JPH06230496A - Silver halide photographic sensitive material and image forming method using the same - Google Patents

Abstract

PURPOSE:To obtain extremely high contrast photographic characteristics even at the time of using a stable low pH developer by using a specific silver halide emulsion. CONSTITUTION:The silver halide emulsion comprises chemically sensitized silver halide grains having a >=50mole% silver chloride content, which contain 1X10<-8> to 5X10<-6> mole rhodium compound per mole of silver and 1X10<-8> to 1X10<-6> mole iridium compound per mole of silver. Further at least one of the emulsion layers or other hydrophilic-colloidal layers contains at least one hydrazine derivative and the silver halide emulsion is spectrally sensitized with at least one dyestuff selected from among compounds represented by the formula, etc. In the formula, each of V31 and V33 is a hydrogen atom or an electron- attracting group; each of V32 and V34 is an electron-attracting group; each of R31-R34 is an alkyl or alkenyl group having <=10 carbon atoms, wherein at least one of R31-R34 is a group contg. a sulfo or carboxyl group; X31 is a counter ion necessary for neutralizing charge; n31 is 0 or 1, wherein n31 is 0 when the compound is an inner salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to an ultrahigh-contrast silver halide photographic light-sensitive material used for photolithography.

[0002]

2. Description of the Related Art In the field of graphic arts, an image forming system showing photographic characteristics of ultra-high contrast (especially γ of 10 or more) in order to favorably reproduce a continuous tone image or a line image by a halftone image. is necessary.
There is a demand for an image forming system which can be developed with a processing solution having good storage stability to obtain ultra-high contrast photographic characteristics. One of them is US Pat. Nos. 4,166,742 and 4,16.
8,977, 4,221,857, 4,22
4,401, 4,243,739, 4,27
Nos. 2,606 and 4,311,781, a surface latent image type silver halide photographic light-sensitive material containing a specific acylhydrazine compound is added to a sulphite preservative.
A system has been proposed which forms a super-high contrast negative image in which γ exceeds 10 by processing with a developer having a pH of 11.0 to 12.3 containing 5 mol / liter or more. This new image forming system can only use silver chlorobromide, which has a high content of silver chloride in conventional ultrahigh contrast image formation, whereas silver iodobromide and silver chloroiodobromide can also be used. There is. Another feature is that the conventional lith developer can contain a very small amount of sulfite preservative, whereas it can contain a large amount of sulfite preservative, so that it has relatively good storage stability. . However, a developer having a pH of 11 or more is easily oxidized by air and is unstable, and cannot be stored or used for a long time. Attempts have been made to develop a high-contrast image by developing a silver halide light-sensitive material containing a hydrazine compound with a developer having a lower pH. In JP-A-1-179939 and JP-A-1-179940, a photosensitive material containing a nucleation development accelerator having an adsorptive group for silver halide emulsion grains and a nucleating agent also having an adsorptive group was used to obtain a pH of 11 A processing method of developing with a developing solution of 0.0 or less is described.

US Pat. Nos. 4,998,604, 4,
994, 365 and 4,975,354 disclose a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However, from the description of the examples, these inventions do not have sufficient contrast, and it is difficult to obtain the contrast and required Dmax under practical development processing conditions. Further, the nucleating hard contrast material using a hydrazine derivative has a wide range of change in photographic property with a change in pH of the developer. The pH of the developer greatly changes due to air oxidation of the developer and increase due to concentration by evaporation of water, or decrease due to absorption of carbon dioxide in the air. Therefore, attempts have been made to reduce the dependence of photographic performance on the pH of the developer. An example using chemically sensitized silver chlorobromide in a system using hydrazines is disclosed in JP-A-53-20921.
No. 60-83028, No. 60-140399,
63-46437, 63-103230, JP-A-3-294844, 3-294845 and 4-.
No. 174424 and Japanese Patent Application No. 3-188230. On the other hand, examples of combined use of silver halide emulsions containing hydrazines and heavy metal complexes such as rhodium and iridium are disclosed in JP-A-60-83028 and 61-47942.
No. 61, No. 61-47943, No. 61-29837, No. 62-201233, No. 62-235947, No. 6
No. 3-103232 and the like.

An example of a system using hydrazines containing a cyanine dye having an anion charge is 5,5'-dichloro-9-ethyl-3,3'-bis (3-sulfopropyl) oxacarbocyanine. Many are disclosed, including alkali salts, and examples thereof include JP-A-61-2.
9837, 62-235947, 62-280.
No. 733, No. 62-280734, and JP-A No. 2-40.
No. 2-124560, No. 2-262655, and No. 3-63641.

[0005]

[Problems to be Solved by the Invention]

The first object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining extremely hard photographic properties with a gamma of more than 10 using a stable developing solution. A second object of the present invention is to provide a silver halide photographic light-sensitive material which is made to have a high contrast with a developing solution having a pH of 11 or less and whose performance does not fluctuate even when processed in a large amount. A third object of the present invention is to provide a silver halide photographic light-sensitive material in which black spots (fine black spots generated in non-image areas) are less likely to occur even when treated with a developer having advanced air oxidation. .

[0007]

The above-mentioned problems are solved in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion is 1 × 10 ⁻ per mol of silver. ⁸ to 5 × 10 ^-6 mol of rhodium compound and 1 × 10 ^-6 to 1 × 10 ^-8 per mol of silver
Consisting of chemically sensitized silver halide grains having a silver chloride content of 50 mol% or more, containing mols of iridium compound,
And at least one hydrazine derivative is contained in at least one layer of the emulsion layer or other hydrophilic colloid layer, and the silver halide emulsion has the following general formula (1):
A silver halide photographic light-sensitive material, which is spectrally sensitized with at least one dye selected from (2) and (3). General formula (1)

[0008]

[Chemical 7]

In the formula, W ₁ and W ₄ represent a hydrogen atom.
W ₃ and W ₆ represent a hydrogen atom, a methyl group or a methoxy group. W ₂ represents an optionally branched alkyl group having a total carbon number of 6 or less, an alkoxy group having a total carbon number of 5 or less, a bromine atom, an iodine atom, or an aryl group having a total carbon number of 9 or less, and W ₁ or W ₃ may form a benzene ring in conjunction with the case where W ₃ represents a methyl group or a or a methoxy group also represent a chlorine atom. W ₅ is an optionally branched alkyl group having a total carbon number of 6 or less, an alkoxy group having a total carbon number of 5 or less, a halogen atom, a hydroxy group, an aryl group having a total carbon number of 9 or less, and an aryloxy having a total carbon number of 9 or less. Group, an arylthio group having a total carbon number of 8 or less, an alkylthio group having a total carbon number of 4 or less, an acylamino group having a total carbon number of 4 or less,
It means that a benzene ring may be formed by linking with W ₄ or W ₆ . R ₁ and R ₂ may be the same or different and each represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms, R ₁ or R ₂
At least one of the groups is a group having a sulfo group or a carboxy group. R ₃ represents an optionally substituted lower alkyl group. X ₁ represents a counter ion necessary for neutralizing the electric charge. n1 represents 0 or 1, and is 0 in the case of an inner salt. General formula (2)

[0010]

[Chemical 8]

In the formula, V ₁ represents a hydrogen atom. V ₂ is a hydrogen atom, a halogen atom, a hydroxy group, an optionally branched lower alkyl group, a lower alkoxy group, an aryl group having a total carbon number of 9 or less, an aryloxy group having a total carbon number of 9 or less,
It represents an arylthio group having a total carbon number of 8 or less, a lower alkylthio group, an acylamino group having a total carbon number of 4 or less, and also represents that a benzene ring may be formed by linking with V ₁ or V ₃ . V ₃ represents a hydrogen atom, a methyl group or a methoxy group. V ₄ represents an electron-withdrawing group, and V ₅ represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom. R ₂₁ , R ₂₂ and R _{23, which} may be the same or different, each represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms, and at least one of R ₂₁ , R _{22 and} R ₂₃ Is a group having a sulfo group or a carboxy group. X ₂₁
Represents a counter ion necessary for neutralizing the charge. n ₂₁ is
Represents 0 or 1, and is 0 in the case of an inner salt. General formula (3)

[0012]

[Chemical 9]

In the formula, V ₃₁ and V ₃₃ represent a hydrogen atom or an electron-withdrawing group, and V ₃₂ and V ₃₄ represent an electron-withdrawing group.
R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ may be the same or different and each represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms, and R ₃₁ , R ₃₂ , R ₃₃ or R _34
At least one of ₃₄ is a group having a sulfo group or a carboxy group. X ₃₁ represents a counter ion necessary for neutralizing the electric charge. n ₃₁ represents 0 or 1, and is 0 in the case of an intramolecular salt. The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention contains, as the silver halide, silver chlorobromide and silver iodochlorobromide having a silver chloride content of 50 mol% or more. The silver iodide content is 3 mol% or less, more preferably 0.5 mol% or less. The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, amorphous and plate-like, but cubic is preferred. The average grain size of silver halide is preferably 0.1 μm to 0.7 μm, more preferably 0.2 μm to 0.5 μm. Regarding the particle size distribution, the coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 is 15% or less, more preferably 10%
The following ones having a narrow particle size distribution are preferable. The silver halide grains may have a uniform inner layer and a surface layer, or may have different layers.

The photographic emulsion used in the present invention is P. Glafki.
by Chimie et Physique Photographique (Paul Mo
ntel, 1967), by GF Dufin Photographic E
mulsion Chemistry (The Forcal Press, 1966
), VL Zelikman et al Making nd Coating Photog
It can be prepared using the method described in raphic Emulsion (The Focal Press, 1964) and the like.

As the method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in the presence of excess silver ion (so-called reverse mixing method)
Can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can 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 preferably, it is a tetra-substituted thiourea compound and is disclosed in JP-A-53-824.
08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinethione. In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016 and Japanese Examined Patent Publication No. 48-3689.
0, No. 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent No. 4,242,44.
As described in JP-A-55-158124 and JP-A-55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow it quickly within a range not exceeding the critical saturation.

The silver halide photographic light-sensitive material of the present invention contains a rhodium compound in order to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, such as a hexachlororhodium (III) complex salt, a hexabromorhodium (III) complex salt, a hexaamminerhodium ( III) complex salts, trizalatrodium (III) complex salts and the like. These rhodium compounds are used by dissolving them in water or a suitable solvent,
A commonly used method for stabilizing a solution of a rhodium compound is an aqueous hydrogen halide solution (eg hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.) or an alkali halide (eg KCl, NaCl, KBr, NaBr).
Etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide.

The total addition amount of the rhodium compound according to the present invention is 1 × per mol of finally formed silver halide.
10 ^{-8 to} 5 × 10 ^-6 mol is suitable, preferably 5 ×
It is 10 ⁻⁸ to 1 × 10 ⁻⁶ mol. The addition of these compounds can be appropriately carried out during the production of silver halide emulsion grains and before each step of coating the emulsion, but it is particularly preferable to add these compounds at the time of emulsion formation and to incorporate them into the silver halide grains. .

The silver halide photographic light-sensitive material of the present invention contains an iridium compound in order to achieve high sensitivity and high contrast. As the iridium compound used in the present invention, various compounds can be used, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium and the like. These iridium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid). Etc.) or an alkali halide (eg KC
1, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which is previously doped with iridium when preparing the silver halide.

The total addition amount of the iridium compound according to the present invention is 1 per mol of the finally formed silver halide.
^{X10 -8 to} 5 X 10 -6 mol is suitable, and preferably 5
It is x10 ^-8 to 1 x 10 ^-6 mol. The addition of these compounds can be appropriately carried out during the production of silver halide emulsion grains and before each step of coating the emulsion, but it is particularly preferable to add these compounds at the time of emulsion formation and to incorporate them into the silver halide grains. .

The silver halide grains used in the present invention include
It may contain metal atoms such as iron, cobalt, nickel, ruthenium, palladium, platinum, gold, thallium, copper, lead and osmium. The metal is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol per mol of silver halide. Further, in order to contain the above metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added and added at the time of preparation of particles.

The silver halide emulsion of the present invention is preferably chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method and a noble metal sensitization method can be used, and they are used alone or in combination. When used in combination,
For example, a sulfur sensitizing method and a gold sensitizing method, a sulfur sensitizing method, a selenium sensitizing method and a gold sensitizing method, a sulfur sensitizing method, a tellurium sensitizing method and a gold sensitizing method are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. As the sulfur sensitizer, known compounds can be used. For example, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines are used. be able to. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer added varies depending on various conditions such as pH, temperature and size of silver halide grains during chemical ripening, but it is 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ⁻⁵ to 10 ⁻³ mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As unstable selenium compounds, JP-B-44-15748 and 43-13489,
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
The compounds described in No. 121798 and the like can be used. Especially, the general formula (VIII) in Japanese Patent Application No. 3-121798.
It is preferable to use the compounds represented by and (IX).

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride, which is presumed to be a sensitizing nucleus, on the surface or inside of the silver halide grain. Regarding the rate of silver telluride formation in a silver halide emulsion, Japanese Patent Application No. 4-
It can be tested by the method described in 146739.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patents 235,211 and 1,121,496.
No. 1, No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33
No. 3819, No. 3-53693, No. 3-131598.
No. 4-129787, Journal of Chemical Society Chemical Communication
(J. Chem. Soc. Chem. Commun.) 635 (1980),
ibid 1102 (1979), ibid 645 (197)
9), Journal of Chemical Society
Perkin Transaction (J. Chem. Soc. Perkin. T
rans.) 1,191 (1980), S. Patai
Hen, The Chemistry of Organic Selenium and Tellurium Companies (The Chemistry
of Organic Serenium and Tellunium Compounds), Vol
1 (1986) and the same Vol 2 (1987) can be used. Particularly preferred are the compounds represented by the general formulas (II) (III) (IV) in Japanese Patent Application No. 4-146739.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, the chemical ripening conditions and the like, but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide, Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to. It is 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium and iridium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide.
About 10 ⁻⁷ to 10 ⁻² mol can be used per mol. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt and the like may coexist in the process of forming silver halide grains or physically ripening. Reduction sensitization can be used in the present invention. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound and the like can be used. To the silver halide emulsion of the present invention, a thiosulfonic acid compound may be added according to the method disclosed in European Patent Publication (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be of one kind or two or more kinds (for example, those having different average grain sizes,
Different halogen compositions, different crystal habits, different chemical sensitization conditions) may be used together.

The sensitizing dye used in the present invention is preferably a compound represented by the following general formulas (1), (2) and (3). General formula (1)

[0027]

[Chemical 10]

In the formula, W ₁ and W ₄ represent a hydrogen atom. W
₃ and W ₅ represent a hydrogen atom, a methyl group or a methoxy group. W ₂ is an optionally branched alkyl group having a total carbon number of 6 or less (for example, a methyl group, an ethyl group, a butyl group, an isobutyl group, a hexyl group, and a methoxyethyl group), and a total carbon number of 5 The following alkoxy group (for example, a methoxy group, an ethoxy group, a pentyloxy group, an ethoxymethoxy group, a hydroxyethoxy group and the like), a bromine atom, an iodine atom or an aryl group having a total carbon number of 9 or less (for example, a phenyl group, Tolyl group, anisyl group, chlorophenyl group, carboxyphenyl group, etc.) and may form a benzene ring by linking with W ₁ or W _{3. When} W ₃ represents a methyl group or a methoxy group, it is chlorine. Also represents an atom. W ₅ is an optionally branched alkyl group having a total carbon number of 6 or less (for example, a methyl group, an ethyl group, a butyl group, an isobutyl group, a hexyl group, and a methoxyethyl group) and a total carbon number of 5 or less. Alkoxy group (for example, methoxy group, ethoxy group, pentyloxy group, ethoxymethoxy group, hydroxyethoxy group, etc.), hydroxy group, halogen atom, aryl group having a total carbon number of 9 or less (eg, phenyl group, tolyl group). Group, anisyl group, chlorophenyl group, carboxyphenyl group, etc.), aryloxy group having a total carbon number of 9 or less (for example, tolyloxy group, anisyloxy group, phenoxy group, chlorophenoxy group),
Arylthio groups having a total carbon number of 8 or less (eg, tolylthio group, chlorophenylthio group, phenylthio group), alkylthio groups having a total carbon number of 4 or less (eg, methylthio group, ethylthio group, hydroxyethylthio group, etc.), total carbon numbers of 4 or less Represents an acylamino group (for example, an acetylamino group, a propionylamino group, a methanesulfonylamino group, etc.) and also represents that it may be linked to W ₄ or W ₆ to form a benzene ring.

R ₁ and R ₂ may be the same or different and each represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms, and at least one of R _{1 and} R ₂ is a sulfo group. Alternatively, it is a group having a carboxy group. More preferable substituents of the alkyl group and the alkenyl group include, for example, a sulfo group, a carboxy group, a halogen atom, a hydroxy group, an alkoxy group having 6 or less carbon atoms, and an optionally substituted aryl group having 8 or less carbon atoms (for example, , Phenyl group, tolyl group, sulfophenyl group,
Carboxyphenyl group, etc.), heterocyclic group (eg, furyl group, thienyl group, etc.), optionally substituted aryloxy group having 8 or less carbon atoms (eg, chlorophenoxy group,
Phenoxy group, sulfophenoxy group, hydroxyphenoxy group), acyl group having 8 or less carbon atoms (eg, benzenesulfonyl group, methanesulfonyl group, acetyl group, propionyl group, etc.), alkoxycarbonyl group having 6 or less carbon atoms (eg, ethoxy) Carbonyl group, butoxycarbonyl group, etc.), cyano group, alkylthio group having 6 or less carbon atoms (eg, methylthio group, ethylthio group, etc.), carbon number 8
The following optionally substituted arylthio groups (eg,
A phenylthio group, a tolylthio group, etc.), an optionally substituted carbamoyl group having 8 or less carbon atoms (eg, carbamoyl group, N-ethylcarbamoyl group, etc.), an acylamino group having 8 or less carbon atoms (eg, acetylamino group, methane) Sulfonylamino group) and the like. It may have one or more substituents. Specific examples of the group represented by R ₁ and R ₂ include, for example, a methyl group, an ethyl group, a propyl group,
Allyl group, pentyl group, hexyl group, methoxyethyl group, ethoxyethyl group, phenethyl group, tolylethyl group, sulfophenethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group ,
Carbamoylethyl group, hydroxyethyl group, 2- (2
-Hydroxyethoxy) ethyl group, carboxymethyl group, carboxyethyl group, ethoxycarbonylmethyl group, sulfoethyl group, 2-chloro-3-sulfopropyl group, 3-sulfopropyl group, 2-hydroxy-3-sulfopropyl group, 3 -Sulfobutyl group, 4-sulfobutyl group, 2- (2,3-dihydroxypropyloxy) ethyl group, 2- [2- (3-sulfopropyloxy) ethoxy] ethyl group and the like can be mentioned.

R ₃ represents an optionally substituted lower alkyl group (eg, methyl group, ethyl group, propyl group, methoxyethyl group, benzyl group, phenethyl group, etc.).
X ₁ represents a counter ion necessary for neutralizing the electric charge. n ₁
Represents 0 or 1, and is 0 in the case of an inner salt. General formula (2)

[0031]

[Chemical 11]

In the formula, V ₁ represents a hydrogen atom. V ₂ is a hydrogen atom, an optionally branched lower alkyl group (more preferably a total carbon number of 6 or less, for example, a methyl group, an ethyl group,
Examples thereof include a butyl group, an isobutyl group, a hexyl group and a methoxyethyl group. ), Lower alkoxy groups (total carbon number 5)
The following are more preferable, and examples thereof include a methoxy group, an ethoxy group, a pentyloxy group, an ethoxymethoxy group, and a hydroxyethoxy group. ), A hydroxy group, a halogen atom, an aryl group having a total carbon number of 9 or less (for example, phenyl group, tolyl group, anisyl group, chlorophenyl group, carboxyphenyl group, etc.), an aryloxy group having a total carbon number of 9 or less (for example, tolyloxy. Group, anisyloxy group,
Phenoxy group, chlorophenoxy group), arylthio group having a total carbon number of 8 or less (for example, tolylthio group, chlorophenylthio group, phenylthio group), alkylthio group having a total carbon number of 4 or less (for example, methylthio group, ethylthio group, hydroxyethylthio group) Etc.) represents an acylamino group having a total carbon number of 4 or less (for example, acetylamino group, propionylamino group, methanesulfonylamino group, etc.) and may form a benzene ring by linking with V ₁ or V _3. Represent V ₃ represents a hydrogen atom, a methyl group or a methoxy group. V ₄ represents an electron-withdrawing group. As a preferable electron-withdrawing group, a halogen atom, a lower perfluoroalkyl group (more preferably a total carbon number of 5 or less, for example, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,
2,3,3-tetrafluoropropyl group and the like), acyl group (total carbon number is preferably 8 or less, for example,
Acetyl group, propionyl group, henzoyl group, mesityl group, benzenesulfonyl group and the like), alkylsulfamoyl group (total carbon number of 5 or less is more preferable, for example, methylsulfamoyl group, ethylsulfamoyl group Etc.), a carboxy group, an alkylcarbonyl group (more preferably a total carbon number of 5 or less, for example,
Methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and the like) and cyano group and the like. V ₅ represents a hydrogen atom or a chlorine atom.

R ₂₁ , R ₂₂ and R _{23, which} may be the same or different, have the same meaning as R ₁ or R _2, and R ₂₁ , R ₂₂
Alternatively, at least one of R ₂₃ is a group having a sulfo group or a carboxy group. X ₂₁ represents a counter ion necessary for neutralizing the charge. n ₂₁ represents 0 or 1,
It is 0 in the case of an inner salt. Next, the sensitizing dye of the general formula (3) will be described. General formula (3)

[0034]

[Chemical 12]

In the formula, V ₃₁ and V ₃₃ have the same meaning as hydrogen atom or V _4, and V ₃₂ and V ₃₄ have the same meaning as V ₄ .
R ₃₁ , R ₃₂ , R ₃₃ and R _{34, which} may be the same or different, have the same meaning as R ₁ or R _2, and R ₃₁ , R ₃₂ , R
_At least one of _{33 and} R ₃₄ is a group having a sulfo group or a carboxy group. X ₃₁ represents a counter ion necessary for neutralizing the electric charge. n ₃₁ represents 0 or 1,
It is 0 in the case of an inner salt.

General formulas (1), (2), used in the present invention,
In order to incorporate the spectral sensitizing dye represented by (3) into the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, acetone, Methyl cellosolve, 2,2
3,3, -Tetrafluoropropanol, 2,2,2-
Trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-
It may be added to the emulsion by dissolving it in a solvent such as 2-propanol or N, N-dimethylformamide alone or in a mixed solvent. Further, as described in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion. As described in JP-B-46-24,185 and the like, a method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved and the dispersion is added to an emulsion, JP-B-44-23. , 389, Japanese Patent Publication No. 44-2
No. 7,555, Japanese Patent Publication No. 57-22,091, etc., a dye is dissolved in an acid and the solution is added to the emulsion, or an aqueous solution is prepared by coexisting an acid or a base into the emulsion. The method of addition, as described in US Pat. No. 3,822,135, US Pat. No. 4,006,025, etc.,
A method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant to an emulsion, JP-A-53-10.
No. 2,733 and JP-A-58-105,141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion, JP-A-51-74,6.
As described in No. 24, it is also possible to use a method in which a dye is dissolved using a compound that causes red shift and the solution is added to an emulsion. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention in any step in the preparation of emulsions which has been found to be useful so far. For example, US Pat. No. 2,735,766, US Pat. No. 3,628,960, US Pat. No. 4,183,756.
No. 4,225,666, JP-A-58-18.
No. 4,142, JP-A-60-196749, and the like, as disclosed in the specification of the silver halide grain formation step or / and before desalting, during the desalting step and / or desalting step. From the time after salting to before the start of chemical aging, JP-A-58-1
As disclosed in the specification of No. 13,920, etc., it may be added at any time or step immediately before or during the chemical ripening, at any time before the emulsion is coated until after the chemical ripening and before the coating. May be. US Pat. No. 4,225,6
66, JP-A-58-7,629 and the like, the same compound alone or in combination with a compound having a different structure, for example, during the grain forming step and the chemical ripening step. Alternatively, it may be added in divided portions such as after completion of chemical aging or before or after chemical aging or after completion of the step, and the type of compound or combination of compounds added in division may be changed. May be added. The sensitizing dye used in the present invention is, for example, JP-B-48-38,406.
No. 43, No. 43,936, No. 48-28,293,
48-25, 652, 43-22, 884, 54-34, 609, 54-34, 610, 5
7-22,368, 57-10,418, JP-A-50-23,220, and the like, and these patent specifications, French Patent 1,108,788, It can be synthesized based on the description in the specification such as Japanese Patent No. 2,174,418. When the present invention is applied to a silver halide emulsion,
For the purpose of broadening the photosensitive wavelength, for example, JP-A-62-15,4
No. 39, No. 62-287, 250, No. 53-71, 8
There is no problem even if it is used together with the sensitizing dyes for use in the blue-sensitive region and the blue-green sensitive region described in JP-A No. 29, U.S. Pat. No. 3,667,960 and the like. When applied to a silver halide photographic light-sensitive material, if it is necessary to spectrally enhance only the sensitivity in a specific wavelength range, it is preferable that an aggregate of sensitizing dyes suitable for it be formed, [1],
Among the sensitizing dyes shown in [2], the so-called J
Those that easily form aggregates are preferable. Further, for example, Japanese Examined Patent Publication No. 49-46, 932 and Japanese Unexamined Patent Publication No. 58-28, 73.
No. 8, US Pat. No. 3,776,738, and other water-soluble bromides and water-soluble additives (for example,
It is preferable to use a bispyridinium salt compound, a mercapto-heterocyclic sulfonated compound, an alkali metal salt, etc.) in combination because it strengthens the J aggregate. These compounds are silver halide 1
About 10 ⁻⁵ to 1 mol is used per mol. Examples of the sensitizing dye used in the present invention are shown below, but the present invention is not limited thereto.

[0038]

[Chemical 13]

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

[0042]

[Chemical 17]

[0043]

[Chemical 18]

[0044]

[Chemical 19]

[0045]

[Chemical 20]

[0046]

[Chemical 21]

[0047]

[Chemical formula 22]

[0048]

[Chemical formula 23]

[0049]

[Chemical formula 24]

[0050]

[Chemical 25]

General formulas (1), (2), used in the present invention,
The addition amount of the spectral sensitizing dye represented by (3) varies depending on the shape and size of silver halide grains, but is 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide. be able to. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount of 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol is preferable per 1 m ² of the surface area of the silver halide grain, The addition amount of 6.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

The hydrazine derivative used in the present invention is
The compounds represented by the general formulas [3] to (6) are preferable.

First, the hydrazine derivative represented by the general formula (4) will be described. General formula (4)

[0054]

[Chemical formula 26]

In the formula, R ₁ represents an aliphatic group or an aromatic group, and -O- (CH ₂ CH _{2) is used} as a part of the substituent.
_{2 O) n -, - O-} (CH 2 CH (CH 3) O) n - or _{-O- (CH 2 CH (OH)} CH 2 O) n - moiety of (where n is an integer of 3 or more) Or a group containing a quaternary ammonium cation as a part of the substituent. G ₁ is a -CO- group, a -COCO- group,-
CS- _{group, -C (= NG 2 R 2} ) - group, -SO- group, -
It represents a SO ₂ — group or a —P (O) (G ₂ R ₂ ) — group.
G ₂ is a simple bond, -O- group, -S- group or -N
(R ₂ )-group, R ₂ represents an aliphatic group, an aromatic group or a hydrogen atom, and when a plurality of R _2's are present in the molecule, they may be the same or different. One of A ₁ and A ₂ is a hydrogen atom, the other is a hydrogen atom or an acyl group,
Represents an alkyl or aryl sulfonyl group.

The general formula (4) will be described in more detail. In the general formula (4), the aliphatic group represented by R ₁ is preferably an aliphatic group having 1 to 30 carbon atoms, and particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
This alkyl group has a substituent. In the general formula (4), 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. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and an isoquinoline ring. Of these, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.

The aliphatic group or aromatic group of R ₁ is substituted, and a typical substituent is, for example, an alkyl group,
Aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, Examples thereof include a halogen atom, a cyano group, a sulfo group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, and a phosphoric acid amide group. Chain, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), aralkyl group (preferably having 7 carbon atoms)
To 30), an alkoxy group (preferably having a carbon number of 1 to 1)
30), substituted amino group (preferably having 1 to 30 carbon atoms)
An amino group substituted with an alkyl group), 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 1 carbon atom). And a phosphoric acid amide group (preferably having 1 to 40 carbon atoms).

The aliphatic group, aromatic group or their substituents for R ₁ is --O-(CH ₂ CH ₂ O) _n- , --O-(CH
_{2 CH (CH 3) O)} n - or -O- (CH ₂ CH
Contains (OH) CH ₂ O) _n − or 4
It contains a quaternary ammonium cation. n is an integer of 3 or more, preferably an integer of 3 or more and 15 or less. R ₁ is preferably represented by the following general formula [H1], general formula [H2], general formula [H3] or general formula [H4].

[0059]

[Chemical 27]

In the formula, L ₁ and L ₂ are --CONR ₇ --groups,
NR ₇ CONR ₈ — group, —SO ₂ NR ₇ — group or —N
And R ₇ SO ₃ NR ₈ — groups, which may be the same or different. R ₇ and R ₈ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a hydrogen atom is preferable. m is 0 or 1. R ₃ , R ₄ and R ₅ are divalent aliphatic groups or aromatic groups, preferably alkylene groups, arylene groups or their groups and —O— groups, —CO— groups, —S— groups, —SO—.
Group, -SO ₂ - group, -NR ₉ - group (R ₉ of the general formula (2), (3), R ₇ as defined in (4)) is a divalent group produced by combining a. More preferably, R ₃ is an alkylene group having 1 to 10 carbon atoms or a divalent group formed by combining them with an —S— group, —SO— group or —SO ₂ — group, and R ₄ , R ₅ Has 6 to 2 carbon atoms
It is an arylene group of 0. Particularly, R ₅ is preferably a phenylene group. R ₃ , R ₄ and R ₅ may be substituted, and preferable substituents include those listed as the substituents for R ₁ .

In formulas [H1] and [H2], Z ₁ represents an atomic group necessary for forming a nitrogen-containing aromatic ring. Z
Preferred examples of the nitrogen-containing heteroaromatic ring formed by ¹ and a nitrogen atom include a pyridine ring, a pyrimidine ring, a pyridazine ring,
Examples thereof include a pyrazine ring, an imidazole ring, a pyrazole ring, a pyrrole ring, an oxazole ring, a thiazole ring, and a benzo-condensed ring thereof, as well as a pteridine ring and a naphthyridine ring. General formula [H2], [H3], [H
In 4], X ⁻ represents a counter anion moiety when forming a counter anion or an inner salt. General formula [H2],
In [H3] and [H4], R ⁶ represents an aliphatic group or an aromatic group. R ⁶ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. General formula [H
The three R ₆ in 3] may be the same or different, and may combine with each other to form a ring.
Z ₁ and R ₆ may be substituted, and preferable substituents include those listed as the substituents for R ₁ . In the general formula [H4], L ₃ is —CH ₂ CH ₂ O—.
_{Group, -CH 2 CH (CH 3)} O- group, or -CH ₂ C,
Represents H (OH) CH ₂ O- groups, n represents the same meaning as in formula [H1].

As G ₁ in the general formula (4), --CO
- group, -SO ₂ - groups are preferred, -CO- group is most preferred. A hydrogen atom is preferable as A ₁ and A ₂ .

The alkyl group represented by R ₂ in the general formula (4) 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, benzene). Including rings). When G ₁ is a —CO— group, preferred among the groups represented by R ₂ are a hydrogen atom, an alkyl group (eg, methyl group, methoxymethyl group, phenoxymethyl group, trifluoromethyl group, 3-hydroxy group). Propyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (eg, o-hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-
Dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc., 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. Also, R
₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule, -G ₁
It may be one that causes a cyclization reaction to form a cyclic structure containing an atom of the —R ₂ portion, and examples thereof include those described in JP-A-63-29751.

R ₁ or R _{2 in} the general formula (4) may have a ballast group or polymer commonly used in a non-moving photographic additive such as a coupler incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can Further, as a polymer, for example, JP-A-1-1005
Those described in No. 30 are mentioned.

R ₁ or R _{2 in} the general formula (4) may be one in which a group which enhances adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include U.S. Pat. No. 4,385,108 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group.
4,459,347, JP-A-59-195,233.
No. 59-200, 231, 59-201, 04
No. 5, No. 59-201, 046, No. 59-201, 0
No. 47, No. 59-201, No. 048, No. 59-201,
049, 61-170, 733, 61-27.
0,744, 62-948, 63-234,2.
44, 63-234, 245, 63-234,
The groups described in No. 246 are mentioned. The compound of the general formula (4) of the present invention is disclosed in, for example, JP-A 61-213,847.
62-260,153, U.S. Pat. No. 4,684.
4,604, Japanese Patent Application No. 63-803, US Pat.
379,529, 3,620,746, 4,3
77,634, 4,332,878, JP-A-49.
-129,536, 56-153,336, 5
6-153,342, U.S. Pat. Nos. 4,988,604 and 4,994,365, and the like. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0066]

[Chemical 28]

[0067]

[Chemical 29]

General formula (5)

[0069]

[Chemical 30]

R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group, which may be substituted. G ¹ is -CO-
Group, -SO ₂ - group, -SO- group, -COCO- group, a thiocarbonyl group, an iminomethylene group or -P (O) (R
₃ )-group, and R ₂ represents a substituted alkyl group in which a carbon atom substituted with G is substituted with at least one electron withdrawing group. R ₃ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group or an amino group.

Next, the compound represented by the general formula (5) will be described in more detail. In the general formula (5), R
_The aliphatic group represented by ₁ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. R ₁
The aromatic group represented by is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The hetero ring of R ₁ is a 3- to 10-membered saturated or unsaturated hetero ring containing at least one of N, O, or S atoms, which may be a single ring, or other A condensed ring may be formed with an aromatic or hetero ring. The heterocycle is preferably a 5- or 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazoline group, a benzthiazolyl group. Those are preferable. R
Preferred as ₁ are aromatic groups, nitrogen-containing heterocycles and groups represented by general formula (b). General formula (b)

[0072]

[Chemical 31]

(In the formula, X _b represents an aromatic group or a nitrogen-containing heterocyclic group, R _b ^{1 to} R _b ⁴ each represent a hydrogen atom, a halogen atom, or an alkyl group, and X _b and R _b ¹
R _b ⁴ may have a substituent if possible.
r and s represent 0 or 1. ) R ₁ is more preferably an aromatic group, and particularly preferably an aryl group.
R ₁ may be substituted with a substituent. Examples of the substituent include, for example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group. Group, hydroxy group, halogen atom,
In addition to cyano group, sulfo group, carboxyl group, alkyl and aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamido group, sulfonamide group, nitro group, alkylthio group, arylthio group, the following general formula The group represented by (c) may be mentioned. General formula (c)

[0074]

[Chemical 32]

In the formula (c), Yc is --CO-- or --SO.
₂-, -P (O) (R_C3)-(Wherein R_C3Is alkoxy
Represents a group or an aryloxy group. ) Or -O
P (O) (R_C3)-, L is a single bond, -O-,-
S- or -NR_C4-(In the formula, R _C4Is a hydrogen atom, Archi
Represents an aryl group or an aryl group. ) Is represented. R_C1And R
_C2Represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
I can be the same or different, and bond to each other
To form a ring. Also R₁Is one general formula (c)
Alternatively, a plurality of them can be included.

In the general formula (c), the aliphatic group represented by R _C1 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R _C1 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The heterocycle of R _C1 is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, or S atoms, which may be a single ring, or other A condensed ring may be formed with an aromatic or hetero ring. The heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, a benzthiazolyl group. Those are preferable. R _C1 may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted. For example, alkyl group, aralkyl group, alkenyl group,
Alkynyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group , Halogen atoms, cyano groups, sulfo groups and carboxyl groups, alkyl and aryloxycarbonyl groups, acyl groups,
Examples thereof include an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a nitro group, an alkylthio group and an arylthio group. When possible, these groups may be linked to each other to form a ring.

The aliphatic group represented by R _C2 in the general formula (c) is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R _C2 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group. R _C2 may be substituted with a substituent. Examples of the substituent include those listed as R _C1 in the general formula (c) and the substituent. If possible, R _C1 and R _C2 may be linked to each other to form a ring. A hydrogen atom is more preferable as R _C2 .

Y _C in the general formula (c) is -CO.
-, - SO ₂ - is particularly preferred, L is a single bond and -N
R _C4 − is preferred. The aliphatic group represented by R _C4 in the general formula (c) is a linear, branched or cyclic alkyl group,
It is an alkenyl group or an alkynyl group. The aromatic group represented by R _C4 is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group. R _C4 may be substituted with a substituent. Examples of the substituent include those enumerated as the substituents of R _C1 in the general formula (c). A hydrogen atom is more preferable as R _C4 .

Most preferably, G in the general formula (5) is a --CO-- group. R _{2 in the} general formula (5) represents a substituted alkyl group in which a carbon atom substituted with G is substituted with at least one electron withdrawing group, and preferably two electron withdrawing groups,
Particularly preferred is a substituted alkyl group substituted with three electron withdrawing groups.

The electron withdrawing group for substituting the carbon atom substituted by G of R ₂ preferably has a δ _p value of 0.2 or more and a δ _m value of 0.3 or more, and examples thereof include halogen, cyano, nitro, and Nitroso, polyhaloalkyl, polyhaloaryl,
An alkyl or aryl carbonyl group, a formyl group,
Alkyl or aryloxycarbonyl group, alkylcarbonyloxy group, carbamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, alkyl or arylsulfonyloxy group, sulfamoyl group, phosphino group, phosphine oxide group, phosphonate group, phosphon It represents an acid amide group, an arylazo group, an amidino group, an ammonio group, a sulfonio group, and an electron-deficient heterocyclic group. R _{2 in the} general formula (5) particularly preferably represents a trifluoromethyl group.

R ₁ and R _{2 in} the general formula (5) may be those in which a ballast group or a polymer commonly used in a non-moving photographic additive such as a coupler is incorporated. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can Further, as a polymer, for example, JP-A-1-100530
The items described in No.

R ₁ and R _{2 in} the general formula (5) may be those in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group, which are disclosed in U.S. Pat. Nos. 4,385,108, 4,459,347, and JP-A-59-195,233.
No. 59-200, 231, 59-201, 04
No. 5, No. 59-201, 046, No. 59-201, 0
No. 47, No. 59-201, No. 048, No. 59-201,
049, 61-170, 733, 61-27.
0,744, 62-948, 63-234,2.
44, 63-234, 245, 63-234,
The groups described in No. 246 are mentioned. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0083]

[Chemical 33]

[0084]

[Chemical 34]

[0085]

[Chemical 35]

[0086]

[Chemical 36]

[0087]

[Chemical 37]

[0088]

[Chemical 38]

[0089]

[Chemical Formula 39]

[0090]

[Chemical 40]

[0091]

[Chemical 41]

The hydrazine derivative of the present invention is obtained by reacting a corresponding hydrazine with a corresponding carboxylic acid in the presence of a condensing agent such as dicyclohexylcarbodiimide, or by reacting an acid halide such as a sulfonyl chloride or an acyl chloride or an acid anhydride or an active ester. It was synthesized by reacting with. Furthermore, when EWG is R ₃ SO ₂ —, the corresponding haloacetylhydrazide derivative and R ₃ SO 2
A method of reacting ₂ H in the presence of a base was also used. A specific example is shown below.

Synthesis Example: Synthesis of Exemplified Compound 4-16 Under a nitrogen atmosphere, triethylamine (15.3 ml) was added to a mixed solution of the starting compound A (63.2 g) and tetrahydrofuran (200 ml), and the mixed solution was heated to 5 ° C. Cool down
Trifluoroacetic anhydride (16.9 ml) was added and stirred overnight at room temperature. The reaction solution was poured into 0.1N HCl aqueous solution and extracted with ethyl acetate, and the organic layer was washed with saturated saline. It was dried over anhydrous magnesium sulfate, ethyl acetate was distilled off, and the product was isolated and purified by silica gel chromatography to obtain the desired product (52.1 g). The structure of the compound was confirmed by nmr spectrum and ir spectrum. The structure of the raw material compound A is shown below.

[0094]

[Chemical 42]

Next, the compound of the general formula (6) will be described in detail.

[0096]

[Chemical 43]

In the general formula (6), the aliphatic group represented by R _a is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by _Ra is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The hetero ring of R _a is a negative saturated or unsaturated hetero ring of 3 to 10 containing at least one of N, O, or S atoms, which may be a single ring or other A condensed ring may be formed with the aromatic ring or the hetero ring of. The heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, and examples thereof include a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, and a benzthiazolyl group. preferable.

R ₂ may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted. For example, alkyl group, aralkyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group, sulfonyl group. Group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group and carboxyl group. When possible, these groups may be linked to each other to form a ring. Preferred as R _a is
An aromatic group, more preferably an aryl group. Among the groups represented by R _b , when G ₁ is a carbonyl group, preferred is a hydrogen atom, an alkyl group (for example, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-
Methanesulfonamidopropyl group etc.), aralkyl group (eg o-hydroxybenzyl group etc.), aryl group (eg phenyl group, 3,5-dichlorophenyl group, o
-Methanesulfonamidephenyl group, 4-methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferable. When G ₁ is a sulfonyl group, R _b is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxyphenylmethyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, Dimethylamino group) and the like are preferable.

When G ₁ is a sulfoxy group, preferred R _b
Is a cyanobenzyl group, a methylthiobenzyl group or the like, and when G ₁ is a phosphoryl group, R _b is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group or a phenyl group, and particularly preferably a phenoxy group. G ₁
When is an N-substituted or unsubstituted iminomethylene group, preferred R _b is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group. As the substituent of R _b , the non-substituted groups listed for R _a can be applied, and for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group or a nitro group can be applied. These substituents may be further substituted with these substituents. If possible, these groups may form a ring in which these groups are connected to each other. R _a or R _b
Adsorption-promoting groups on silver halide which can be substituted with X _1- (L
₁ ) It can be represented by _q −. Here, X ₁ is an adsorption promoting group to silver halide, and L ₁ is a divalent linking group.
q is 0 or 1. Preferred examples of the adsorption accelerating group represented by X ₁ on silver halide include a thioamide group, a mercapto group, a group having a disulphide bond or a 5- or 6-membered nitrogen-containing heterocyclic group. The thioamide adsorption-promoting group represented by X ₁ is a divalent group represented by —CS-amino-, which may be a part of the ring structure or an acyclic thioamide group. . Useful thioamide adsorption promoting groups are described, for example, in US Pat. No. 4,030,9.
No. 25, No. 4,031, 127, No. 4,080, 20
No. 7, No. 4,245,037, No. 4,255,511
Nos. 4,266,013 and 4,276,36
No. 4 and "Research Disclosure" (Re
search Disclosure) Vol. 151 No. 15162 (19)
1976), and Vol. 176, No. 17626 (1)
(December 978).

Specific examples of the acyclic thioamide group include, for example, thioureido group, thiourethane group, dithiocarbamic acid ester group and the like, and specific examples of the cyclic thioamide group include, for example, 4-thiazoline-2-thione and 4-thiazoline-2-thione group. Imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3.
4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione and the like can be mentioned. It may be substituted. The mercapto group of X ₁ is an aliphatic mercapto group, an aromatic mercapto group, or a heterocyclic mercapto group (when the carbon atom to which the —SH group is bonded is a nitrogen atom next to it, a cyclic thioamide having a tautomeric relationship therewith Synonymous with the group, and specific examples of this group are the same as those listed above).

The 5-membered to 6-membered nitrogen-containing heterocyclic group represented by X _{1 includes} 5-membered to 6-membered nitrogen-containing heterocycle consisting of a combination of nitrogen, oxygen, sulfur and carbon. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine and the like. These may be further substituted with appropriate substituents. As the substituent, those mentioned as the substituent of R _a can be mentioned. Among those represented by X ₁ , preferred ones are the present thioamide groups (that is, mercapto-substituted nitrogen-containing heterocycles, such as 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole. Group, 2-mercapto-
1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.) or a nitrogen-containing heterocyclic group (eg, benzotriazole group, benzimidazole group, indazole group, etc.).

Two or more X _1- (L ₁ ) _q groups may be substituted and may be the same or different. The divalent linking group represented by L ₁ is an atom or atomic group containing at least one of C, N, S and O. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group,
Arylene group, -O-, -S-, -NH-, -N =,-
CO—, —SO ₂ — (these groups may have a substituent), etc., or a combination thereof. These may be further substituted with appropriate substituents. As the substituent, those mentioned as the substituent of R _a can be mentioned.

A ₁ and A ₂ are substituted with a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or Hammett's substituent constant sum of -0.5 or more). Phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or the sum of Hammett's substituent constants is −).
A benzoyl group substituted to have a concentration of 0.5 or more, or a linear, branched, or cyclic unsubstituted or substituted aliphatic acyl group (eg, a substituent is a halogen atom, an ether group, a sulfonamide group, or a carbonamido group). , Hydroxyl group,
Examples thereof include a carboxy group and a sulfonic acid group. ), And
The sulfinic acid residues represented by A ₁ and A ₂ are specifically those described in US Pat. No. 4,478,928. A hydrogen atom is most preferable as A ₁ and A ₂ . A carbonyl group is most preferable as G _{1 in the} general formula (6). Among those represented by the general formula (6), preferred ones can be represented by the general formula (6-a). General formula (6-
a)

[0104]

[Chemical 44]

[0105] In the formula, R _'a are those from R _a in formula (6) by removing one hydrogen atom. Here, at least one of R ′ _a , R _{b and} L ₁ has a group capable of dissociating into an anion having a pKa of 6 or more or an amino group. pKa6
Among the groups capable of dissociating into the above anions, the preferable ones are substituents capable of dissociating into anions of pKa8 to 13, which hardly dissociate in a neutral or weakly acidic medium (alkaline aqueous solution such as a developer). Preferably pH 10.5-1
It does not have to be a specific one as long as it can be sufficiently dissociated in 2.3).

For example, a hydroxyl group, a group represented by --SO ₂ NH--, a hydroxyimino group, an active methylene group, or an active methine group (eg --CH ₂ COO--, --CH ₂ CO--,
-CH (CN) -COO- and the like).
The amino group may be primary, secondary, or tertiary, and the conjugate acid preferably has a pKa of 6.0 or more. A ₁ , A ₂ , G ₁ , R _b , L ₁ , X ₁ and q
Has the same meaning as described in the general formula (6). Among those represented by the general formula (6), particularly preferable ones are those represented by the general formula (6-b). General formula (6-b)

[0107]

[Chemical formula 45]

In the formula, L ₂ has the same meaning as L _{1 of} formula (6) and formula (6-a), and Y ₁ has the same meaning as the substituent of R ₁ of formula (6). And q represents 0 or 1, 1 represents 0, 1, or 2, and when 1 is 2, Y may be the same or different. A ₁ , A ₂ , G ₁ , R _b ,
L ₁ and X ₁ have the same meanings as described in the general formulas (6) and (6-a). Furthermore, preferably X _1- (L ₂ ) _q
—SO ₂ NH is a hydrazino group substituted at the p-position. The compound of the general formula (6) is disclosed in JP-A-56-678.
43, ibid. 60-179734, Japanese Patent Application No. 60-7818.
2. Japanese Patent Application No. 60-111936, Japanese Patent Application No. 61-1150
36, etc. according to the method described in. Specific examples of the compound represented by the general formula (6) are shown below. However, the present invention is not limited to the following compounds.

[0109]

[Chemical formula 46]

[0110]

[Chemical 47]

The addition amount of the hydrazine compound in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol per mol of silver halide, particularly 1 × 1.
0 ^-5 mol to 2 × 10 ^-2 mol per mol of silver is preferred. The hydrazine compound of the present invention is a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone,
Methyl ethyl ketone), dimethylformylamide, dimethylsulfoxide, and methyl cellosolve can be used by dissolving them. Also, by well-known emulsification and dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexane are dissolved to mechanically emulsify the dispersion. Can also be prepared and used. Alternatively, the hydrazine compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and then used.

The amine derivative, onium salt, disulfide derivative, or hydroxymethyl derivative used in the present invention functions as a release accelerator. Examples of amine derivatives include those disclosed in JP-A-60-140,340 and JP-A-65-25.
0,829, 62-222,241, 62-2
50,439, 62-280,733, 63-
124, 045, 63-133, 145, 63
Examples thereof include compounds described in No. 286,840. More preferably, the amine derivative is preferably JP-A-63-63.
-124,045, 63-133,145, 6
Compounds having a group capable of adsorbing to silver halide, such as those described in JP-A-3-286840, or JP-A-62-22.
It is a compound having 20 or more carbon atoms as described in No. 2,241. The onium salt is preferably an ammonium salt or a phosphonium salt. Examples of preferable ammonium salts include JP-A-62-250439.
The compounds described in JP-A-62-280,733 and the like can be mentioned. Further, examples of preferable phosphonium salts include JP-A-61-167,939 and JP-A-62-162.
The compound described in No. 80,733 etc. can be mentioned. Examples of the disulfide derivative include the compounds described in JP-A No. 61-198,147. Examples of the hydroxymethyl derivative include, for example, U.S. Patent Nos. 4,693,956 and 4,777,118,
Examples thereof include compounds described in EP231,850 and JP-A-62-50,829, more preferably diarylmethanol derivatives.

Next, specific examples of the release accelerator will be shown. However, the present invention is not limited to the following compounds.

[0114]

[Chemical 48]

[0115]

[Chemical 49]

[0116]

[Chemical 50]

[0117]

[Chemical 51]

[0118]

[Chemical 52]

[0119]

[Chemical 53]

[0120]

[Chemical 54]

[0121]

[Chemical 55]

[0122]

[Chemical 56]

[0123]

[Chemical 57]

[0124]

[Chemical 58]

The optimum addition amount of these compounds varies depending on the kind thereof, but is 1.0 × 1 per mol of the redox compound.
0 ⁻² mol to 1.0 × 10 ² mol, preferably 1.0 ×
It is desirable to use it in the range of 10 ⁻¹ mol to 1.0 × 10 mol. These compounds are dissolved in a suitable solvent (H ₂ O) alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution. Plural kinds of these compounds may be used in combination.

As the binder or protective colloid for the photographic emulsion, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, sugar derivatives such as starch derivatives, polyvinyl alcohol, Various synthetic hydrophilic polymer substances such as single or copolymers of polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl butyral and the like can be used.

In order to obtain ultrahigh contrast and high sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or pH 13 described in US Pat. No. 2,419,975 is used.
It is not necessary to use a highly alkaline developing solution close to the above, and a stable developing solution can be used. That is, the silver halide light-sensitive material of the present invention has a sulfite ion as a preservative of 0.
A developer containing 15 mol / liter or more and having a pH of 9.6 to 11.0 can sufficiently obtain a super-high contrast negative image. There is no particular limitation on the developing agent used in the developer used in the present invention, but it is preferable to contain dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality, and dihydroxybenzenes and 1-phenyl-3- A combination of pyrazolidones or a combination 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, 2,
There are 5-dimethylhydroquinone and the like, but hydroquinone is particularly preferable.

The developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention includes 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-4-pyrazolidone and 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. As the p-aminophenol-based developing agent used in the present invention, N-methyl-p-aminophenol, p
-Aminophenol, N- (β-hydroxyethyl)-
p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p
-Benzylaminophenol, etc., but among them N-
Methyl-p-aminophenol is preferred. The developing agent is usually preferably used in an amount of 0.05 mol / liter to 0.8 mol / liter. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols is used, the former is 0.05 mol / liter to 0.5 mol / liter and the latter is 0.06 mol. It is preferably used in an amount of 1 / liter or less.

As the preservative of sulfite used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite is preferably 0.15 mol / liter or more, and particularly preferably 0.3 mol / liter or more. The upper limit is 2.
It is preferably up to 5 mol / liter. The alkaline agent used for setting the pH includes a pH adjusting agent and a buffering agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate. The pH of the developer is set between 9.6 and 11.0.

As additives used in addition to the above components, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, toluethylene glycol, dimethylformamide , Organic solvents such as methyl cellosolve, hexylene glycol, ethanol, methanol: 1-phenyl-5-mercaptotetrazole, 5-
An indazole compound such as nitroindazole, an antifoggant such as 5-methylbenztriazole or a benztriazole compound such as a benztriazole compound or a black pepper inhibitor: may be contained, and if necessary, a toning agent and a surfactant. , Antifoaming agent, water softener, hardener, JP-A-56-10
The amino compound described in No. 6244 may be included. In the developer of the present invention, a silver stain preventing agent is disclosed in JP-A-56-2.
The compounds described in 4,347 can be used. As a dissolution aid to be added to the developing solution, Japanese Patent Application No. 60-109,
The compound described in No. 743 can be used. Further, as a pH buffer agent used in a developing solution, JP-A-60-93,4
33 or the Japanese Patent Application No. 61-28708
The compounds described in No. 1 can be used.

As the fixing agent, those having a generally used composition can be used. Thiosulfate as a fixing agent,
In addition to thiocyanate, an organic sulfur compound known to be effective as a fixing agent can be used. The fixing solution may contain water-soluble aluminum (for example, aluminum sulfate, light vane, etc.) as a hardening agent. Here, the amount of the water-soluble aluminum salt is usually 0.4 to 2.0 g-Al /
It is a liter. Furthermore, a trivalent iron compound can be used as a complex with ethylenediaminetetraacetic acid as an oxidizing agent. The developing treatment temperature is usually selected from 18 ° C to 50 ° C, more preferably 25 ° C to 43 ° C.

There are no particular restrictions on various additives used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used. Item 1) Nucleation accelerator A compound represented by the general formula (I), (II), (III), (IV), (V) or (VI) described in Japanese Patent Application No. 4-237366. JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 General formulas (II-m) to (II-p) and compound examples II-1 to II-22, The compound described in JP-A-1-179939. 2) Spectral sensitizing dyes JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4; JP-A-2-103536, page 16, lower right column, line 3 to page 17, lower left Spectral sensitizing dyes described in column 20, line 20 and JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, and Japanese Patent Application Nos. 3-189532 and 3-411064. 3) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, left lower column, line 13 to 4 Lower right column, line 18 4) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5; further JP-A 1-237538 Thiosulfinic acid compounds described in the public notice. 5) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compounds having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 7) Matting agent, slipping agent, JP-A-2-103536, page 19, upper left column 15, plasticizer line to page 19, upper right column, line 15 8) Hardeners, JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 9) Dyes: Dyes in the lower right column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and JP-A-3-185773. 10) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 11) Anti-black spot agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 12) Redox compound A compound represented by the general formula (I) in JP-A No. 2-301743 (particularly compound examples 1 to 50), a general formula (page 3 to page 20 in JP-A No. 3-174143). R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648. 13) Monomethine compound Compounds of the general formula (II) described in JP-A-2-287532 (compound examples II-1 to II-26). 14) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to genus, page 12, lower left column, and EP452772A.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

[0134]

【Example】

Example 1 An emulsion was prepared by the following method. Emulsion A: 0.13 M silver nitrate aqueous solution and K ₂ Rh (H ₂ O) Cl ₅ corresponding to 1.5 × 10 ⁻⁷ mol per mol of silver
And K ₃ IrCl ₆ corresponding to 2 × 10 ⁻⁷ mol,
An aqueous solution of halogen salt containing 0.04M potassium bromide and 0.09M sodium chloride was added to
To the aqueous gelatin solution containing 3-dimethyl-2-imidazolidinethione was added by the double jet method at 38 ° C. for 12 minutes while stirring, and the average particle size was 0.14 μm.
The nucleation was carried out by obtaining silver chlorobromide grains having a m content of 70 mol% and a silver chloride content of 70 mol%. Subsequently, similarly, a 0.87 M silver nitrate aqueous solution, 0.26 M potassium bromide, and a halogen salt aqueous solution containing 0.65 M sodium chloride were added over 20 minutes by the double jet method. Table 1 in the same way
Emulsions A to D shown in Table 1 were prepared.

Then, 1 × 10 ⁻³ mol of KI solution was added to each emulsion for conversion, and the emulsion was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added per mol of silver, pH 6.5 and pAg 7.5. The sensitizing dye of the present invention and the following comparative compound were added as shown in Table 2. Further, 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, 8 mg of chloroauric acid, 200 mg of potassium thiocyanate and 5 mg of sodium thiosulfate were added per mol of silver.
After heating at 60 ° C. for 45 minutes for chemical sensitization, 4-hydroxy-6-methyl-1,3,3a, 7- was used as a stabilizer.
150 mg of tetrazaindene was added, and further 100 mg of proxel was added as a preservative. The obtained grains were cubic grains of silver iodochlorobromide having an average grain size of 0.25 μm and a silver chloride content of 69.9 mol%. (Variation coefficient 10
%)

Emulsion E A 0.13 M silver nitrate aqueous solution and 1.5 × per mol of silver
K ₂ Rh (H ₂ O) Cl ₅ and 2 corresponding to 10 ^-7 mol
0.09 containing K ₃ IrCl ₆ corresponding to × 10 ^-7 mol
An aqueous solution of a halogen salt containing M potassium bromide and 0.04 M sodium chloride is added to an aqueous gelatin solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione with stirring at 38 ° C. for 12 minutes by the double jet method. Nucleation was performed to obtain silver chlorobromide grains having an average grain size of 0.14 μm and a silver chloride content of 30 mol%. Subsequently, similarly, a 0.87 M silver nitrate aqueous solution, a 0.61 M potassium bromide, and a 0.30 M sodium chloride-containing halogen salt aqueous solution were added over 20 minutes by the double jet method.

Thereafter, 1 × 10 ⁻³ mol of KI solution was added for conversion, and the product was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added per mol of silver to prepare pH 6.5 and pAg 7.5. 60 ℃
The sensitizing dyes of the present invention and the following comparative compounds are shown in Table 2 below.
Was added as shown in. Further, 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, 8 mg of chloroauric acid, 200 mg of potassium thiocyanate and 5 mg of sodium thiosulfate were added per 1 mol of silver, and the mixture was heated at 60 ° C for 45 minutes for chemical sensitization and then stabilized. 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (150 mg) was added as a preservative, and Proxel 100 was added as a preservative.
mg was added. The obtained particles have an average particle size of 0.25μ.
m, and silver iodochlorobromide cubic grains having a silver chloride content of 29.9 mol%. (Variation coefficient 10%)

[0138]

[Chemical 59]

Preparation of Coating Sample In the above emulsion, 3 × 10 ⁻⁴ mol of the mercapto compound represented by the following (a) per mol of silver, 4 × 10 ⁻⁴ mol of the mercapto compound represented by the (b), 4 × 10 ⁻⁴ mol of the triazine compound represented by (c), 2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline, 3 × 10 ⁻⁴ mol of the compound of (d), the hydrazine derivative shown in Table 2 Was added in an amount of 5 × 10 ⁻³ mol per mol of silver. Furthermore, N-
Oleyl-N-methyltaurine sodium salt 30 mg /
m ² is added so as to be applied, and 200 mg / m ^{2 of the} water-soluble latex represented by (e), and 200 mg of a dispersion of the nucleation accelerator represented by the following structural formula and polyethyl acrylate are added.
/ M ² , methyl acrylate and 2-acrylamido-2-
200 mg / m ² of latex copolymer of methyl propane sulfonic acid sodium salt and 2-acetoacetoxyethyl methacrylate (weight ratio 88: 5: 7), and 200 mg of 1,3-divinylsulfonyl-2-propanol as a hardening agent. / M ² was added. The pH of the solution was adjusted to 6.0. These were coated on an undercoated polyethylene terephthalate film so that the coating silver amount was 3.0 g / m ² .

[0140]

[Chemical 60]

[0141]

[Chemical formula 61]

[0142]

[Chemical formula 62]

On these emulsion layers, as a protective layer, 1.0 g / m ² of gelatin, 40 mg / m ^{2 of} amorphous SiO ₂ matting agent having an average particle size of about 3.5 μm, and methanol silica of 0.1.
1 g / m ² , polyacrylamide 100 mg / m ² , hydroquinone 200 mg / m ² , silicone oil 20 mg / m ^2, and a fluorosurfactant 5 mg / m ^{2 represented by the following} structural formula (e) as a coating aid and dodecylbenzenesulfone. Sodium acid 100 mg / m ² was applied to prepare samples as shown in Table 2. The back layer and the back protective layer were applied by the following formulation.

[0144]

[Chemical formula 63]

[Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ²

[0146]

[Chemical 64]

SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20 μm) 200 mg / m ² dye Mixture of dye [a], dye [b], dye [c] dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ²

[0148]

[Chemical 65]

[Back protective layer] Gelatin 0.8 mg / m ² polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² p-dodecylbenzenesulfonic acid Sodium 15 mg / m ² Sodium acetate 40 mg / m ²

[0150]

[Table 1]

The sample thus obtained was exposed to tungsten light through a step wedge, and a developing solution having the following formulation was used as a developing solution and GR-D1 (manufactured by Fuji Photo Film Co., Ltd.) was used as a fixing solution, and FG-680A automatic development was performed. Machine (made by Fuji Photo Film Co., Ltd.)
Processed. The evaluation results are shown in Table 2. Here, the sensitivity is indicated by the relative value of the reciprocal of the exposure amount that gives a density of 1.5 at 38 ° C. for 30 seconds. γ is represented by the following formula

[0152]

[Equation 1]

It is defined in. The black spots are obtained by observing the actual portion when developed at 38 ° C. and 30 ″ with a microscope, and “5” is the best and “1” is the worst quality.
"5" or "4" is practical, "3" is poor but can be practically managed, and "2" or "1" is not practical.

Developer 1 Replenisher 1,2-Dihydroxybenzene-3,5-disulfonate sodium 0.5 g Diethylenetriamine-pentaacetic acid 2.0 g Sodium carbonate 5.0 g Boric acid 10.0 g Potassium sulfite 85.0 g Sodium bromide 6 0.0 g diethylene glycol 40.0 g 5-methylbenzotriazole 0.2 g hydroquinone 30.0 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.6 g 2,3,5,6,7,8-hexahydro 2-Thioxo-4- (1H) -quinazolinone 0.09 g 2-mercaptobenzimidazole-5-sodium sulfonate 0.3 g Potassium hydroxide is added, water is added to 1 liter, and the pH is adjusted to 10.7. . 1 liter Starter acetic acid (90%) 366 g Water was added to 1 liter To 1 liter of the replenisher, 10 ml of the starter was added to prepare Developer 1.

Developer 2 Concentrate Sodium metabisulfite 145 g Potassium hydroxide (45%) 178 g Diethylenetriamine pentaacetic acid pentasodium salt 15 g Sodium bromide 12 g Hydroquinone 65 g 1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.9 g Benzotriazole 0.4 g 1-Phenyl-5-mercaptotetrazole 0.05 g Sodium hydroxide (50%) 46 g Boric acid 6.9 g Diethylene glycol 120 g Potassium carbonate (47%) 120 g Water 1 liter Concentrated liquid 1 Diluted with water to the ratio of 2 to pH 1
A developer 2 of 0.5 was made.

Developer 3 A developer 3 was prepared by using the developer 1 and running each sample (blackening rate 100%) after exposure in an amount corresponding to 30 sheets in total conversion without replenishment. Developer 4 Developer 1 was left unreplenished at 38 ° C. for 1 month without treating the sample to prepare Developer 4.

[0157]

[Table 2]

As is clear from Table 2, it is understood that the samples of the present invention maintain good performance even with variations in developer composition.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 19, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

The hydrazine derivative used in the present invention is
The compounds represented by the general formulas (4) to (6) are preferable.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction content]

[0059]

[Chemical 27]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction content]

In the formula, L ₁ and L ₂ are --CONR ₇ --groups,
NR ₇ CONR ₈ — group, —SO ₂ NR ₇ — group or —N
And R ₇ SO ₃ NR ₈ — groups, which may be the same or different. R ₇ and R ₈ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a hydrogen atom is preferable. m is 0 or 1. R ₃ , R ₄ and R ₅ are divalent aliphatic groups or aromatic groups, preferably alkylene groups, arylene groups or their groups and —O— groups, —CO— groups, —S— groups, —SO—.
Group, —SO ₂ — group, —NR ₉ — group (R ₉ is represented by the general formula [H
1], [H2], [H3], and [H4] (synonymous with R ₇ )) is a divalent group formed by combining them.
More preferably, R ₃ is an alkylene group having 1 to 10 carbon atoms or a divalent group formed by combining them with an —S— group, —SO— group or —SO ₂ — group, and R ₄ and R ₅ Is an arylene group having 6 to 20 carbon atoms. Particularly, R ₅ is preferably a phenylene group. R ₃ , R ₄ and R ₅ may be substituted, and preferable substituents include those listed as the substituents for R ₁ .

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

In formulas [H1] and [H2], Z ₁ represents an atomic group necessary for forming a nitrogen-containing aromatic ring. Z
Preferred examples of the nitrogen-containing heteroaromatic ring formed by ¹ and a nitrogen atom include a pyridine ring, a pyrimidine ring, a pyridazine ring,
Examples thereof include a pyrazine ring, an imidazole ring, a pyrazole ring, a pyrrole ring, an oxazole ring, a thiazole ring, and a benzo-condensed ring thereof, as well as a pteridine ring and a naphthyridine ring. General formula [H1], [H2], [H
In 3], X ⁻ represents a counter anion or a counter anion when it forms an inner salt. General formula [H2],
In [H3] and [H4], R ⁶ represents an aliphatic group or an aromatic group. R ⁶ is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. General formula [H
The three R ₆ in 3] may be the same or different, and may combine with each other to form a ring.
Z ₁ and R ₆ may be substituted, and preferable substituents include those listed as the substituents for R ₁ . In the general formula [H4], L ₃ is —CH ₂ CH ₂ O—.
_{Group, -CH 2 CH (CH 3)} O- group, or -CH ₂ C,
Represents H (OH) CH ₂ O- groups, n represents the same meaning as in formula [H1].

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0096

[Correction method] Change

[Correction content]

[0096]

[Chemical 43]

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0112

[Correction method] Change

[Correction content]

The amine derivative, onium salt, disulfide derivative or hydroxymethyl derivative used in the present invention functions as a nucleation accelerator. Examples of amine derivatives include those disclosed in JP-A-60-140,340 and JP-A-65-25.
0,829, 62-222,241, 62-2
50,439, 62-280,733, 63-
124, 045, 63-133, 145, 63
Examples thereof include compounds described in No. 286,840. More preferably, the amine derivative is preferably JP-A-63-63.
-124,045, 63-133,145, 6
Compounds having a group capable of adsorbing to silver halide, such as those described in JP-A-3-286840, or JP-A-62-22.
It is a compound having 20 or more carbon atoms as described in No. 2,241. The onium salt is preferably an ammonium salt or a phosphonium salt. Examples of preferable ammonium salts include JP-A-62-250439.
The compounds described in JP-A-62-280,733 and the like can be mentioned. Further, examples of preferable phosphonium salts include JP-A-61-167,939 and JP-A-62-162.
The compound described in No. 80,733 etc. can be mentioned. Examples of the disulfide derivative include the compounds described in JP-A No. 61-198,147. Examples of the hydroxymethyl derivative include, for example, U.S. Patent Nos. 4,693,956 and 4,777,118,
Examples thereof include compounds described in EP231,850 and JP-A-62-50,829, more preferably diarylmethanol derivatives.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0113

[Correction method] Change

[Correction content]

Specific examples of the nucleation accelerator are shown below. However, the present invention is not limited to the following compounds.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0125

[Correction method] Change

[Correction content]

These compounds are optimally added depending on their kind.
1.0 x 1 per 1 mol of hydrazine compound, although the amount added is different
0^-2Mol ~ 1.0 x 10²Mole, preferably 1.0 x
10 ^-1Desirable to use in the range of 1.0 to 10 mol
Good These compounds are suitable solvents (H₂O) methano
Alcohol such as alcohol and ethanol, acetone, dimethyl
Dissolve in formaldehyde, methyl cellosolve, etc.)
It is added to the cloth liquid. Multiple combinations of these compounds
You may.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0143

[Correction method] Change

[Correction content]

On these emulsion layers, as a protective layer, 1.0 g / m ² of gelatin, 40 mg / m ^{2 of} amorphous SiO ₂ matting agent having an average particle size of about 3.5 μm, and methanol silica of 0.1.
1 g / m ² , polyacrylamide 100 mg / m ² , hydroquinone 200 mg / m ² , silicone oil 20 mg / m ² and a fluorosurfactant 5 mg / m ^{2 represented by the following} structural formula (f) as a coating aid and dodecylbenzenesulfone. Sodium acid 100 mg / m ² was applied to prepare samples as shown in Table 2. The back layer and the back protective layer were applied by the following formulation.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0151

[Correction method] Change

[Correction content]

The sample thus obtained was exposed to tungsten light through a step wedge, and a developing solution having the following formulation was used as a developing solution and GR-F1 (manufactured by Fuji Photo Film Co., Ltd.) was used as a fixing solution, and FG-680A automatic development was performed. Machine (made by Fuji Photo Film Co., Ltd.)
Processed. The evaluation results are shown in Table 2. Here, the sensitivity is indicated by the relative value of the reciprocal of the exposure amount that gives a density of 1.5 at 38 ° C. for 30 seconds. γ is represented by the following formula

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The silver halide emulsion contains 1 × 10 ⁻⁸ to 5 per mol of silver.
× 10 ^-6 mol of rhodium compound and 1 per mol of silver
Of chemically sensitized silver halide grains having a silver chloride content of 50 mol% or more containing from 10 to ⁸ × 10 ^-6 mol of an iridium compound, and comprising the emulsion layer or another hydrophilic colloid layer. At least one hydrazine derivative is contained in at least one layer, and the silver halide emulsion is spectrally sensitized with at least one dye selected from the following general formulas (1), (2) and (3). A characteristic silver halide photographic light-sensitive material. General formula (1) In the formula, W ₁ and W ₄ represent a hydrogen atom. W ₃ and W
₆ represents a hydrogen atom, a methyl group or a methoxy group. W ₂
Is an optionally branched alkyl group having a total carbon number of 6 or less,
It represents an alkoxy group having a total carbon number of 5 or less, a bromine atom, an iodine atom or an aryl group having a total carbon number of 9 or less, and may form a benzene ring by linking with W ₁ or W _3, and W ₃ is a methyl group. Or or, when representing a methoxy group, also represents a chlorine atom. W ₅ is an optionally branched alkyl group having a total carbon number of 6 or less, an alkoxy group having a total carbon number of 5 or less, a halogen atom, a hydroxy group, an aryl group having a total carbon number of 9 or less, and an aryloxy having a total carbon number of 9 or less. Group, an arylthio group having a total carbon number of 8 or less, an alkylthio group having a total carbon number of 4 or less, an acylamino group having a total carbon number of 4 or less, and W ₄ or W ₆
Represents that it may be linked with to form a benzene ring. R
₁ and R ₂ may be the same or different and each represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms, and at least one of R _{1 and} R ₂ is a sulfo group or A group having a carboxy group. R ₃ represents an optionally substituted lower alkyl group. X ₁ represents a counter ion necessary for neutralizing the electric charge.
n1 represents 0 or 1, and is 0 in the case of an inner salt. General formula (2) In the formula, V ₁ represents a hydrogen atom. V ₂ is a hydrogen atom, a halogen atom, a hydroxy group, an optionally branched lower alkyl group, a lower alkoxy group, an aryl group having a total carbon number of 9 or less, an aryloxy group having a total carbon number of 9 or less, a total carbon number of 8 The following arylthio groups, lower alkylthio groups, total carbon number 4
In addition to representing the following acylamino groups, it represents that they may be linked to V ₁ or V ₃ to form a benzene ring. V ₃ represents a hydrogen atom, a methyl group or a methoxy group. V ₄ represents an electron-withdrawing group, and V ₅ represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom. R ₂₁ , R ₂₂ and R _{23, which} may be the same or different, each represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms,
At least one of R ₂₁ , R _{22 and} R ₂₃ is a group having a sulfo group or a carboxy group. X ₂₁ represents a counter ion necessary for neutralizing the charge. n ₂₁ is 0 or 1
And is 0 in the case of an inner salt. General formula (3) In the formula, V ₃₁ and V ₃₃ represent a hydrogen atom or an electron-withdrawing group, and V ₃₂ and V ₃₄ represent an electron-withdrawing group. R ₃₁ , R ₃₂ ,
R ₃₃ and R ₃₄ may be the same or different and each represents an alkyl group or an alkenyl group having a total carbon number of 10 or less, and at least one of R ₃₁ , R ₃₂ , R _{33 and} R ₃₄ is a sulfo group. A group having a group or a carboxy group. X ₃₁ represents a counter ion necessary for neutralizing the electric charge. n ₃₁ represents 0 or 1, and is 0 in the case of an intramolecular salt. 2. A hydrazine derivative is represented by the following general formula (4):
2. The method is selected from (5) and (6).
The silver halide photographic light-sensitive material described in. General formula (4) In the formula, R ₁ represents an aliphatic group or an aromatic group, further the -O- as part of a substituent group _{(CH 2 CH 2 O) n} - or _{-O- (CH 2 CH (OH)} CH 2 O ) It is a group containing a partial structure of n- (where n is an integer of 3 or more) or containing a quaternary ammonium cation as a part of the substituent. G ₁ is -CO- group, -COCO- group, -C
S- _{groups, -C (= NG 2 R 2} ) - group, -SO- group, -S
O ₂ - group or _{-P (O) (G 2 R} 2) - represents a group. G
₂ is a mere bond, -O- group, -S- group or -N (R
₂ )-group, R ₂ represents an aliphatic group, an aromatic group, or a hydrogen atom, and when a plurality of R _2's are present in the molecule, they may be the same or different. One of A ₁ and A ₂ is a hydrogen atom, and the other is a hydrogen atom or an acyl group, an alkyl group or an arylsulfonyl group. General formula (5) In the formula, R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group, and may be substituted. G is -CO- group, -SO ₂
A group, a —SO— group, a —COCO— group, a thiocarbonyl group, an iminomethylene group or a —P (O) (R ₃ ) — group, and R ₂ is an electron having at least one carbon atom substituted with G. Represents a substituted alkyl group substituted with an attractive group. R ₃
Represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group or an amino group. General formula (6) In the formula, A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a sulfinic acid residue or an acyl group,
_a represents an aliphatic group, an aromatic group, or a heterocyclic group,
_b represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group, and G ₁ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group. Where R _a and R _b
At least one of them has an adsorption promoting group for silver halide. 3. A silver halide emulsion layer or another hydrophilic colloid layer containing at least one compound selected from amine derivatives, onium salts, disulfide derivatives and hydroxymethyl derivatives in at least one layer. The silver halide photographic light-sensitive material according to claim 2. 4. An image forming method, which comprises developing the silver halide photographic light-sensitive material according to claim 1 with a developer having a pH of 9.6 or more and less than 11.0.