JP2604243B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide using a silver halide emulsion having a novel structure exhibiting excellent photographic characteristics. It relates to a photographic material.

BACKGROUND OF THE INVENTION Much work has been done over the years to obtain high image densities (Dmax) and high sensitivity with less silver in the study of silver halide photographic materials. Particularly in recent years, the need for rapid processing has increased, and it has become an important issue to reduce silver, that is, to obtain fine and highly sensitive emulsions, from the viewpoint of shortening the time for fixing, washing and drying.

On the other hand, in the field of photoengraving, the versatility of printed matter,
In order to cope with the complexity, there is a demand for a photographic light-sensitive material having good original reproducibility, a stable processing solution, or a simple replenishment.

Particularly in the line drawing photographing process, the manuscript is made by pasting typesetting characters, handwritten characters, illustrations, halftone pictures, and the like. Therefore, originals contain images having different densities and line widths, and there is a strong demand for a plate-making camera, a photographic photosensitive material, or an image forming method for finishing these originals with good reproducibility. On the other hand, in plate making of catalogs and large posters, enlargement (enlargement) or reduction (shrinkage) of a halftone picture is widely performed, and in plate making using enlarged 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, an image forming method having a wider latitude is required 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 the photographic sensitivity to these light sources, the 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.

As a system that meets the demands of a wide latitude, the effective concentration of sulphite ions in a lithographic silver halide photosensitive material composed of silver chlorobromide (at least silver chloride content of 50% or more) is extremely low (usually 0.1 mol / l 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 portion and a non-image portion 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, the surface latent image type silver halide photographic material to which a specific acylhydrazine compound is added contains a sulfurous acid preservative of 0.15 mol / l or more at pH 11.0 to 12.3, and has good storage stability. Is treated with a developing solution 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.

Although the above image system shows excellent performance in terms of sharp halftone dot quality, processing stability, quickness and original reproducibility, the original reproducibility has been further improved to cope with the variety of printed matter in recent years. A system is desired.

In a system containing hydrazine, silver iodide is introduced into silver halide grains for various purposes, and in addition to the above-mentioned patents, JP-A-61-29837, JP-A-62-55643, and JP-A-64-55643. −
No. 61744.

Silver halides having different halogen compositions with respect to host grains, emulsions containing silver halide grains grown epitaxially, U.S. Pat.No. 4,142,900,
4,463,087, 4,471,050, JP-A-59-119344,
59-119350, 55-163532, 56-27134, 5
Nos. 5,161,229, 58,108,526 and 62,7040. An example of converting the corner of a cubic grain having a silver chloride content of 90 mol% with silver bromide is as follows.
It is described in Japanese Patent Application No. 62-324567.

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.

(Problems to be Solved by the Invention) A first object of the present invention is to provide a silver halide photographic material having high sensitivity and high contrast.

A second object of the present invention is to provide a very high-sensitivity and ultra-hard silver halide photographic material excellent in line image quality and having a γ exceeding 10 using a stable developer.

(Means for Solving the Problems) An object of the present invention is to provide a support having at least one silver halide emulsion layer, wherein the silver halide emulsion has a thickness of 0.3 to 3.0.
In a silver halide photographic light-sensitive material comprising regular silver halide grains having an average grain size of 0.2 μm or more and less than 0.5 μm containing mol% of silver iodide, the silver halide grains transform the host emulsion grain crystals into total halide grains. Per silver particle
It is formed by conversion with a previously prepared ultrafine silver halide emulsion having a silver iodide content corresponding to 0.1 to 2.5 mol% silver iodide of 90 mol% or more and an average grain size of 0.1 μm or less. This has been achieved by a negative working silver halide photographic material.

On the other hand, the second object is characterized in that the emulsion layer or the other hydrophilic colloid layer of the photosensitive material contains a hydrazine derivative and a redox compound which releases a development inhibitor when oxidized. After exposing the negative-working silver halide photographic material to image exposure, 0.15 mol
This was achieved by developing with a developer having a pH of 10.5-12.3 containing sulfite ions of at least / l.

Hereinafter, the silver halide grains of the present invention will be described in detail. The halogen composition of the host crystal is preferably silver bromide or silver iodobromide. In the case of silver iodobromide, the silver iodide content is preferably 2.5 mol% or less, more preferably 1 mol%.
It is as follows. The halogen composition of the silver halide used in the conversion is preferably silver iodide, silver iodobromide, silver iodochlorobromide, or silver iodochloride having a silver iodide content of 90 mol% or more.
Silver iodide is particularly preferred.

The amount of silver iodide used for the conversion is an amount giving a silver iodide content of 0.1 mol% to 2.5 mol% with respect to all silver halide grains (host grains + conversion grains), and more preferably. 0.3 mol% to 1.5 mol%. If it is 3.0 mol% or more, black spots frequently occur, which is not preferable. The average silver iodide content in one grain of the converted silver halide grains (host grains + conversion grains) is 3 mol% or less, preferably 2.5 mol% or less, more preferably 0.5 mol% to 2.0 mol. %.

The average particle size of the host crystal in the present invention is 0.5 μm.
m, more preferably 0.2 μm or more and 0.5 μm
Is less than. The particle size distribution is preferably monodisperse.

The monodisperse grains as used herein mean a silver halide emulsion having a grain size distribution having a coefficient of variation defined below of 20% or less, particularly preferably 15% or less.

The particles of the present invention begin with the preparation of a regular host crystal. Cubic, tetradecahedral or octahedral grains can be prepared by adding an aqueous solution of a soluble silver salt and an aqueous solution of a soluble silver halide under a condition of a constant silver ion concentration.

Conversion particles can be introduced by simultaneously adding an aqueous solution of soluble iodide and an aqueous solution of a soluble silver salt corresponding to a predetermined number of moles to a tank containing a host crystal, or adding a previously prepared ultrafine grain emulsion having a silver iodide content of 90 mol% or more. By doing so, you can achieve it.

For the introduction of a fine grain emulsion prepared in advance, refer to Japanese Patent Application
It can be carried out using an apparatus as described in Japanese Patent Application Nos. 7851, 63-310651 and Japanese Patent Application No. 1-27172.

In the present invention, in order to further enhance the selectivity of silver iodide conversion, it is preferable to carry out the reaction in the presence of a compound having adsorptivity to silver halide represented by the following general formula (A).

 Hereinafter, the general formula (A) will be described in detail.

General formula (A) In the formula, Z ₁₁ and Z ₁₂ are thiazole nucleus, thiazoline nucleus, benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, benzoxazole nucleus, oxazoline nucleus, naphthoxazole nucleus, imidazole nucleus, benzimidazole nucleus, imidazoline nucleus, selenazole nucleus, A group of atoms necessary to form a selenazoline nucleus, a benzoselenazole nucleus or a naphthoselenazole nucleus.

R ₁₁ and R ₁₂ represent an alkyl group or a substituted alkyl group. However, at least one of R ₁₁ and R ₁₂ has a sulfo group or a carboxy group.

L ₁₁ and L ₁₂ represent a substituted or unsubstituted methane group.

 n represents the integer of 0-2.

The nucleus formed by Z ₁₁ and Z ₁₂ may have a substituent introduced therein, as is well known in the field of cyanine dyes. Examples of the substituent include an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an aralkyl group, and a halogen atom.

R ₁₁ and R ₁₂ may be the same or different.
The alkyl of R ₁₁ and R ₁₂ preferably has 1 to 1 carbon atoms.
And 8 such as methyl, ethyl, propyl, butyl, pentyl, heptyl and the like. Examples of the substituent of the substituted alkyl group include a carboxy group, a sulfo group, a cyano group, a halogen atom (such as a fluorine atom, a chlorine atom, and a bromine atom), a hydroxy group, and an alkoxycarbonyl group (having 8 or less carbon atoms, such as methoxycarbonyl). Group, ethoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group (having 7 or less carbon atoms, for example, methoxy group, ethoxy group, propoxy group, butoxy group,
A benzyloxy group or the like), an aryloxy group (for example, a phenoxy group, a p-tolyloxy group or the like), an acyloxy group (for example, having 3 or less carbon atoms, for example, an acetyloxy group or a propionyloxy group), or an acyl group (for example, having 8 or less carbon atoms). For example, acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N , N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.),
There are aryl groups (for example, phenyl group, p-hydroxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group, α-naphthyl group, etc.). The preferred carbon number of the substituted alkyl group is 6 or less.

Examples of the substituted methine group of L ₁₁ and L ₁₂ include a lower alkyl group (for example, a methyl group, an ethyl group, a propyl group and the like), a phenyl group, a benzyl group and the like.

The following are specific examples of cyanine dyes suitable for use in the present invention.

In the present invention, the compound of the general formula (A) is preferably added in an amount of 10 ^-6 to 10 ^-1 mol per mol of silver, more preferably 10 ^-4 to 10 ^-2 mol per mol of silver. is there.

The host crystal used in the present invention is Chim by P. Glafkides.
ie et Physique Photographique (published by Paul Montel, 1
967), Photographic Emulsion Chemis by GFDuffin
try (The Focal Press, 1966), VLZelikman e
t al Making and Coating Photographic Emulsion (T
he Focal Press, 1964) and the like.

That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt with a soluble halide may be any one of a one-sided mixing method, a double-sided mixing method, and a combination thereof. Good.

A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. PA in the liquid phase where silver halide is formed as a form of the double jet method.
A method of keeping g constant, that is, a so-called controlled,
The double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In order to make the particle size uniform, British Patent 1,
No. 535,016, JP-B-48-36890 and JP-B-52-16364, a method in which the addition rate of silver nitrate or alkali halide is changed according to the grain growth rate,
It is preferable to use a method of changing the concentration of the aqueous solution as described in JP-A-Sho 4,242,445 and JP-A-55-158124 to grow the solution quickly within a range not exceeding the critical saturation.

As the silver halide solvent used in the present invention, U.S. Patent Nos. 3,271,157, 3,531,289, and 3,574,628
(A) organic thioethers described in
(B) Thiourea derivatives described in JP-A-82408 and JP-A-55-77737; (c) Silver halide solvent having an oxygen or carbonyl group described in JP-A-53-144319;
(D) imidazoles (e) sulfites (f) thiocyanates described in JP-100717. Of these, thioethers are particularly preferred.

 The specific compounds are shown below.

HO- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -OH The silver halide emulsion used in the present invention contains a cadmium salt during the formation of silver halide grains or physical ripening.
A sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, and the like may coexist.

A silver halide particularly suitable for use in the present invention is prepared in the presence of 10 ^-8 to 10 ^-5 mol of an iridium salt or a complex salt thereof per mol of silver, and before completion of physical ripening in the production process of a silver halide emulsion. In particular, it is desirable to add the above amount of iridium salt at the time of particle formation.

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

The emulsion of the present invention may not be chemically sensitized, but may be. As the method of chemical sensitization, known methods such as sulfur sensitization, reduction sensitization, and gold sensitization can be used, and they are used alone or in combination. The preferred chemical sensitization method is 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
Symp. 2nd, 301-309 (1970), et al., using polyvinyl pyrrolidone and thiosulfate in combination 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.

Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer, and specific examples thereof are described in U.S. Pat. Nos. 2,487,850 and 2,518,6.
No. 98, 2,983,609, 2,983,610, and 2,694,637.

The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, those having chemical sensitization, Those with different conditions) may be used in combination.

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, a hydrazino group, a carbamoyl group or an oxycarbonyl group, G ₁ is a carbonyl group, a sulfonyl group, a sulfoxy group, Represents a thiocarbonyl group or an iminomethylene group; A ₁ and A ₂ are each a hydrogen atom or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted group; Represents a substituted 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. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. The alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, and a carbonamide group.

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 a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring.

Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, and an acylamino group. Group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group,
Alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group,
Sulfo group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group,
Acyloxy group, carbonamide group, sulfonamide group and carboxyl group, phosphoric acid amide group, diacylamino group, imide group, And the like. Preferred substituents are a straight-chain, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or 2-alkyl group having 1 to 3 carbon atoms in the alkyl portion). Ring), 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 20 carbon atoms) 30), a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), a phosphoric amide group (preferably having 1 to 30 carbon atoms) Things).

The alkyl group represented by R ₂ in the general formula (I) is preferably an alkyl group having 1 to 4 carbon atoms,
For example, halogen atom, cyano group, carboxy group, sulfo group, alkoxy group, phenyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfo group, arylsulfo group, sulfamoyl group, nitro group, heteroaromatic Ring group, And the like, and these groups may be further substituted.

As the aryl group, a monocyclic or bicyclic aryl group is preferable, and for example, those containing a benzene ring. The aryl group may be substituted, and examples of the substituent are the same as those in the case of the alkyl group.

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

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

As the amino group, an unsubstituted amino group and a group having 1 to 10 carbon atoms
Are preferred, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, or the like.

The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms, or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or an aryloxycarbonyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Among the groups represented by R ₂ , when G ₁ is a carbonyl group, a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl) Group, phenylsulfonylmethyl group, etc.), aralkyl group (for example, o
-Hydroxybenzyl group), an aryl group (for example,
Phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, etc.), and particularly preferably a hydrogen atom.

When G ₁ is a sulfonyl group, R ₂ represents an alkyl group (eg, a methyl group), an aralkyl group (eg, o
A hydroxyphenylmethyl group), an aryl group (e.g., a phenyl group) or a substituted amino group (e.g.,
And a dimethylamino group.

When G ₁ is a sulfoxy group, preferred R ₂ includes a cyanobenzyl group and a methylthiobenzyl group, and G ₁ is In the case of a group, R ₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, or a phenyl group, and particularly preferably a phenoxy group.

When G ₁ is an N-substituted or unsubstituted iminomethylene group,
Desirable R ₂ is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

As the substituent for R _2, the substituents listed for R ₁ can be applied.

G in the general formula (I) is most preferably a carbonyl group.

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 rise to cyclization reaction to form a cyclic structure containing a is such that it can specifically represented by the general formula (a).

In the general formula (a) -R ₃ -Z ₁ formula, Z ₁ is nucleophilically attacked to G _1, is a group capable of splitting the G ₁ -R ₃ -Z ₁ moiety from the remainder molecule, R ₃ than that removing one hydrogen atom from R _2, Z ₁ is a nucleophilic attack to G _1, G _1,
A cyclic structure can be formed by R ₃ and Z ₁ .

More specifically, Z ₁ is easily prepared when the hydrazine compound of the general formula (I) produces the next reaction intermediate by oxidation or the like.
G ₁ and nucleophilic reaction with _{R 1 -N = N-G 1} -R 3 -Z 1 R 1 -N = N group is a group capable of splitting from G _1, in particular OH, SH or NHR ₄ (R ₄ is a hydrogen atom, an alkyl group, an aryl group, —COR ₅ , or —SO ₂ R ₅ , and R ₅ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.), COOH, etc. It may be a functional group which reacts directly with G ₁ to _{(wherein, OH, SH, NHR 4,} -COOH is be temporarily protected so as to generate these groups by hydrolysis such as an alkali Good) or (R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group) and react with G ₁ by reacting with a nucleophile such as a hydroxide ion or a sulfite ion. It may be a functional group capable of performing the above.

The ring formed by G ₁ , R ₃ and Z ₁ is preferably a 5- or 6-membered ring.

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

General formula (b) Wherein, R ¹ _b ~R ⁴ _b represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), (those of preferably 2 to 12 carbon atoms) alkenyl group, an aryl group (preferably having a carbon number of 6 ~
12), which may be the same or different. B is an atom necessary to complete a 5- or 6-membered ring which may have a substituent, m and n are 0 or 1, and (n
+ M) is 1 or 2.

As the 5- or 6-membered ring formed by B, for example,
A cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and the like.

Z ₁ has the same meaning as in formula (a).

General formula (c) In the formula, R _C ¹ and R _C ² represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, or the like, and may be the same or different.

R _C ³ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

 p represents 0 or 1, and q represents 1-4.

R _C ¹ , R _C ² and R _C ³ may be bonded to each other to form a ring as long as Z ₁ is capable of intramolecular nucleophilic attack on G ₁ .

R _C ¹ and R _C ² are preferably a hydrogen atom, a halogen atom, or an alkyl group, and R _C ³ is preferably an alkyl group or an aryl group.

q preferably represents 1-3, p is 0 or 1 when q is 1, p is 0 or 1 when q is 2, p is 0 or 1 when q is 3, and q is 2 Or 3 for R _C ¹ , R
_C ² may be the same or different. Z ₁ has the same meaning as in formula (a).

A ₁ and A ₂ are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more) An acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more, or a straight-chain, branched or cyclic unsubstituted or substituted fatty acid; Group acyl group (for example, a halogen atom, an ether group, a sulfonamide group,
Examples thereof include a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group. )) 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-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.

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item23516 (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-
Nos. 294,562 and 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.

Examples of the redox group of the redox compound capable of releasing the development inhibitor by being oxidized for use in the present invention include hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines, Reductones and the like. As the redox group, hydrazines are preferable, and as the redox group, a compound represented by the following general formula (II) is particularly preferable.

General formula (II) (Wherein B ₁ and B ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a sulfinic acid residue or (Wherein R ₀ is an alkyl group, an alkenyl group, an aryl group,
Represents an alkoxy group or an aryloxy group;
Or 2 is represented. ). Time represents a divalent linking group, and t represents 0 or 1. PUG represents a development inhibitor. V is a carbonyl group, Sulfonyl group, sulfoxy group, (R ₁ represents an alkoxy group or an aryloxy group.) An iminomethylene group or a thiocarbonyl group. R represents an aliphatic group, an aromatic group or a heterocyclic group.

 Hereinafter, the general formula (II) will be described.

In the general formula (II), B ₁ and B ₂ represent a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or a substituent such that the sum of the substituent constants of Hammett is -0.5 or more) Phenylsulfonyl group, (R ₀ is preferably a straight-chain, branched or cyclic alkyl group, alkenyl group, or aryl group having 30 or less carbon atoms (preferably, the sum of the substituent constants of phenyl group or Hammett is-
A phenyl group substituted to be 0.5 or more), an alkoxy group (for example, an ethoxy group or the like), an aryloxy group (preferably a monocyclic group), and the like, and these groups may have a substituent. Examples of the substituent include the following. These groups may be further substituted.

For example, alkyl, aralkyl, alkenyl, alkynyl, alkoxy, aryl, substituted amino, acylamino, sulfonylamino, ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio Group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, albonamide group, sulfonamide group, nitro group, alkylthio Group, arylthio group, and the like. ), And the sulfinic acid residues represented by B ₁ and B ₂ specifically represent those described in US Pat. No. 4,478,928.

Further, B ₁ may form a ring by linking with the later of Time _t.

As B ₁ and B ₂ , a hydrogen atom is most preferred.

Time represents a divalent linking group, and may have a timing adjusting function. t represents 0 or 1, and when t = 0, it means that the PUG is directly bonded to V.

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.

As a divalent linking group represented by Time, a photographically useful group (PUG) is released by an intramolecular ring closure reaction of a p-nitrophenoxy derivative described in, for example, US Pat. No. 4,248,962 (Japanese Patent Application Laid-Open No. 54-145,135). US Patent No. 4,31
U.S. Pat. Nos. 4,330,617 and 4,446,216, which release PUG by an intramolecular ring closure reaction after ring opening described in U.S. Pat. Nos. 0,612 (JP-A-55-53,330) and 4,358,252.
U.S. Pat. No. 4,409,323, which releases PUG with the formation of an acid anhydride by an intramolecular ring-closure reaction of a carboxyl group of a succinic acid monoester or an analog thereof described in JP-A No. 4,483,919 and JP-A-59-121328; No. 4,421,845, Research Disclosure Magazine No. 21,228 (Dec. 1981
U.S. Pat. No. 4,416,977 (JP-A-57-135,944).
Quinomonomethane or an analog thereof by electron transfer via a double bond conjugated with an aryloxy or heterocyclic oxy group described in JP-A-58-209,736 and JP-A-58-209,738. U.S. Pat. No. 4,420,554 (JP-A-57-136,640) and JP-A-57-13.
No. 5,945, No. 57-188,035, No. 58-98,728 and No. 58
-209,737 PUG from the γ-position of the enamine by electron transfer of the portion having an enamine structure of the nitrogen-containing heterocyclic ring described in
Which release 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 described in JP-A-57-56,837; No. 4,146,396 (JP-A-52-909)
No. 32), JP-A-59-93,442, JP-A-59-75475, etc., which release PUG with generation of aldehydes; JP-A-51-146,828, JP-A-57-179,842; Id. 59-10
Those releasing PUG accompanied by decarbonization of the carboxyl group as described in JP 4,641; -O-COOCR ₂ has the structure R _b -PUG, those which release PUG with the formation of aldehydes and subsequent decarboxylation Release of PUG with formation of isocyanate described in JP-A-60-7,429; U.S. Pat. No. 4,438,1
No. 93, which releases PUG by a coupling reaction with an oxidized form of a color developer.

Specific examples of the divalent linking group represented by Time are also described in detail in JP-A-61-236,549 and Japanese Patent Application No. 63-98,803, but preferred specific examples are shown below. It is.

Here, (*) represents a site where Time _t PUG binds to V in the general formula (II), and (*)
(*) Indicates the site to which PUG binds.

T- (33) (*) - O-CH 2 - (*) (*) 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, 1996, published by Macmillan, p.344, p.346. Specifically, mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, mercaptopyrimidines, mercaptobenzimidazoles, mercaptobenzthiazoles, mercaptobenzoxazoles, mercaptothiadiazoles, benztriazoles, benzimidazoles, indazoles, Adenines, guanines, tetrazoles, tetraazaindenes, triazaindenes, mercaptoaryls and the like can be mentioned.

The development inhibitor represented by PUG may be substituted. Examples of the substituent include the following, but these groups may be further substituted.

For example, alkyl, aralkyl, alkenyl, alkynyl, alkoxy, aryl, substituted amino, acylamino, sulfonylamino, ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio Group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxycarbanyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carboxamide group, sulfonamide group and carboxyl group , A sulfooxy group, a phosphono group, a phosphinico group, a phosphoric amide group and the like.

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 main development inhibitors are shown below.

1 Mercaptotetrazole derivative (1) 1-phenyl-5-mercaptotetrazole (2) 1- (4-hydroxyphenyl) -5-mercaptotetrazole (3) 1- (4-aminophenyl) -5-mercaptotetrazole (4) 1- (4-carboxyphenyl) -5-mercaptotetrazole (5) 1- (4-chlorophenyl) -5-mercaptotetrazole (6) 1- (4-methylphenyl) -5-mercaptotetrazole (7) 1- ( 2,4-dihydroxyphenyl) -5-mercaptotetrazole (8) 1- (4-sulfamoylphenyl) -5-mercaptotetrazole (9) 1- (3-carboxyphenyl) -5-mercaptotetrazole (10 ) 1- (3,5-dicarboxyphenyl) -5-mercaptotetrazole (11) 1- ( 4-methoxyphenyl) -5-mercaptotetrazole (12) 1- (2-methoxyphenyl) -5-mercaptotetrazole (13) 1- [4- (2-hydroxyethoxy) phenyl] -5-mercaptotetrazole ( 14) 1- (2,4-dichlorophenyl) -5-mercaptotetrazole (15) 1- (4-dimethylaminophenyl) -5-mercaptotetrazole (16) 1- (4-nitrophenyl) -5-mercapto Tetrazole (17) 1,4-bis (5-mercapto-1-tetrazolyl) benzene (18) 1- (α-naphthyl) -5-mercaptotetrazole (19) 1- (4-sulfophenyl) -5-mercaptotetrazole ( 20) 1- (3-sulfophenyl) -5-mercaptotetrazole (21) 1- (β-naphthyl) -5-mercaptothesol (22 ) 1-methyl-5-mercaptotetrazole (23) 1-ethyl-5-mercaptotetrazole (24) 1-propyl-5-mercaptotetrazole (25) 1-octyl-5-mercaptotetrazole (26) 1-dodecyl-5 -Mercaptotetrazole (27) 1-cyclohexyl-5-mercaptotetrazole (28) 1-palmityl-5-mercaptotetrazole (29) 1-carboxyethyl-5-mercaptotetrazole (30) 1- (2,2-diethoxyethyl) ) -5-Mercaptotetrazole (31) 1- (2-aminoethyl) -5-mercaptotetrazole hydrochloride (32) 1- (2-Diethylaminoethyl) -5-mercaptotetrazole (33) 2- (5-mercapto- 1-tetrazole) ethyltrimethylammonium chloride (34 1- (3-phenoxyethanol carbonyl phenylalanine) -5
-Mercaptotetrazole (35) 1- (3-maleimidophenyl) -6-mercaptotetrazole 2 mercaptotriazole derivative (1) 4-phenyl-3-mercaptotriazole (2) 4-phenyl-5-methyl-3-mercapto Triazole (3) 4,5-diphenyl-3-mercaptotriazole (4) 4- (4-carboxyphenyl) -3-mercaptotriazole (5) 4-methyl-3-mercaptotriazole (6) 4- ( 2-dimethylaminoethyl) -3-mercaptotriazole (7) 4- (α-naphthyl) -3-mercaptotriazole (8) 4- (4-sulfophenyl) -3-mercaptotriazole (9) 4- (3-nitrophenyl ) -3-mercaptotriazole 3 mercaptoimidazole derivative ( 1) 1-phenyl-2-mercaptoimidazole (2) 1,5-diphenyl-2-mercaptoimidazole (3) 1- (4-carboxyphenyl) -2-mercaptoimidazole (4) 1- (4-hexylcarbamoyl) ) -2-mercaptoimidazole (5) 1- (3-nitrophenyl) -2-mercaptoimidazole (6) 1- (4-sulfophenyl) -2-mercaptoimidazole 4 mercaptopyrimidine derivative (1) thiouracil (2) methylthiouracil ( 3) ethylthiouracil (4) propylthiouracil (5) nonylthiouracil (6) aminothiouracil (7) hydroxythiouracil 5 mercaptobenzimidazole derivative (1) 2-mercaptobenzimidazole (2) 5-carboxy-2 -Mercapto Benz Midazole (3) 5-amino-2-mercaptobenzimidazole (4) 5-nitro-2-mercaptobenzimidazole (5) 5-chloro-2-mercaptobenzimidazole (6) 5-methoxy-2-mercaptobenzimidazole ( 7) 2-mercaptonaphthimidazole (8) 2-mercapto-5-sulfobenzimidazole (9) 1- (2-hydroxyethyl) -2-mercaptobenzimidazole (10) 5-caproamide-2-mercaptobenzimidazole (11) ) 5- (2-Ethylhexanoylamino) -2-mercaptobenzimidazole 6 mercaptothiadiazole derivative (1) 5-methylthio-2-mercapto-1,3,4-thiadiazole (2) 5-ethylthio-2-mercapto- 1,3,4-thiadiazole (3) 5- 2-dimethylaminoethylthio) -2-mercapto-1,3,4-thiadiazole (4) 5- (2-carboxypropylthio) 2-mercapto-1,3,4-thiadiazole (5) 2-phenoxy Carbonylmethylthio-5-mercapto-1,3,4-thiadiazole 7 Mercaptobenzthiazole derivative (1) 2-mercaptobenzthiazole (2) 5-nitro-2-mercaptobenzthiazole (3) 5-carboxy-2-mercaptobenz Thiazole (4) 5-Sulfo-2-mercaptobenzothiazole 8 Mercaptobenzoxazole derivative (1) 2-mercaptobenzoxazole (2) 5-Nitro-2-mercaptobenzoxazole (3) 5-carboxy-2-mercaptobenzoxazole (4) 5-sulfo-2-mercaptobenzo Xazole 9 benztriazole derivative (1) 5,6-dimethylbenzotriazole (2) 5-butylbenzotriazole (3) 5-methylbenzotriazole (4) 5-chlorobenzotriazole (5) 5-bromobenzotriazole (6) 5,6-dichlorobenzotriazole (7) 4,6-dichlorobenzotriazole (8) 5-nitrobenzotriazole (9) 4-nitro-6-chloro-benzotriazole (10) 4,5,6-trichlorobenzotriazole (11) 5-carboxybenzotriazole (12) 5-sulfobenzotriazole Na salt (13) 5-methoxycarbonylbenzotriazole (14) 5-aminobenzotriazole (15) 5-butoxybenzotriazole (16) 5-ureidobenzo Triazole (17) Benzotriazole (18) 5-phenoxycarbonylbenzotriazole (19) 5- (2,3-dichloropropyloxycarbonyl) benzotriazole 10 benzimidazole derivative (1) benzimidazole (2) 5-chlorobenzimidazole (3) 5-nitrobenzimidazole (5) 5-n-butylbenzimidazole (5) 5-methylbenzimidazole (6) 4-chlorobenzimidazole (7) 5,6-dimethylbenzimidazole (8) 5-nitro-2- (trifluoromethyl) Benzimidazole 11 Indazole derivative (1) 5-nitroindazole (2) 6-nitroindazole (3) 5-aminoindazole (4) 6-aminoindazole (5) Indazole (6) 3-nitroindazole (7) 5-nitro -3-Chloroindazole (8 3-chloro-5-nitroindazole (9) 3-carboxy-5-nitroindazole 12 tetrazole derivative (1) 5- (4-nitrophenyl) tetrazole (2) 5-phenyltetrazole (3) 5- (3-carboxy) (Phenyl) -tetrazole 13 tetrazaindene derivative (1) 4-hydroxy-6-methyl-5-nitro-1,3,
3a, 7-Tetraazaindene (2) 4-mercapto-6-methyl-5-nitro-1,3,3
3a, 7-Tetraazaindene 14 mercaptoaryl derivative (1) 4-nitrothiophenol (2) thiophenol (3) 2-carboxythiophenol V is a carbonyl group, Sulfonyl group sulfoxy group, (R ₁ represents an alkoxy group or an aryloxy group.), An iminomethylene group, or a thiocarbonyl group, and V is preferably a carbonyl group.

The aliphatic group represented by R is a linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group;
The preferred number of carbon atoms is 1 to 30, especially 1 carbon atoms.
~ 20 things. Here, the branched alkyl group has 1
It may be cyclized to form a saturated heterocycle containing one or more heteroatoms.

For example, methyl group, t-butyl group, n-octyl group, t
-Octyl, cyclohexyl, hexenyl, pyrrolidyl, tetrahydrofuryl, n-dodecyl and the like.

The aromatic group is a monocyclic or bicyclic aryl group, such as a phenyl group and a naphthyl group.

The heterocyclic group is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O and S atoms, which may be a single ring or further condensed with another aromatic or heterocyclic ring. A ring may be formed. Preferred as the hetero ring are 5- or 6-membered aromatic hetero rings such as pyridine ring, imidazolyl group, quinolinyl group, benzimidazolyl group, pyrimidinyl group, pyrazolyl group, isoquinolinyl group, benzothiazolyl group, thiazolyl group and the like. Is mentioned.

R may be substituted with a substituent. Examples of the substituent include the following. These groups may be further substituted.

For example, alkyl, aralkyl, alkenyl, alkynyl, alkoxy, aryl, substituted amino, acylamino, sulfonylamino, ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio Group, sulfotyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group and carboxy group And a phosphoric amide group.

In the general formula (II), R or Time _t PUG
May incorporate therein a ballast group commonly used in immobile photographic additives such as couplers or a group which promotes adsorption to silver halide.

The ballast group is an organic group giving a molecular weight sufficient to prevent the compound represented by the general formula (II) from substantially diffusing into another layer or the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, It comprises one or more combinations of ether groups, thioether groups, amide groups, ureido groups, urethane groups, sulfonamide groups 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.

Hereinafter, specific examples of the compound used in the present invention will be described, but the present invention is not limited thereto.

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 1.0 × 10 ^{−6 to} 5.0 × 10 ⁻² mol, preferably 1.0 × 10 ⁻⁵ to 1 × 10 ⁻⁶ mol per mol of silver halide.
It is used within the range of 1.0 × 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 the well-known emulsification dispersion method, it is dissolved in an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate using an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified. A dispersion can also be prepared 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.

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, sodium alginate, sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl prolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, Various kinds of synthetic hydrophilic high molecular substances such as a single or copolymer such as polyvinylimidazole 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, in addition to the general formula (A), JP-A-55-52
Sensitizing dyes having an absorption maximum in the visible region described in 050, pages 45 to 53 (for example, cyanine dyes, merocyanine dyes, 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,
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 may be contained in the emulsion.

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 benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, 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 may 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 (mucochlores, etc.), etc. They 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 taurates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphorus 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 acid esters; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfate or phosphoric acid Amphoteric surfactants such as esters, alkyl betaines, and amine oxides; alkyl amine 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 fluorinated surfactant described in JP-A-60-80849 or the like for antistatic.

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.

In order to obtain ultra-high contrast and high sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, it is necessary to use a conventional infectious developer or a highly alkaline developer close to pH 13 described in U.S. Patent No. 2,419,975. And a stable developer can be used.

That is, the silver halide light-sensitive material of the present invention contains sulfite ions as a preservative in an amount of 0.15 mol / l or more, and has a pH of 10.5 to
With a developer having a pH of 12.3, particularly pH 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.

It is preferable that the developing agent is generally used in an amount of 0.05 mol / l to 0.8 mol / l. In addition, dihydroxybenzels and 1-
When a combination with phenyl-3-pyrazolidones or p-amino-phenols is used, the former is used in an amount of 0.05 mol / l to
It is preferred to use 0.5 mol / l and the latter in an amount of 0.06 mol / l or less.

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 sulfite is preferably at least 0.15 mol / l, particularly preferably at least 0.5 mol / l. The upper limit is preferably up to 2.5 mol / l.

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 / l. Further, a trivalent iron compound can be used as a complex with ethylenediaminetetraacetic acid as an oxidizing agent.

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 developer used in Example 1 used the following formulation.

(Developer formulation) Hydroquinone 45.0 g (N-methyl-p-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 18.0 g Potassium hydroxide 55.0 g 5-Sulfosalicylic acid 45.0 g Boric acid 25.0 g Potassium sulfite 110.0 g Ethylenediamine Disodium acetate salt 1.0 g Potassium bromide 6.0 g 5-methylbenzotriazole 0.6 g n-butyldiethanolamine 15.0 g 1 (pH = 11.6) by adding water (Example 1) Emulsions a to d was prepared.

(Emulsion a) A mixed aqueous solution of potassium iodide and potassium bromide and an aqueous solution of silver nitrate were added to a gelatin aqueous solution containing 1,8-dihydroxy-3,6-dithiaoctane at 75 ° C. for 15 minutes under vigorous stirring.
= 8.0 to obtain a monodispersed, octahedral silver iodobromide emulsion having an average grain size of 0.22 μm and an iodine content of 6 mol%. Using this silver iodobromide emulsion as a core, an aqueous solution of potassium bromide containing 10 ^-7 mol of K ₃ IrCl ₆ per mol of Ag and an aqueous solution of silver nitrate were added so that pAg = 7.4. I got The emulsion was desalted according to a conventional method, and 2 × 10 ^-4 mol of sensitizing dye A-25 per mol of silver was used.
And 1.9 × 10 ^-5 mol of sodium thiosulfate and 1.2 × 10 ^-5 mol of chloroauric acid per mol of silver were added.
Degrees were chemically sensitized for 70 minutes. 30 ml per mole of silver of a 1% solution of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer and proxel as a preservative, and finally an average silver iodide content 1.5
A 0.40 .mu.m mol% monodisperse emulsion was obtained. (Coefficient of variation 10
%) (Emulsion b) In the same manner as in the preparation method of Emulsion A, except that a monodisperse, octahedral core silver iodobromide emulsion having an average grain size of 0.22 μm and an iodine content of 4 mol% was obtained, finally, A monodisperse emulsion having an average silver iodide content of 1.0 mol% and an average grain size of 0.40 μm was obtained.
(Coefficient of variation 9%) (Emulsion c) A mixed aqueous solution of potassium iodide and potassium bromide and an aqueous solution of silver nitrate were added to an aqueous gelatin solution containing 1,8-dihydroxy-3,6-dithiaoctane at 75 ° C. under vigorous stirring. PA per minute
It was added while controlling so that g = 8.0 to obtain a monodispersed, octahedral silver iodobromide emulsion having an average particle size of 0.20 μm and an iodine content of 4 mol%. Using this silver iodobromide emulsion as a core, an aqueous solution of potassium bromide containing 10 ^-7 mol of K ₃ IrCl ₆ per mol of Ag and an aqueous solution of silver nitrate were added so that pAg = 7.4.
A shell silver iodobromide emulsion was obtained. After desalting this emulsion according to a conventional method, 2 × 10 ^-4 mol of sensitizing dye (A-25) was added per 1 mol of silver at 50 ° C., and grains corresponding to 5 × 10 ^-3 mol were added. A silver iodide emulsion prepared in advance having a size of 0.04 μm was added thereto, and after stirring for 10 minutes, 1.9 × 10 ⁻⁵ mol of sodium thiosulfate and 1.2 × 10 ⁻⁵ mol of chloroauric acid per mol of silver were added, and at 65 ° C. Chemical sensitization was applied for 70 minutes. 30 ml per mol of silver of a 1% solution of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer and proxel as a preservative were added to give an average silver iodide content of 1.5%. A monodisperse emulsion having a mol% of 0.40 μm in average grain size (coefficient of variation: 9%) was obtained.

(Emulsion d) Except for reducing the amount of 1,8-dihydroxy-3,6-dithiaoctane in Emulsion c to prepare a monodispersed, octahedral silver iodobromide emulsion having an iodine content of 4 mol% of 0.18 μm. In the same manner, a monodispersed emulsion having an average silver iodide content of 1.5 mol% and an average grain size of 0.37 μm was finally obtained. (Coefficient of variation: 9%) 1-phenyl-5-mercaptotetrazole as an antifoggant was 25 mg per mol of silver, and hydroquinone was 150 m.
g / m ² , polyethyl acrylate latex as a plasticizer, a gelatin binder ratio of 25%, 2-bis (vinylsulfonylacetamide) ethane as a hardener, 80 mg / m ² ,
2,4-dichloro-6-hydroxy-s-triazine 40 mg /
m ^2, and the mixture was coated to a silver 4.5 g / m ² on a polyester support. Gelatin was 4.7 g / m ² .

On top of this, gelatin 0.7g / m ² , particle size 3 ~
4μ polymethyl methacrylate 60mg / m ² , particle size 10-20m
μ colloidal silica 70 mg / m ² , silicone oil 100 mg
/ m ² , dodecylbenzenesulfonic acid sodium salt as a coating aid, proxel and phenoxyethanol as preservatives, a protective layer upper layer to which a fluorine-based surfactant having the following structural formula was added, and Gelatin 0.9 g / m ² , polyethyl acrylate latex 2
The lower layer of the protective layer to which 25 mg / m ² and sodium dodecylbenzenesulfonate as a coating aid were added was simultaneously coated.

The base used in this example has a back layer and a back protective layer having the following composition (both contain proxel and phenoxyethanol as preservatives).

(Back layer) Gelatin 3.9 g / m ² Sodium dodecylbenzene sulfonate 80 mg / m ² Dye 80 mg / m ² 〃 30 mg / m ² 〃 150 mg / m ² 1,3-Divinylsulfonyl-2-propanol 80 mg / m ² Polyvinyl Potassium benzenesulfonate 30mg / m ² (Back protective layer) Gelatin 0.75 g / m ² Polymethyl methacrylate (particle size 4.7μ) 30mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² Fluorine-based surfactant (the compound) 2 mg / m ² silicone oil 100mg / m ^{2 The} obtained samples 1 to 4 were exposed through a light wedge with a W light source, and developed at 34 ° C. for 30 seconds with the above-mentioned developer to obtain sensitivity, γ, and Dmax.
Was evaluated. The sensitivity was represented by the relative value of the reciprocal of the exposure amount giving a density of 1.5, and the value of Sample 1 was set to 100. Table 1 shows the results. As is clear from Table 1, Samples 3 and 4 of the present invention have high sensitivity, γ and Dmax, and show good performance.

Example 2 Emulsions A to G were prepared as shown below.

[Emulsion A]

Gelatin aqueous solution maintained at 50 ° C (gelatin concentration 3.5%) 8
In the presence of ammonia in 00 cc, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were added simultaneously for 60 minutes, and the pAg
Was maintained at 7.8 to prepare a cubic monodisperse silver bromide emulsion having an average grain size of 0.28 μm (coefficient of variation: 10%).

The emulsion was cooled to 40 ° C., desalted by flocculation, and further treated with gelatin, KBr aqueous solution (p
Ag was adjusted to 9.0), and phenoxyethanol was added as a preservative. Thereafter, the temperature was raised to 50 ° C., 5 × 10 ⁻⁴ mol of compound A-13 was added as a sensitizing dye per mol of silver, and after 5 minutes, a KI solution of 10 ⁻³ mol per mol of silver was added. Ten
After a lapse of minutes, conversion was performed, and then the temperature was lowered.

[Emulsion B]

In Emulsion A, 5 instead of 10 ^-3 mole per mole of silver
Emulsion B was prepared in exactly the same way, except that a × 10 ^-3 molar KI solution was added.

[Emulsion C]

Gelatin aqueous solution maintained at 50 ° C (gelatin concentration 3.5%) 8
In the presence of ammonia in 00 cc, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were added simultaneously for 60 minutes, and the pAg
Was maintained at 7.8 to prepare a cubic monodisperse silver bromide emulsion having an average grain size of 0.28 μm (coefficient of variation: 10%).

The emulsion was cooled to 40 ° C., desalted by flocculation, and further treated with gelatin, KBr aqueous solution (p
Ag was adjusted to 9.0), and phenoxyethanol was added as a preservative. Thereafter, the temperature was raised to 50 ° C., and 5 × 10 ⁻⁴ mol of compound A-13 was added as a sensitizing dye per mol of silver, and after 5 minutes, an aqueous solution of silver nitrate corresponding to 10 ⁻³ mol per mol of silver was added. (Concentration 1%) and a KI solution (concentration 1%) were added simultaneously to perform conversion.

[Emulsion D]

Emulsion D was prepared in exactly the same manner as in Emulsion C except that an aqueous solution of silver nitrate and a KI solution equivalent to 3 × 10 ⁻² mol were added instead of 5 × 10 ⁻³ mol per mol of silver.

[Emulsion E]

In Emulsion C, instead of simultaneously adding an aqueous silver nitrate solution and an KI solution equivalent to 5 × 10 ⁻³ mol per mol of silver, a silver iodide prepared in advance having a grain size of 0.04 μ corresponding to 5 × 10 ⁻³ mol was used. Emulsion E was prepared in exactly the same manner except that the emulsion was added.

[Emulsion F]

Emulsion F was prepared in exactly the same manner as in Emulsion E, except that 1 × 10 ⁻² mol of silver iodide emulsion was added instead of adding 5 × 10 ⁻³ mol of silver iodide emulsion. .

[Emulsion G]

Emulsion G was prepared in exactly the same manner as in Emulsion E except that 3 × 10 ⁻² mol of silver iodide emulsion was added instead of adding 5 × 10 ⁻³ mol of silver iodide emulsion.

 The characteristics of each of the emulsions A to G are summarized in the following table.

To this emulsion were added 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 5-methylbenzotriazole, and the following compounds (a) and (b) as stabilizers at 5 mg / each.
was added such that the m ² coating.

As a hydrazine compound, 5 × 10 ⁻⁵ mol of I-19 and 1 × 10 ⁻⁴ mol of I-5) per mol of silver were added, and polyethylene glycol having an average molecular weight of 600 was further added to 75 mg / m ^2. Then, a dispersion of polyethyl acrylate was added to a polyethylene terephthalate film so as to have a silver content of 3.5 g / m ² by adding a solid content to a gelatin ratio of 30% by weight and 1,3-divinylsulfonyl-2-propanol as a hard film. (Gelatin 2 g / m ² ) On top of this, gelatin 1.2 g / m ² as a protective layer,
Amorphous SiO ₂ matting agent with particle size of about 3μ 40mg / m ² , methanol silica 0.1g / m ² , polyacrylamide 100mg / m
m ² , 200 mg / m ^{2 of} hydroquinone and silicone oil, proxel and phenoxyethanol as preservatives, and a fluorine surfactant represented by the following structural formula as a coating aid And an amount containing sodium dodecylbenzenesulfonate were simultaneously applied to prepare Samples 5 to 11 as shown in Table 2.

 The back layer was applied according to the following formulation.

(Back layer formulation)

Gelatin 4g / m ² Matting agent polymethyl methacrylate (particle size 3.0~4.0μ) 10mg / m ² latex polyethyl acrylate 2 g / m ² Surfactant p- dodecyl benzene sulfonic acid sodium 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 Proxel and phenoxyethanol were added as preservatives to the back layer coating solution.

The evaluation in each example was performed by the following test method.

Test method 1. Evaluation of enlargement image quality (1) Preparation of manuscript Fuji Photo Film Co., Ltd. monochrome scanner-SCAN
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) Photographing The above-mentioned original was set on a plate making camera C-440 manufactured by Dainippon Screen Co., Ltd. so that the magnification was equal, and then the Xe lamp was irradiated to expose the evaluation sample to exposure.

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 A sample with good halftone reproducibility (the difficulty of halftone dot collapse) of the shard part of the sample adjusted to the halftone dot percentage on the small dot side (highlight part) adjusted in exposure amount as in (2). , A five-step evaluation (5-1) was performed in order.

2. Evaluation of copy dots (1) Creation of manuscript Fuji Photo Film Co., Ltd. monochrome scanner-SCAN
ART30 and special paper SP-100WP were used to make a step wedge with a step change of net percent. The exposure was performed with a screen ruling of 150 lines and 1 inch.

(2) Photographing The original and the sample were set at predetermined positions on a plate making camera C-690 (Auto Companica) manufactured by Dainippon Screen Co., Ltd., and an Xe lamp was irradiated on the reflective original to photograph.

At this time, the exposure time is 80% of the step wedge on the original
Was adjusted to be 10% on the sample. In addition, the filter of this invention was installed before the light source.

(3) Evaluation The exposure time was adjusted as described in (2), and the sample whose dot percentage on the small dot side was 10% had good gradation reproducibility (the difficulty of dot collapse) of the shadow portion was evaluated as 5, A five-step relative evaluation was performed with the bad one as one.

The obtained sample was exposed with a xenon light source, and a developer and a fixer, GR-D1, manufactured by Fuji Photo Film Co., Ltd. were used.
Using GR-F1 and an automatic developing machine FG-660F, development was performed at 34 ° C. for 30 seconds, and the drawing performance and copy dot performance were evaluated.

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.

 Dmax was indicated by a density corresponding to Dmax of the practical skill.

(On the characteristic curve, logE +
Density at 0.5 exposure) Example 3 Emulsions (H) to (N) were prepared as shown below.

[Emulsion H]

Gelatin aqueous solution maintained at 50 ° C (gelatin concentration 3.5%) 8
Silver nitrate aqueous solution and silver 1 in the presence of ammonia
An aqueous solution of potassium iodide and potassium bromide containing 4 × 10 ⁻⁷ mol / mol Ag of K ₃ IrCl ₆ per mol was simultaneously added over 60 minutes, and the average particle size was 0.28 A cubic monodispersed silver iodobromide emulsion having a μ and a silver iodide content of 0.5 mol% (coefficient of variation: 10%) was prepared.

The emulsion was cooled to 40 ° C., desalted by flocculation, and further treated with gelatin, KBr aqueous solution (p
Ag was adjusted to 9.0), and phenoxyethanol was added as a preservative. Thereafter, the temperature was raised to 50 ° C., and compound A-13 as a sensitizing dye was added in an amount of 5 × 10 ⁻⁴ mol per mol of silver, and after 5 minutes, a KI solution of 10 ⁻³ mol per mol of silver was added. ,
The mixture was allowed to age for 10 minutes, and the temperature was lowered. (Total AgI content 0.6 mol%) [Emulsion I] In Emulsion H, 5 instead of 10 ^-3 mol per mol of silver was used.
An emulsion was prepared in exactly the same manner except that a × 10 ⁻³ mol KI solution was added. (Total AgI content 1.0 mol%) [Emulsion J] particles an aqueous silver nitrate solution and KI solution corresponding to 5 × 10 ^-3 mol per 1 mol of silver in the emulsions H, corresponding to 5 × 10 ^-3 mol, instead of adding simultaneously Emulsion J was prepared in the same manner except that a previously prepared silver iodide emulsion having a size of 0.04 μm was added. (Total AgI content: 1.0 mol%) [Emulsion K] Aqueous gelatin solution maintained at 50 ° C. (gelatin concentration: 3.5%) 8
In the presence of ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were added at the same time in the presence of ammonia for 60 minutes.
By maintaining the g at 8.2, a tetrahedral monodispersed silver iodobromide emulsion having an average grain size of 0.3 μm (coefficient of variation 10%) was prepared.

The emulsion was cooled to 40 ° C., desalted by flocculation, and further treated with gelatin, KBr aqueous solution (pAg
Was adjusted to 9.0), and phenoxyethanol was added as a preservative. Thereafter, the temperature was raised to 50 ° C., 5 × 10 ⁻⁴ mol of compound A-13 was added as a sensitizing dye per mol of silver, and after 5 minutes, a KI solution of 10 ⁻³ mol per mol of silver was added. The mixture was allowed to age for 10 minutes, and the temperature was lowered.

[Emulsion L]

5% instead of 10 ^-3 mole per mole silver in emulsion K
Emulsion L was prepared in exactly the same manner except that a × 10 ⁻³ mol KI solution was added. (Total AgI content: 0.5 mol%) [Emulsion M] In the emulsion K, a KI solution corresponding to 1 × 10 ⁻³ mol per mol of silver was added at the same time, and instead, a particle size of 0.04 μm corresponding to 1 × 10 ⁻³ mol was used. Emulsion M was prepared in exactly the same manner except that the previously prepared silver iodide emulsion was added. (Total AgI content: 0.1 mol%) [Emulsion N] In the emulsion K, the silver nitrate aqueous solution and the KI solution corresponding to 5 × 10 ⁻³ mol per mol of silver were added simultaneously, instead of the grains being equivalent to 5 × 10 ⁻³ mol. Emulsion N was prepared in exactly the same manner, except that a previously prepared silver iodide emulsion having a size of 0.04 μm was added. (Total AgI content 0.5 mol%) The characteristics of each emulsion are shown in the table below.

Using these emulsions, coating was carried out in the same manner as in Example 2 to prepare Samples 12 to 18 as shown in Table 3. These samples were evaluated in the same manner as in Example 2. As is clear from Table 3, Samples 10 and 14 of the present invention have high sensitivity, high Dmax, and good image quality.

(Example 4) Emulsions C and E used in Example 2 were added to the general formula (II) of the present invention.
Was added as shown in Table 5, and the same compound as in Example 2 was further added, followed by coating to prepare Samples 19 to 36.
These samples were evaluated in the same manner as in Example 2. Table 4 shows the results. As is clear from the table, the general formula (I
The presence of the compound (I) further improves the image. (20-2
7, 29-36)

Claims (4)

(57) [Claims] 1. A silver halide emulsion comprising at least one silver halide emulsion layer on a support, wherein the silver halide emulsion comprises 0.3 to 3.0 mol%
Average grain size containing silver iodide of 0.2 μm or more and 0.5 μm
m or less, the silver halide grains contain host emulsion grain crystals in an amount of 0.1 to 2.5 per total silver halide grains.
It was formed by conversion with a previously prepared ultrafine silver halide emulsion having a silver iodide content of 90 mol% or more corresponding to mol% of silver iodide and an average grain size of 0.1 μm or less. Characteristic negative type silver halide photographic material. 2. The converted silver halide grains having a silver iodide content of 90 mol% or more and an average grain size of 0.1 μm in the host emulsion in the presence of the compound represented by formula (A). 2. A negative-working silver halide photographic material according to claim 1, which is converted by adding the following pre-prepared ultrafine silver halide emulsion. General formula (A) In the formula, Z ₁₁ and Z ₁₂ are a thiazole nucleus, a thiazoline nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, an oxazole nucleus,
It represents a group of atoms necessary to form a benzoxazole nucleus, an oxazoline nucleus, a naphthoxazole nucleus, an imidazole nucleus, a benzimidazole nucleus, an imidazoline nucleus, a selenazole nucleus, a selenazoline nucleus, a benzoselenazole nucleus or a naphthoselenazole nucleus. R ₁₁ and R ₁₂ represent an alkyl group or a substituted alkyl group. However, at least one of R ₁₁ and R ₁₂ has a sulfo group or a carboxy group. L ₁₁ and L ₁₂ represent a substituted or unsubstituted methane group. n represents the integer of 0-2. 3. A negative-working silver halide photographic material according to claim 1, wherein the emulsion layer or another hydrophilic colloid layer contains a hydrazine derivative. 4. The negative-working silver halide photographic material according to claim 4, further comprising a redox compound which releases a development inhibitor by being oxidized into an emulsion layer or another hydrophilic colloid layer.