftone picture is widely performed, and in plate making using halftone dots, the number of lines becomes coarse and blurred. Shooting. In the reduction, the number of lines / inch is larger than that of the original, and a thin point is photographed. Therefore, there is a demand for an image forming method having a wider latitude in order to maintain the reproducibility of halftone.

A halogen lamp or a xenon lamp is used as a light source of a plate making camera. In order to obtain a photographic sensitivity with respect to these light sources, a photographic light-sensitive material is usually subjected to orthosensitization. However, it has been found that the ortho-sensitized photographic material is more strongly affected by the chromatic aberration of the lens, so that the image quality is liable to deteriorate. This deterioration is more remarkable for a xenon lamp light source.

The lith-type silver halide photographic material composed of silver chlorobromide (with a silver chloride content of at least 50%) has a very low effective concentration of sulfite ions (usually 0.1 mol / or less). There is known a method of obtaining a line image or a halftone image having a high contrast and a high blackening density in which an image area and a non-image area are clearly distinguished by processing with a hydroquinone developer. However, in this method, since the concentration of sulfurous acid in the developer is low, development is extremely unstable against air oxidation, and various efforts and efforts have been made to keep the solution activity stable. Was extremely slow, and the work efficiency was reduced at present.

For this reason, an image forming system that eliminates instability of image formation by the above-described developing method (lith developing system), develops with a processing solution having good storage stability, and obtains ultra-high contrast photographic characteristics is provided. U.S. Pat. Nos. 4,166,742, 4,168,977, 4,221,857,
4,224,401, 4,243,739, 4,272,606, 4,31
As shown in No. 1,781, a surface latent image type silver halide photographic material to which a specific acylhydrazine compound has been added contains 0.15 mol / or more of a sulfite preservative at pH 11.0 to 12.3 and has good storage stability. Is treated with a developer having
Systems have been proposed for forming over 10 ultra-high contrast negative images. This new image forming system can use only silver chlorobromide having a high silver chloride content in conventional ultra-high contrast image formation, but can also use silver iodobromide and silver chloroiodobromide. There is.

The above image system has excellent performance in terms of sharp halftone dot quality, processing stability, speed and original reproducibility, but is more stable and improved in original reproducibility to deal with the recent variety of printed matter. A desired system is desired.

Examples containing a redox compound which releases a development inhibitor when oxidized in a system using hydrazine are disclosed in JP-A-61-213847 and JP-A-64-72140.

On the other hand, examples using silver chlorobromide are disclosed in JP-A-60-83028 and JP-A-60-83028.
Nos. 1-112034, 62-235947 and 63-103232.

(Problems to be Solved by the Present Invention) A first object of the present invention is to provide a silver halide photographic light-sensitive material having excellent image quality such as line drawing or elongation and shrinkage suitability.

A second object of the present invention is to provide a silver halide photographic light-sensitive material in which the sensitivity, γ, and Dmax are small even when the pH is lowered or the bromine ion concentration is increased by processing a large amount of film. It is.

(Means for Solving the Problems) An object of the present invention is to provide a photosensitive silver halide emulsion layer containing at least one hydrazine derivative on a support and an emulsion layer or other hydrophilic colloid layer. A silver halide photographic light-sensitive material containing at least one type of redox compound which releases a development inhibitor when the silver halide emulsion layer has a silver chloride content of 50 mol% or more and increases the amount of gold and sulfur. Felt and
This has been attained by a negative-working silver halide photographic material characterized by being monodisperse grains having a dispersion coefficient of 20% or less.

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

General formula (I) In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group,
G ₁ -SO ₂ -group, -SO- group, Represents a thiocarbonyl group or an iminomethylene group, A ₁ ,
A ₂ represents a hydrogen atom or a hydrogen atom on one side and a substituted or unsubstituted alkylsulfonyl group on the other side, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

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

In the general formula (I), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.
Here, the unsaturated heterocyclic group may be condensed with the aryl group.

Preferred as R ₁ is an aryl group, particularly preferably a group containing a benzene ring.

The aliphatic group or the aromatic group of R ₁ may be substituted, and typical substituents include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group,
Aryl group, substituted amino group, ureido group, urethane group,
Aryloxy, sulfamoyl, carbamoyl, alkyl or arylthio, alkyl or arylsulfonyl, alkyl or arylsulfinyl, hydroxy, halogen, cyano, sulfo, aryloxycarbonyl, acyl, alkoxycarbonyl An acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, an imide group, And the like. Preferred substituents are an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably having 7 to 30 carbon atoms), and an alkoxy group (preferably having 1 to 20 carbon atoms). ), A substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 30 carbon atoms),
Examples thereof include a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), and a phosphoric amide group (preferably having 1 to 30 carbon atoms).

In formula (I), the alkyl group represented by R ₂ 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, those containing a benzene ring ).

G ₁ In the case of, preferred among the groups represented by R ₂ are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, a phenylsulfonylmethyl group and the like). ), Aralkyl groups (eg, o-hydroxybenzyl group), aryl groups (eg, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl) And the like), and a hydrogen atom is particularly preferable.

R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied.

As G in the general formula (I), Is most preferred.

Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule, -G ₁
-R ₂ moiety of atoms may be such as to occur a cyclic structure cyclization reaction to form a containing, include those described in, for example, JP 63-29751 as an example.

A ₁ and A ₂ are most preferably hydrogen atoms.

R ₁ or R _{2 in} the general formula (I) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. Can be. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (I) may have a group in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of such adsorbing groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, and the like, U.S. Patent Nos. 4,385,108 and 4,459,347;
-195,233, 59-200,231, 59-201,045, 5
Nos. 9-201,046, 59-201,047, 59-201,048,
59-201,049, JP-A-61-170,733, JP-A-61-270,744
No. 62-948, Japanese Patent Application No. 62-67,508, No. 62-67,501
And the groups described in JP-A Nos. 62-67,510.

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

4 As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 23516 (1983
November, p. 346) and references cited therein,
U.S. Pat.Nos. 4,080,207, 4,269,929, 4,276,364
No. 4,278,748, No. 4,385,108, No. 4,459,347,
4,560,638, 4,478,928, UK Patent 2,011,391B,
JP-A-60-179934, JP-A-62-270,948, JP-A-63-29,751
Nos. 61-170,733, 61-270,744, 62-948
No., EP217,310, or US 4,686,167, JP-A-62-17
No. 8,246, No. 63-32,538, No. 63-104,047, No. 63-12
Nos. 1,838, 63-129,337, 63-223,744, 63-2
Nos. 34,244, 63-234,245, 63-234,246, 63-
294,552, 63-306,438, JP-A-1-100,530,
No. 1-105,941, No. 1-105,943, JP-A-64-10,233
No., JP-A-1-90,439, Japanese Patent Application No. 63-105,682, 63
-114,118, 63-110,051, 63-114,119, 6
3-116,239, 63-147,339, 63-179,760,
63-229,163, Japanese Patent Application No. 1-18,377, 1-18,378
Nos. 1-18,379, 1-15,755, 1-16,814
Nos. 1-40,792, 1-42615, 1-42616
And those described in Nos. 1-123,693 and 1-126,284 can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1.times.10.sup.- ⁶ mol to 5.times.10.sup.- ² mol, more preferably 1.times.10.sup.- ⁵ mol to 2.times.10.sup.- ⁵ mol per mol of silver halide.
A range of × 10 ^-2 mol is a preferable addition amount.

The redox compound of the present invention that can release a development inhibitor by being oxidized will be described.

The redox group of the redox compound is preferably a hydroquinone, a catechol, a naphthohydroquinone, an aminophenol, a pyrazolidone, a hydrazine, a hydroxylamine, or a reductone, and more preferably a hydrazine.

The hydrazines used as a redox compound capable of releasing a development inhibitor by being oxidized according to the present invention are preferably those represented by the following general formulas (R-1) and (R-2).
It is represented by the general formula (R-3). The compound represented by formula (R-1) is particularly preferred.

In these formulas, R ¹ represents an aliphatic group or an aromatic group. G ₁ -SO- group, -SO ₂ - group or Represents G ₂ is a mere bond, -O-, -S- or And R ₂ represents a hydrogen atom or R ₁ .

A ₁ and A ₂ represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. In the general formula (R-1), at least one of A ₁ and A ₂ is a hydrogen atom. A ₃ is synonymous with A ₁ or Represents

A ₄ represents a nitro group, a cyano group, a carboxyl group, a sulfo group or -G ₁ -G ₂ -R _1.

Time represents a divalent linking group, and t represents 0 or 1. PUG represents a development inhibitor.

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

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

In formulas (R-1), (R-2) and (R-3), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group.

For example, among those having a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, an isoquinoline ring, etc., those containing a benzene ring are preferable.

Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and typical substituents include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, Ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio, sulfonyl, sulfinyl, hydroxy, halogen, cyano, sulfo, aryloxycarbonyl, acyl, alkoxycarbonyl Groups, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, and the like. Preferred substituents are a linear, branched, or cyclic alkyl group (preferably having 1 to 20 carbon atoms). Aralkyl group (preferably having 7 to 30 carbon atoms), aralkyl group Coxy group (preferably having 1 to 30 carbon atoms), substituted amino group (preferably having 1 to 30 carbon atoms)
An amino group substituted with 30 alkyl groups), an acylamino group (preferably having 2 to 40 carbon atoms), a sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having A compound having 1 to 40, a phosphoric acid amide group (preferably having 1 to 40 carbon atoms) and the like.

As the general formulas (R-1), (R-2) and (R-3), -SO ₂ - group are preferred, Is most preferred.

A ₁ and A ₂ are preferably hydrogen atoms, A ₃ is a hydrogen atom, Is preferred.

In the general formulas (R-1), (R-2) and (R-3)
Time represents a divalent linking group, and may have a timing adjusting function.

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

The divalent linking group represented by Time can be used as a linking group by, for example, an intramolecular ring closure reaction of a p-nitrophenoxy derivative described in U.S. Pat. No. 4,248,962 (JP-A-54-145135).
U.S. Pat. No. 4,310,612 (Japanese Unexamined Patent Publication No.
Which release PUG by an intramolecular ring-closure reaction after ring opening described in US Pat. Nos. 4,330,617, 4,446,216, 4,483,919, and JP-A-59-121,328. Etc., which release PUG with the formation of an acid anhydride by an intramolecular ring-closure reaction of a carboxyl group of a succinic monoester or an analog thereof; U.S. Pat. Nos. 4,409,323 and 4,421,845, Research Disclosure No. 21,228 (December 1981), U.S. Patent No.
4,416,977 (JP-A-57-135,944), JP-A-58-209,
No. 736, No. 58-209,738, etc., which produce quinomonomethane or an analog thereof by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group to release PUG; US Pat. No. 4,420,554 (Japanese Unexamined Patent Publication No.
57-136,640), JP-A-57-135,945 and JP-A-57-188,03.
No. 5,58-98,728 and 58-209,737, which release PUG from the γ-position of enamine by electron transfer of a portion having an enamine structure of a nitrogen-containing heterocyclic ring;
7-56,837 which releases PUG by an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated to a nitrogen atom of a nitrogen-containing heterocyclic ring; U.S. Pat. -90932), JP-A-59-93,4
No. 42, JP-A-59-75475, JP-A-60-249148, with formation of aldehydes described in JP-A-60-249149 and the like.
Those which release PUG; JP-A-51-146,828, 57-179,
Nos. 842 and 59-104,941 which release PUG with decarboxylation of carboxyl group; -O-COOCR _a R _b -PUG
(R _a and R _b represent monovalent groups), which release PUG with decarboxylation and subsequent formation of aldehydes; isocyanates described in JP-A-60-7,429 And PUG is released by the coupling reaction of a color developer with an oxidized product described in U.S. Pat. No. 4,438,193.

Specific examples of the divalent linking group represented by Time are described in detail in JP-A-61-236,549 and Japanese Patent Application No. 63-98,803.

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

The development inhibitors represented by PUG or (Time _t PUG are known development inhibitors having a heteroatom and bonded through a heteroatom, such as CEKMess and "The Theory of Photographic Process" by THJames
Processes), 3rd Edition, 1966 Macmillan
It is described in company publications, pages 344 to 346.

The development inhibitor represented by PUG may be substituted. Examples of the substituent include those exemplified as the substituent of R ¹ , and these groups may be further substituted.

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

The general formula (R-1), (R -2), in (R-3), R ₁ or Time ▲ ▼ PUG is a ballast group which is commonly used in immobile photographic additives such as couplers And a group which promotes the compounds represented by formulas (R-1), (R-2) and (R-3) to be adsorbed to silver halide.

The ballast group has the general formula (R-1), (R-2), (R-
An organic group that gives a molecular weight sufficient to prevent the compound represented by 3) from substantially diffusing into another layer or the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, It comprises one or more combinations of an amide group, a ureido group, a urethane group, a sulfonamide group and the like. The ballast group is preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

Specific examples of the group for promoting adsorption to silver halide include 4
-Thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3,4 Cyclic thioamide groups such as oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3-imidazoline-2-thione, and chain thioamides Group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (when the carbon atom to which the -SH group is bonded is a nitrogen atom, this is synonymous with a cyclic thioamide group having a tautomeric relationship with the nitrogen atom) Specific examples of this group are the same as those listed above.), A group having a disulfide bond, benzotriazole, triazole, tetrazo Le, indazole, benzimidazole, imidazole, benzothiazole,
Nitrogen, oxygen, such as thiazole, thiazoline, benzoxazole, oxazole, oxazoline, thiadiazole, oxathiazole, triazine, azaindene,
Examples thereof include a 5- or 6-membered nitrogen-containing heterocyclic group composed of a combination of sulfur and carbon, and a heterocyclic quaternary salt such as benzimidazolinium.

These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent of R ₁ .

Hereinafter, specific examples of the compound used in the present invention are listed, but the present invention is not limited thereto.

As the redox compound used in the present invention, in addition to the above, for example, JP-A-61-213,847 and JP-A-62-260,1
No. 53, Japanese Patent Application No. 1-102,393, No. 1-102,394, No. 1-
Nos. 102,395 and 1-114,455 can be used.

The method for synthesizing the redox compound used in the present invention is described in, for example, JP-A-61-213,847 and JP-A-62-260,153, U.S. Pat.
No. 4,684,604, Japanese Patent Application No. 63-98,803, U.S. Pat.
No. 29, 3,620,746, 4,377,634, 4,332,878
No., JP-A-49-129,536, JP-A-56-153,336, JP-A-56-15
No. 3,342.

The redox compound of the present invention is used in an amount of 1 × 10 ^{−6 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁵ per mol of silver halide.
It is used in the range of １1 × 10 ^-2 mol.

The redox compound of the present invention may be used in a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like.

Also, by an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. Objects can also be created and used. Alternatively, a redox compound powder can be dispersed in water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

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

Various methods known in the field of silver halide photographic materials are used for preparing the monodispersed silver halide emulsion used in the present invention. For example, P. Glafkide
s) "Simimy Physik Photographic (C
himie et Physique Photograhieue ”(Paul Montel, 1967), GFDuffin,“ Photographic Emulsion Chemistry ”
ry) (The Focal Press) 1
966), VLZelikman et
al) “Making and Coating Photographic Emulsion”
tographic Emulsion) "(The Focal Press (Th
e Focal Press) (published in 1964).

The monodisperse emulsion of the present invention has a coefficient of variation of 20% or less,
Particularly preferably, it means a silver halide emulsion having a grain size distribution of 15% or less.

Where the coefficient of variation is Is defined as

The average grain size of the grains in a monodispersed silver halide emulsion is
0.5 μm or less, particularly preferably 0.1 μm to 0.4 μm
It is.

As a method of reacting a water-soluble silver salt (aqueous silver nitrate solution) with a water-soluble halogen salt, any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. As one form of the double jet method, pA in the liquid phase where silver halide is formed
A method of keeping g constant, that is, a control 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 tetra-substituted thiourea.

More preferred are tetrasubstituted thiourea compounds.
Nos. 53-82408 and 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione.

According to the control double jet method and the grain forming method using a silver halide solvent, it is easy to form a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is an effective means.

The monodispersed emulsion preferably has a regular crystal form such as a cubic, octahedral, or tetradecahedral, and particularly preferably a cubic.

In the silver halide grains, the inside and the surface layer may be composed of a uniform phase or may be composed of different phases.

The silver halide emulsion used in the present invention contains a cadmium salt during the formation or physical ripening of silver halide grains.
A sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof may coexist.

In the present invention, a silver halide emulsion particularly suitable as a light-sensitive material for line drawing and halftone dot formation is per mole of silver.
This is an emulsion prepared in the presence of 10 ^-8 to 10 ^-5 mol of an iridium salt or a complex salt thereof.

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

The iridium salt used here is a water-soluble iridium salt or iridium complex salt, for example, iridium trichloride,
Iridium tetrachloride, potassium hexachloroiridate (III), potassium hexachloroiridium (IV),
And ammonium hexachloroiridate (III).

The monodispersed emulsion of the present invention is preferably subjected to chemical sensitization, and known methods such as sulfur sensitization, reduction sensitization, and gold sensitization can be used, and these are used alone or in combination. A preferred chemical sensitization method is gold sulfur sensitization.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. Specific examples are U.S. Pat.Nos. 1,574,944 and 2,278,947.
No. 2,410,689, 2,728,668, 3,501,313,
No. 3,656,955. Preferred sulfur compounds are thiosulfates and thiourea compounds, and the pAg at the time of chemical sensitization is preferably 8.3 or less, more preferably 7.3 to 8.0. Moisar, Klein Gelat
The method using polyvinylpyrrolidone and thiosulfate in combination as reported by ine. Proc. Syme. 2nd, 301-309 (1970) also gives good results.

Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and iridium may be contained. Specific examples are U.S. Patent No. 2,448,060,
It is described in British Patent 618,061 and the like.

Gelatin is advantageously used as a binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives,
Graft polymer of gelatin and other polymers, albumin, protein hydroxyethyl cellulose such as casein,
Carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sugar derivatives such as sodium alginate, starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as imidazole and polyvinylpyrazole can be used.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

In the present invention, a sensitizing dye having an absorption maximum in the visible region described in JP-A-55-52050, pp. 45-53 (for example, a cyanine dye, a merocyanine dye, etc.) can also be added. As a result, spectral sensitization can be performed on the longer wavelength side than the intrinsic sensitivity region of silver halide.

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with sensitizing dye,
The emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and which exhibits supersensitization.

Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Rese
arch Disclosure) Volume 176 17643 (Issued December 1978) No. 23
It is described in section J on page IV.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitro Benzotriazoles, etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7 ) Tetrazaindenes), pentaazaindenes, etc .; as antifoggants or stabilizers such as benzenethiosulfonate, benzenesulfonate, benzenesulfonate, etc. It can be added known many compounds. Among these, benzotriazole (eg, 5-methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole) are preferred. Further, these compounds may be contained in the treatment liquid. Further, a compound capable of releasing an inhibitor during development described in JP-A-62-30243 can be contained for the purpose of stabilizing or preventing black spots.

The photographic light-sensitive material of the present invention can contain a developing agent such as a hydroquinone derivative or a phenidone derivative for various purposes such as a stabilizer and an accelerator.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chrome alum, chromium acetate, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, active vinyl compounds (1,3,5-triacryloyl) -Hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, etc.), etc. Can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, slipperiness improvement, emulsification / dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, high contrast For various purposes such as sensitization), various surfactants may be contained.

For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol) Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone, glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), and alkyl esters such as fatty acid esters of polyhydric alcohols. Agent: alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfo Acid salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl Anionic surfactants containing an acidic group such as a carboxy group, a sulfo group, a phospho group, a sulfate group or a phosphate group, such as phosphate esters; amino acids, aminoalkylsulfonic acids, aminoalkyl sulfate or phosphorus Amphoteric surfactants such as acid esters, alkyl betaines and amine oxides; alkylamine salts,
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

Particularly, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412.

It is preferable to use a fluorine-containing surfactant described in JP-A-60-80849 or the like for preventing static charge.

The photographic light-sensitive material of the present invention includes a hydroquinone derivative (a so-called DIR-) which releases a development inhibitor in a photographic emulsion layer or other hydrophilic colloid layer in accordance with the density of an image during development.
(Hydroquinone).

Examples thereof are U.S. Pat.No. 3,379,529 and U.S. Pat.
20,746, U.S. Patent 4,377,634, U.S. Patent 4,332,878
JP-A-49-129,536, JP-A-54-67,419, JP-A-56-153,336, JP-A-56-153,342, JP-A-59-27
No. 8,853, No. 59-90435, No. 59-90436, No. 59-13880
No. 8 and the like.

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

The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of dimensional stability. For example, use is made of a polymer having, as a monomer component, an alkyl (meth) acrylate, an alkoxyacryl (meth) acrylate, a glycidyl (meth) acrylate, or the like alone or in combination, or a combination thereof with acrylic acid, methacrylic acid, or the like. 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 salicylic acid, acetic acid, organic acids such as ascorbic acid and acrylic acid, maleic acid,
Examples thereof include polymers or copolymers having an acid monomer such as phthalic acid as a repeating unit. These compounds are described in JP-A-61-223834 and JP-A-61-228437.
Nos. 62-25745 and 62-55642 can be referred to. Among these compounds, particularly preferred are ascorbic acid as a low molecular compound, and a high molecular compound composed of an acid monomer such as acrylic acid and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene. It is a water-dispersible latex of a copolymer.

The emulsion used in the present invention is coated on a suitable support such as glass, acetic acid, cellulose film, polyethylene terephthalate film, paper, baryta coated paper, polyolefin coated paper.

To obtain ultra-high contrast and high sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or a US patent
There is no need to use a highly alkaline developer close to pH 13 described in 2,419,975, and a stable developer can be used.

That is, the silver halide light-sensitive material of the present invention contains 0.15 mol / or more of sulfite ion as a preservative, and has a pH of 10.5
With a developer having a pH of from about 12.3 to 12.3, particularly from 11.0 to 12.0, a negative image having a sufficiently high contrast can be obtained.

The developing agent used in the developing solution used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes in that good halftone dot quality can be easily obtained. Combinations of pyrazolidones or combinations of dihydroxybenzenes and p-aminophenols may be used.

As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
Although there are 2,5-dimethylhydroquinone and the like, hydroquinone is particularly preferred.

As the developing agents of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-4-pyrazolidone, 1-phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-
Methyl-3-pyrazolidone, 1-p-aminophenyl-
4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-
4,4-dimethyl-3-pyrazolidone and the like.

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

The developing agent is preferably used usually in an amount of 0.05 mol / to 0.8 mol /. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / to 0.5 mol /, and the latter is used in an amount of 0.06 mol / or less. preferable.

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

Alkaline agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic, and potassium phosphate tribasic.
Contains pH adjusters and buffers. The pH of the developer is set between 10.5-12.3.

Additives other than the above components include compounds such as boric acid and borax, and development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve Organic solvents such as hexylene glycol, ethanol and methanol: antifoggants such as indazole compounds such as 1-phenyl-5-mercaptotetrazole and 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole; Potato (black pepper) inhibitor: may further contain a color tone agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, and an amino compound described in JP-A-56-106244, if necessary. May be included.

The developer of the present invention contains a silver stain inhibitor as disclosed in JP-A-56-24,3.
The compound described in No. 47 can be used. Compounds described in Japanese Patent Application No. 60-109,743 can be used as a solubilizing agent to be added to the developer. Furthermore, compounds described in JP-A-60-93,433 or compounds described in Japanese Patent Application No. 61-28708 can be used as a pH buffer used in the developer.

As the fixing agent, those having a commonly used composition can be used. As a fixing agent, thiosulfates and thiocyanates, and organic sulfur compounds known to have an effect as a fixing agent can be used. The fixing solution may contain water-soluble aluminum (for example, aluminum sulfate, bright bun, etc.) as a hardener. Here, the amount of the water-soluble aluminum salt is usually 0.4 to 2.0 g-Al /. Further, a trivalent iron compound can be used as an oxidizing agent as a complex with ethylenediaminetetraacetic acid.

The development temperature is usually selected between 18 ° C and 50 ° C, but is more preferably between 25 ° C and 43 ° C.

(Examples) Next, the present invention will be described more specifically based on examples. The following formulation was used for the developer.

(Developer formulation) Hydroquinone 50.0 g N-methyl-p-aminophenol 0.3 g Sodium hydroxide 18.0 g 5-sulfosalicylic acid 30.0 g Boric acid 20.0 g Potassium sulfite 110.0 g Ethylenediaminetetraacetic acid disodium 1.0 g Potassium bromide 10.0 g 5 -Methylbenzotriazole 0.4 g 2-mercaptobenzimidazole-5-sulfonic acid
0.3 g Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2 g 6-Dimethylamino-1-hexanol 4.0 g Sodium toluenesulfonate 15.0 g Add water to adjust to 11 pH = 11.7 (add potassium hydroxide Example 1 (Preparation of Emulsion of the Present Invention) Emulsion A: 0.13 M aqueous silver nitrate solution and 1 × 10 5 per mol of silver
^An aqueous solution of a halogen salt containing 0.04 M potassium bromide and 0.09 M sodium chloride containing (NH ₄ ) ₃ RhCl ₆ , equivalent to ^-7 mol, was added to an aqueous gelatin solution containing sodium chloride at 45 ° C. with stirring. Minutes by double jet method,
Nucleation was performed by obtaining silver chlorobromide grains having an average grain size of 0.15 μm and a silver chloride content of 70 mol%. Subsequently, similarly, an aqueous solution of silver nitrate of 0.87 M, potassium bromide of 0.26 M,
A halogen salt aqueous solution containing 0.65 M sodium chloride was added by a double jet method over 20 minutes.

After that, 1 × 10 ⁻³ mol of K1 solution was added to perform conversion, washed with flocculation method according to a conventional method, added with 40 g of gelatin, adjusted to pH 6.5 and pAg 7.5, and further added thiosulfate per mol of silver. 5 mg sodium and 8 chloroauric acid
mg, and heated at 60 ° C for 60 minutes, subjected to chemical sensitization treatment,
150 mg of 1,3,3a, 7-tetrazaindene was added as a stabilizer. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.27 μm and a silver chloride content of 70 mol%. (Coefficient of variation
15%).

Emulsion B: 0.13M silver nitrate aqueous solution and 1 × 10
^An aqueous solution of a halogen salt containing 0.04 M potassium bromide and 0.09 M sodium chloride containing (NH ₄ ) ₃ RhCl ₆ corresponding to ^-7 mol, containing sodium chloride and 1,3-dimethyl-2-imidazolidinthione The mixture was added to an aqueous gelatin solution at 38 ° C. for 12 minutes with stirring by a double jet method to form silver chlorobromide grains having an average grain size of 0.15 μm and a silver chloride content of 70 mol%, thereby forming nuclei. Then likewise 0.
87M silver nitrate aqueous solution, 0.26M potassium bromide and 0.65M
Was added over 20 minutes by a double jet method of a halogen salt aqueous solution containing sodium chloride.

Thereafter, 1 × 10 ^-3 mol of KI solution was added to perform conversion, washed with water by a flocculation method according to a conventional method, added with 40 g of gelatin, adjusted to pH 6.5 and pAg 7.5, and further, thiosulfuric acid was added per mol of silver. 5 mg sodium and 8 chloroauric acid
mg, and heated at 60 ° C for 60 minutes, subjected to chemical sensitization treatment,
150 mg of 1,3,3a, 7-tetrazaindene was added as a stabilizer. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.27 μm and a silver chloride content of 70 mol%. (Coefficient of variation
Ten%).

Emulsion C Emulsion C was prepared in the same manner as Emulsion B, except that 1,8-dihydroxy-3,6-dithiaoctane was used as a silver halide solvent instead of 1,3-dimethyl-2-imidazolidinethione. . (Coefficient of variation 12%) Emulsion D: 0.13M silver nitrate aqueous solution and 1 × 10
^An aqueous solution of a halogen salt containing 0.052 M potassium bromide and 0.078 M sodium chloride containing (NH ₄ ) ₃ RhCl ₆ corresponding to ^-7 mol, containing sodium chloride and 1,3-dimethyl-2-imidazolidinthione The mixture was added to an aqueous gelatin solution at 45 ° C. for 12 minutes with stirring by a double jet method to obtain silver chlorobromide particles having an average particle size of 0.15 μm and a silver chloride content of 60 mol%, thereby forming nuclei. Then likewise
0.87M silver nitrate aqueous solution, 0.34M potassium bromide and 0.52M
A halogen salt aqueous solution containing M sodium chloride was added by a double jet method over 20 minutes.

Thereafter, 1 × 10 ^-3 mol of KI solution was added to perform conversion, washed with water by a flocculation method according to a conventional method, added with 40 g of gelatin, adjusted to pH 6.5 and pAg 7.5, and further, thiosulfuric acid was added per mol of silver. 5 mg sodium and 8 chloroauric acid
mg, and heated at 60 ° C for 60 minutes, subjected to chemical sensitization treatment,
150 mg of 1,3,3a, 7-tetrazaindene was added as a stabilizer. The resulting grains were cubic silver chlorobromide grains having an average grain size of 0.27 μm and a silver chloride content of 60 mol%. (Coefficient of variation
Ten%).

(Preparation of Comparative Emulsion) Emulsion E: 0.13 M silver nitrate aqueous solution and 1 × 10
^-7 mol of (NH ₄ ) ₃ RhCl ₆ containing 0.078 M potassium bromide and 0.052 M sodium chloride aqueous solution containing sodium chloride in a gelatin aqueous solution containing sodium chloride,
Nucleation was carried out by adding the mixture by stirring at 45 ° C. for 12 minutes by a double jet method to obtain silver chlorobromide grains having an average grain size of 0.15 μm and a silver chloride content of 70 mol%. Subsequently, a silver salt aqueous solution containing 0.87 M silver nitrate aqueous solution, 0.522 M potassium bromide and 0.348 M sodium chloride was similarly added by a double jet method over 20 minutes.

Thereafter, 1 × 10 ^-3 mol of KI solution was added to perform conversion, washed with water by a flocculation method according to a conventional method, added with 40 g of gelatin, adjusted to pH 6.5 and pAg 7.5, and further, thiosulfuric acid was added per mol of silver. 5 mg sodium and 8 chloroauric acid
mg, and heated at 60 ° C for 60 minutes, subjected to chemical sensitization treatment,
150 mg of 1,3,3a, 7-tetrazaindene was added as a stabilizer. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.27 μm and a silver chloride content of 40 mol%. (Coefficient of variation
11%).

(Emulsion F) Emulsion F was prepared in exactly the same manner as in Emulsion A, except that stirring was changed to change the degree of supersaturation during grain formation. (Emulsion G) Emulsion G was prepared in the same manner as Emulsion D, except that stirring was changed to change the degree of supersaturation during grain formation. (Coefficient of variation 25%) [Emulsion H] An aqueous solution of silver nitrate (1 mol) was added to an aqueous solution of gelatin maintained at 50 ° C. in the presence of ammonia at a concentration of 1.2 × 10 5
^An aqueous solution of potassium iodide and potassium bromide containing ^-7 mol of (NH ₄ ) ₃ RhCl ₆ was simultaneously added over 60 minutes, and the average pAg was maintained at 7.8 during the addition, whereby the average particle size was 0.25 μm and the average silver iodide content was 1%.
Mol% of a cubic monodispersed emulsion, desalting by flocculation method, adding 40 g of gelatin, pH = 6.0 pAg
= 8.5, sodium thiosulfate 5mg and chloroauric acid 6m
g, and heated at 60 ° C. for 60 minutes to perform chemical sensitization treatment, and 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer. (Coefficient of variation: 9%) Emulsions A to H are summarized in Table 1.

These emulsions were divided and used as sensitizing dyes in an amount of 1 × 10 ^-3 mol of 5- [3- (4-sulfobutyl)-/ mol of silver.
5-chloro-2-oxazolidylidene] -1-hydroxyethyl-3- (2-pyridyl) -2-thiohydantoin, and 2 × 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole, × 10 ^-4 mol of a short cyanine dye represented by the following structural formula (a), a water-soluble latex represented by ^{(b) (200mg / m 2} ) and a dispersion of polyethyl acrylate (200mg / m ²⁾ hardener 1,3-divinyl-sulfonyl-2-propanol (200 mg / m ² ),
The hydrazine compounds of the present invention were added as shown in Table 2.

(Preparation of Redox Compound-Containing Layer Emulsion) Emulsion A: 1.0 M silver nitrate aqueous solution and 3 × 10 ⁻⁷ per mol of silver
Containing (NH ₄ ) ₃ RhCl ₆ and 0.3 M potassium bromide
An aqueous halogen salt solution containing 0.74 M sodium chloride was added to sodium chloride and an aqueous gelatin solution containing 1,3-dimethyl-2-imidazolidinethione at 45 ° C. while stirring.
For 30 minutes by a double jet method to obtain silver chlorobromide grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. Thereafter, the mixture was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added to adjust the pH and pAg to 7.5. Further, 5 mg of sodium thiosulfate and 8 mg of chloroauric acid were added per 1 mol of silver, and the mixture was added at 60 ° C. for 60 minutes. Heated, subjected to chemical sensitization treatment, and 4-hydroxy-6-methyl-1,3,3
150 mg of a, 7-tetrazaindene was added. The obtained grains were silver chlorobromide cubic grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%).

This emulsion was divided and used as a sensitizing dye in an amount of 1 per mole of silver.
× 10 ^-3 mol of 5- [3- (4-sulfobutyl) -5-chloro-2-oxazolidylidene] -1-hydroxyethyl-3- (2-pyridyl) -2-thiohydantoin was added, and A dispersion of 2 × 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole and polyethyl acrylate was added to 50
mg / m ² , 1,2-bis (vinylsulfonylacetamido) ethane 40 mg / m ² , and the redox compound of the present invention were added as shown in Table 2.

Hydrazine content in the lowermost layer (Ag 3.6 g / m ² , gelatin 2 g /
m ² ) and a layer containing a redox compound (Ag 0.4 g / m ² , gelatin 0.5 g / m ² ) via an intermediate layer (gelatin 0.5 g / m ² ).
m ² ) and gelatin 1.0 g / m ² as a protective layer thereon, an amorphous SiO ₂ matting agent 40 mg / m ² having a particle size of about 3.5 μm, methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² ,
Hydroquinone 200 mg / m ² and silicone oil and fluorine surfactant represented by the following structural formula as a coating aid And a layer containing sodium dodecylbenzenesulfonate were simultaneously applied to prepare samples as shown in Table 2.

The back layer and the back layer protective layer were applied according to the following formulation.

(Back layer formulation)

Gelatin 3 g / m ² Latex Polyethyl acrylate 2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / m ² Dye Mixture of dyes [a], [b], and [c] Dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ² [Back protective layer] Gelatin 0.8 g / m ² Polymethyl methacrylate fine particles (average particle size 4.5
μ) 30 mg / m ² dihexyl-α-sulfosacnate sodium salt 15 mg
/ m ² dodecylbenzenesulfonic acid sodium salt 15 mg / m ² fluorinated surfactant 5 mg / m ² Sodium acetate 40mg / m ² FIG. 1 schematically shows the layer structure.

 The evaluation was performed by the following test method.

(Photo Characteristics) Photo characteristics 1 are the results obtained by performing a 30 ° C. treatment at 34 ° C. using the FG-660F automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) with the developer having the above formulation.

 GR-F1 was used as the fixing solution.

Photographic characteristic 2 is 100% blackened Fujiris Orthofilm GA
This is the result of processing in the same manner as in photographic characteristics 1 using a developing solution after processing 150 sheets of -100 large and all sizes (50.8 cm × 61 cm).

Here, the sensitivity is a relative value of the reciprocal of the exposure amount that gives a density of 1.5 in the development at 34 ° C. for 30 seconds.

Where γ is Defined by

〔image quality〕

1.Evaluation of enlargement image quality (1) Manuscript creation Monochrome scanner SCAN manufactured by Fuji Photo Film Co., Ltd.
Using ART30 and the special photosensitive material SF-100, a transmission image of a person consisting of halftone dots and a step wedge in which the halftone percentage was changed stepwise were created. At this time, the screen frequency was set to 150 lines / inch.

(2) Shooting After setting the original to the plate making camera C-440 manufactured by Dainippon Screen Co., Ltd. so that the magnification becomes equal, Xe
The evaluation sample was exposed by irradiating a lamp.

At this time, the exposure was performed such that 95% of the step wedge of the original became 5%. The filter of the present invention was installed between the original and the light source.

(3) Evaluation The gradation reproducibility (the difficulty of halftone dot collapse) of the shard part of the sample obtained by adjusting the exposure amount as in (2) and adjusting the halftone dot% on the small dot side (highlight part) Five-step evaluations (5-1) were performed in the order of good to bad.

2. Evaluation of image quality of line drawing A 7th class Mincho and Gojik typesetting original with reflection density in the range of 0.5 to 1.2 was photographed with a Dainippon Screen camera (DSC351), and the photograph characteristics were the same. Under the condition
This is the result of performing development processing (34 ° C., 30 ″).
Performed in five stages, "5" represents the best and "1" represents the worst quality. "5" or "4" is practical and "3" is bad, but practically available, "2" or "1" is practically impossible.

As is clear from Table 3, the sample of the present invention has a small fluctuation due to the processing and has good image quality. In particular, emulsions prepared using thiourea show better performance with smaller processing variations.

Example 2 (Preparation of Emulsion I of the Present Invention) Emulsion A: 0.13 M aqueous silver nitrate solution and 1 × 10 5 per mol of silver
^-7 mol of (NH ₄ ) ₃ RhCl ₆ and 2 × 10 ^-7 mol of K ₃ IrC
The halogen salt aqueous solution containing sodium chloride potassium bromide and 0.09M of 0.04M include l _6, and sodium chloride, 1,3
By adding to a gelatin aqueous solution containing dimethyl-2-imidazolidinthione by a double jet method at 38 ° C. for 12 minutes with stirring to obtain silver chlorobromide particles having an average particle size of 0.15 μm and a silver chloride content of 70 mol%. Nucleation was performed. Subsequently, similarly, a 0.87 M silver nitrate aqueous solution, a 0.26 M potassium bromide solution, and a halogen salt aqueous solution containing 0.65 M sodium chloride were added by a double jet method over 20 minutes. Thereafter, the mixture was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added to adjust the pH to 6.5 and pAg7.5. Heat, subject to chemical sensitization treatment, 1,3,3a, 7-tetrazaindene 15 as a stabilizer
0 mg was added. The resulting particles have an average particle size of 0.28μ
m, silver chlorobromide cubic grains having a silver chloride content of 70 mol%. (Coefficient of variation 10%).

Emulsion B and Emulsion I used in Example 1) were divided, and the same additives and layer constitutions as in Example 1 were used for Sample 31 as shown in Table 4.
~ 45 were made.

These samples were evaluated for photographic performance in the same manner as in Example 1. The results are shown in Table 5. As is evident from Table 5, all the samples show good results, but especially the sample containing the iridium compound gives good photographic performance.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a layer configuration of a light-sensitive material in Example-1.

Claims (5)

(57) [Claims] 1. A redox compound which releases a development inhibitor by being oxidized on a photosensitive silver halide emulsion layer containing at least one hydrazine derivative on a support, said emulsion layer or another hydrophilic colloid layer. Silver halide photographic light-sensitive material containing at least one silver halide emulsion layer is monodisperse grains having a silver chloride content of 50 mol% or more, gold-sulfur sensitized, and a dispersion coefficient of 20% or less. A negative silver halide photographic light-sensitive material, characterized in that: 2. A silver halide photographic material according to claim 1, wherein the silver halide emulsion is formed in the presence of a tetrasubstituted thiourea compound. 3. A silver halide photographic material according to claim 1, wherein the silver halide emulsion is formed in the presence of an iridium complex salt. 4. The halogen according to claim 1, wherein the redox compound has, as a redox group, hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines, and reductones. 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.