JPH11327068A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To decrease changes in density by exposure with low illuminance and exposure with high illuminance and to obtain a white-and-black image from a dye image. SOLUTION: This material has at least one silver halide emulsion layer on a supporting body, and the silver halide emulsion layer has >=95 mol.% silver chloride content in silver halide particles and contains a yellow coupler, a magenta coupler and a cyan coupler. The silver halide particle in the silver halide emulsion has a local layer essentially comprising silver bromide on its surface, and the local layer contains iridium. The silver halide particle is not chemically sensitized. In the image forming method, the silver halide photographic sensitive material is treated with a color developer which does not substantially contain benzyl alcohol.

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 an image forming method, and more particularly, to a color which can be used for both low-light exposure and high-light exposure and is substantially free of benzyl alcohol. Monotone using dye images that can be processed with a developer (e.g.,
The present invention relates to a photographic light-sensitive material capable of forming an image (black and white, sepia tone) and an image forming method.

[0002]

2. Description of the Related Art Normally, a black-and-white photographic image is formed by processing a black-and-white photographic light-sensitive material with a black-and-white developer to form a black-and-white image with a silver image. Further, by processing this black and white image, a sepia tone image can be obtained. On the other hand, it is also known to obtain a black-and-white image by adjusting the filter of a multilayer color photographic material using a yellow coupler for a regular photosensitive layer, a magenta coupler for an orthophotosensitive layer, and a cyan coupler for a panchromatic photosensitive layer. Further, the panchromatic sensitized silver halide emulsion layer, using a yellow coupler, a magenta coupler and a cyan coupler, color development processing,
It is also known to obtain a black and white image (for example,
0-20432). A photographic light-sensitive material that forms a black-and-white image by this color developing process is a color developing process.
At present, a so-called mini-lab development processor is widely used, and it can be said to be a preferable black-and-white image forming material. However, this photographic light-sensitive material is suitable for low-illumination exposure, for example, tungsten exposure, but soft illumination occurs in high-illumination exposure, for example, exposure using a laser such as a light emitting diode or a semiconductor as a light source. The inventors have found. At present, there are few mini-lab development processors using this laser as a light source, but at present, digitization is progressing, and photographic photosensitive materials suitable for this laser as a light source are preferable.

[0003]

SUMMARY OF THE INVENTION A first object of the present invention is to form a black-and-white or sepia-tone monotone image from a dye image, which can be applied to both low-light exposure and high-light exposure. The object of the present invention is to provide a silver halide photographic light-sensitive material which can be used. A second object of the present invention is to provide an image forming method capable of forming a black-and-white, sepia-tone monotone image by a dye image by processing with a color developer containing substantially no benzyl alcohol. is there.

[0004]

An object of the present invention is to provide a silver halide emulsion layer comprising a silver halide emulsion layer having a silver halide content of 95 mol% or more, a yellow coupler, a magenta coupler and a cyan coupler. In a silver halide photographic material having at least one silver halide emulsion layer containing a coupler, silver halide grains of the silver halide emulsion have a localized layer mainly composed of silver bromide on the surface, The localized layer contains iridium, and the silver halide grains are not chemically sensitized. A silver halide photographic light-sensitive material, and a color developer containing the silver halide photographic light-sensitive material substantially free of benzyl alcohol This was achieved by an image forming method in which development processing was performed. On this occasion,
The amount of iridium contained in the silver halide grains of the silver halide emulsion is 10 ^-6 to 10 based on 1 mol of the silver halide.
When it is in the range of ^-8 mol, more preferable photographic characteristics can be obtained.

For the exposure of the silver halide photographic light-sensitive material of the present invention, both low illuminance exposure and high illuminance exposure can be used. Low illuminance exposure means that the exposure time is usually 10 ^-2 seconds or more, and high illuminance exposure means that the exposure time is shorter than 10 ^-2 seconds. As a light source for low-illumination exposure, tungsten light is generally used. Xenon lamps, light-emitting diodes, He-Ne lasers, argon lasers, He-Cd lasers, semiconductor lasers, light sources in which a semiconductor laser and a wavelength conversion element made of a nonlinear optical material are combined, and the like are used as light sources for high-illuminance exposure.

[0006] The halogen composition of the silver halide emulsion used in the present invention is such that 95 mol% or more of the silver halide grains are silver chloride and substantially consist of silver chlorobromide containing no silver iodide. preferable. The silver halide grains used in the present invention are characterized in that a layer mainly composed of silver bromide is localized on the surface of the grains, and that the localized layer contains iridium. This localized layer of silver bromide may cover the entire surface of silver halide grains mainly composed of silver chloride, may partially cover the surface, or may be formed by epitaxy bonding to the surface. May be used. A layer mainly composed of silver bromide means that 60 mol% or more of silver halide contained in the layer is composed of silver bromide. The silver bromide content of the layer is preferably high,
More preferably, 80 mol% or more is composed of silver bromide.
The interface between the silver bromide localized layer and the other portions may have a clear boundary or may have a transition region.

In the silver halide grains of the present invention, 0.1 to 5.0 mol% of the silver halide constituting the grains is made of silver bromide. The silver bromide may be present not only in the localized layer of silver bromide on the surface of the silver halide grains but also inside the silver halide grains, but it is preferred that almost all of the silver bromide be present on the surface of the grains. The average grain size of the silver halide grains (the grain size in the case of spheres or grains similar to spheres, the grain size in the case of cubic grains is the length of the ridge, and the average based on the projected area) is not particularly limited, but is 3 μm. The following is preferred. The particle size distribution may be narrow or wide. The silver halide grains may have a regular crystal form such as a cube or an octahedron, or may have an irregular crystal form such as a sphere or a plate, or a composite of these crystal forms. May be. It may consist of a mixture of particles of various crystal forms. Further, an emulsion may be used in which tabular silver halide grains having a diameter of 5 times or more of the thickness thereof occupy 50% or more of the total projected area.

The silver halide emulsion used in the present invention is:
P. Chimie et Ph. By Glafkids
ysque Photographique (Pau
1Montel, 1967); F. Duff
in, Photographic Emulsion
Chemistry (The Focal Pres
s company, 1966); L. Zelikman e
tal, Making and Coating
Photographic Emolsion (The
Focal Press, 1964) and the like. That is,
Any of the acidic method, neutral method, ammonia method, etc. may be used,
As a method for reacting a soluble silver salt with a soluble halogen salt, any of a forward flow method, a reverse flow method, a simultaneous mixing method, and a combination thereof may be used.

As one method of the double jet method, a method of maintaining a constant pAg in a solution in which silver halide is formed,
The so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained. A method for producing epitaxial silver halide grains is described in EP-A-273,430.
A method for producing silver halide grains having a transition region is described in German Patent No. 2,921,164. Two or more types of silver halide emulsions formed separately may be used as a mixture.

The localized layer mainly composed of silver bromide on the surface of the present invention contains iridium. The amount of iridium contained is from 1.0 × 10 ⁻⁶ to 1 mol of silver halide.
A range of 1.0 × 10 ⁻⁸ mol is preferred. In order to contain iridium in a localized layer mainly composed of silver bromide, it is possible to form the localized layer by using an iridium compound. As the iridium compound, trivalent or tetravalent salts or complex salts, for example, iridium (III) chloride, iridium (III) bromide, iridium (II) chloride, sodium hexachloroiridium (III), Hexachloroiridium (I
V) Potassium acid and the like. When preparing the silver halide grains of the present invention, cadmium salt, zinc salt,
A lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, and the like may coexist. The silver halide emulsion of the present invention does not undergo so-called chemical sensitization. By not performing chemical sensitization, the preferable effects of the present invention can be obtained.

The silver halide emulsion of the present invention comprises at least one sensitizing dye represented by the general formula (I), at least one sensitizing dye represented by the general formula (II), and
It is preferable that at least one of the sensitizing dyes represented by the general formula (III) or (IV) is spectrally sensitized.

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In the general formula (I), R ₁ and R _{2 each} have 1 carbon atom.
To 6 alkyl groups (e.g., methyl group, ethyl group, n-
Propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group, isohexyl group, etc.), carbon number 1
To 6 substituted alkyl groups [e.g., hydroxylalkyl group (e.g., 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, etc.), sulfoalkyl group (e.g., 2-sulfoethyl group, 3-sulfopropyl) Group, 3-sulfobutyl group, 4-sulfobutyl group, etc.), carboxyalkyl group (eg, 2-carboxyethyl group, 3-carboxypropyl group, 3-carboxybutyl group, 4-carboxybutyl group, etc.)], aralkyl group ( For example, a benzyl group or a 2-phenylethyl group). It is preferable that _one of R ₁ and R ₂ is a substituted alkyl group. Z ₁ and Z ₂ represent a substituent (for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a cyano group, an alkoxycarbonyl group, a trifluoromethyl group, an alkylsulfonyl group, an alkylsulfamoyl group, an acylamino group, an alkylcarbamoyl Group, acetoxy group, etc.) represents a group of non-metallic atoms necessary for forming a benzene nucleus or a naphthalene nucleus which may have a nucleus. X ₁ ^- represents a commonly used anion group (for example, chloride ion, bromine ion, iodine ion, perchlorate ion, p-toluenesulfonic acid ion, ethyl sulfate ion, etc.). P ₁ represents 1 or 2, and when P ₁ is 1, an internal salt is formed. Next, specific examples of the sensitizing dye represented by formula (I) will be described.

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In the general formula (II), R ₃ and R _{4 each} have 1 carbon atom.
To 6 alkyl groups (e.g., methyl group, ethyl group, n-
Propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group, isohexyl group, etc.), carbon number 1
To 6 substituted alkyl groups [e.g., hydroxylalkyl group (e.g., 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, etc.), sulfoalkyl group (e.g., 2-sulfoethyl group, 3-sulfopropyl) Group, 3-sulfobutyl group, 4-sulfobutyl group, etc.), carboxyalkyl group (eg, 2-carboxyethyl group, 3-carboxypropyl group, 3-carboxybutyl group, 4-carboxybutyl group, etc.)], aralkyl group ( For example, a benzyl group or a 2-phenylethyl group). It is preferable that _one of R ₁ and R ₂ is a substituted alkyl group. A ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc.), an aryl group (eg, a phenyl group, etc.), and Y ₁ and Y ₂ sulfur atom, an oxygen atom, a selenium atom, an N-R _5, R ₅ represents an alkyl group having 1 to 3 carbon atoms (e.g., methyl group, ethyl group, n- propyl group, an isopropyl group, etc.). Z ₃ and Z ₄ form a benzene ring or a naphthalene ring which may have a substituent (eg, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a carbonyl group, an alkoxycarbonyl group, a cyano group, etc.) Represents a group of nonmetallic atoms required for X ₂ ^- represents an anion group (for example, chloride ion, bromine ion, iodine ion, perchlorate ion, p-toluenesulfonic acid ion, ethyl sulfate ion, etc.). P ₂ represents 1 or 2, and when P ₂ is 1, an internal salt is formed. Next, specific examples of the sensitizing dye represented by the general formula (II) will be described.

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In the general formulas (III) and (IV),
R ₆ , R ₇ , R ₈ and R ₉ are an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-hexyl group) , Isohexyl group, etc.), a substituted alkyl group having 1 to 6 carbon atoms [eg, a hydroxylalkyl group (eg, 2-
Hydroxyethyl group, 3-hydroxypropyl group, 2-
Hydroxypropyl group, etc.), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 3-
Sulfobutyl group, 4-sulfobutyl group, etc.), carboxyalkyl group (eg, 2-carboxyethyl group, 3-carboxypropyl group, 3-carboxybutyl group, 4-carboxybutyl group, etc.)], aralkyl group (eg, benzyl group) , 2-phenylethyl group, etc.). R ₆ and R ₇
Is preferred when any one of them is a substituted alkyl group. Similarly, it is preferable that one of R ₈ and R ₉ is a substituted alkyl group. A ₂ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, n
-Propyl group, isopropyl group, etc.) and aryl group (for example, phenyl group etc.). Z ₅ , Z ₆ , Z ₇ and Z ₈ represent a substituent (for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a cyano group, an alkoxycarbonyl group,
Trifluoromethyl group, alkylsulfonyl group, alkylsulfamoyl group, acylamino group, alkylcarbamoyl group, acetoxy group, etc.), which represents a group of non-metallic atoms necessary for forming a benzene nucleus or a naphthalene nucleus. . Z ₉ represents a nonmetallic atom group necessary for forming a 6-membered ring nucleus which may have a substituent (for example, an alkyl group). X ₃ ^- and X ₄ ^- represent commonly used anion groups (for example, chloride ion, bromine ion, iodine ion, perchlorate ion, p-toluenesulfonic acid ion, ethyl sulfate ion, etc.). P ₃ and P ₄ represent 1 or 2, and P ₃
And when P ₄ is 1, an inner salt is formed. Next, specific examples of the sensitizing dyes represented by formulas (III) and (IV) will be described.

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These sensitizing dyes can be easily synthesized by the method described in Heterocyclic Compounds, Cyanine Soybean and Released Compounds. These sensitizing dyes are used at a concentration of 10 ^-6 to 10 ^-3 mol per mol of silver halide in the silver halide emulsion. When such a sensitizing dye is added to a silver halide emulsion, a method of directly dispersing the sensitizing dye in the silver halide emulsion may be used, or a suitable solvent such as methyl alcohol, ethyl alcohol, Acetone, N, N-
A method of dissolving in dimethylformamide, ethyl acetate or a mixed solvent of these, or a solvent containing a surfactant therein, and then adding the resultant to a silver halide emulsion can be applied. These sensitizing dyes can be added to a silver halide emulsion during silver halide grain formation or after completion of physical ripening. Preferably, it is added to a silver halide emulsion after completion of physical ripening. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, aminostyryl compounds substituted with a nitrogen-containing heterocyclic group (for example, US Pat. No. 2,933,390)
No. 3,635,721), an aromatic organic acid formaldehyde condensate (for example,
Compounds described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like.

Examples of the yellow coupler that can be used in the present invention include oil-protected acylacetamide couplers. Specific examples are:
U.S. Pat. Nos. 2,407,210 and 2,875,0
No. 57 and No. 3,265,506. In the present invention, the use of 2-equivalent yellow couplers is described in U.S. Pat. No. 3,408,19.
No. 4, No. 3,447,928, No. 3,933,5
No. 01 and 4,401,752, etc., and an oxygen atom-elimination type yellow coupler described in Japanese Patent Publication No.
No. 8-10739, U.S. Pat. No. 4,022,620
No. 4,326,024, Research Disclosure 18,053 (April 1987), British Patent No. 1,425,020, West German Published Patent No. 2,219,917, No. 2 , 261,361, 2,329,587, and 2,433,812, and the like. α-pivaloylacetanilide-based couplers are characterized by the fastness of coloring dyes, while α-benzoylacetanilide-based couplers are characterized by good coloration.

Examples of the magenta coupler that can be used in the present invention include oil-protected indazolone-based or cyanoacetyl-based couplers, and preferably pyrazoloazole-based couplers such as 5-pyrazolone- and pyrazolotriazole-based couplers. Can be. As the 5-pyrazolone-based coupler, those in which the 3-position is substituted with an arylamino group or an acylamino group are preferable from the viewpoint of the hue and color developing speed of the coloring dye, and specific examples thereof are described in US Pat.
No. 1,082, No. 2,343,703, No. 2,6
No. 00,788, No. 2,908,573, No. 3,
No. 3,152,896 and 3,936,015, and the couplers described in the respective specifications. 2-equivalent 5-pyrazolone couplers are particularly preferred, and the leaving group is US Pat.
A nitrogen atom leaving group described in JP-A-310,619;
An arylthio group described in U.S. Pat. No. 4,351,897 can be mentioned. Further, a 5-pyrazolone-based coupler having a ballast group described in European Patent No. 73,636 is a preferred coupler having high color-forming reactivity. Examples of pyrazoloazole-based couplers include pyrazolo [1,5-b] [1,2,4] triazoles described in European Patent No. 119,860 and US Pat. No. 3,369,897. , The pyrazolotetrazole described in Research Disclosure 24, 220 (June 1984), and the pyrazolopyrazoles described in Research Disclosure 24, 230 (June 1984). Can be mentioned. JP 59
The imidazopyrazoles and pyrazolo [1,5-b] [1,2,4] triazoles described in JP-A-162548 are preferable because they have little yellow sub-absorption of the coloring dye and have high light fastness.

The cyan couplers usable in the present invention include oil-protected naphthol couplers and phenol couplers, and the naphthol couplers described in US Pat. No. 2,474,293 can be used. Couplers, preferably U.S. Pat. No. 4,052,21
No. 2, No. 4,143,396, No. 4,228,2
No. 33, No. 4,296,200, and high-activity two-equivalent naphthol couplers of the oxygen atom-elimination type described in the respective specifications. Examples of phenol couplers include U.S. Pat. Nos. 2,369,929 and 2,42.
No. 3,730, No. 2,772,162, No. 2,8
And couplers described in each specification such as No. 01,171 and No. 2,895,826.
Cyan couplers which are robust to temperature and humidity are preferred, and phenolic cyan couplers described in U.S. Pat. No. 3,772,022, U.S. Pat. Nos. 2,772,162, 3, 2,5-diacylamino-substituted phenols described in JP-A Nos. 758,308, 4,126,396, and 4,327,137, and JP-A-59-166956. Couplers, U.S. Pat. Nos. 3,446,622 and 4,3
No. 33,999, No. 4,451,559 and No. 4,427,767.
A phenolic coupler having a phenylureido group at the -position and an acylamino group at the 5-position. Hereinafter, specific examples of the coupler used in the present invention are shown.

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The coupler used in the present invention can be introduced into a silver halide emulsion by various dispersion methods. For example, a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, more preferably an oil-in-water dispersion method can be used. In the oil-in-water dispersion method, a high-boiling organic solvent having a boiling point of 175 ° C. or higher and a low-boiling auxiliary solvent are dissolved in a single solution or a mixture thereof, and then water or gelatin is dissolved in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. The high boiling point organic solvent is described in U.S. Pat. No. 2,322,027. The dispersion may be accompanied by a phase inversion, and if necessary, the auxiliary solvent can be used for coating after being removed or reduced by distillation, noodle washing, ultrafiltration or the like.
In the silver halide photographic light-sensitive material of the present invention, the preferred amounts of the yellow coupler (Y), magenta coupler (M) and cyan coupler (C) are in a molar ratio, and in a black-and-white monotone image, Y: M: C = 2. 0.0-4.0: 1: 2.5
To 5.0, and for a sepia monotone image, Y: M: C = 4.5 to 8.0: 1: 1.5 to 3.5.
Range.

Examples of the high boiling organic solvent include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), and esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate) ,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, trididecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, benzoate (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethyloxyl-p-hydroxybenzoate, etc.), amide (diethyldodecaneamide, N-tetradecylpyrrolidone, etc.), alcohol or phenol (isostearyl alcohol, 2,4-di-
t-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-t-) Octylaniline, etc.), and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, those having a boiling point of about 30 ° C. to about 60 ° C. can be used. Specific examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-ethoxyethyl acetate. And dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Published Patent Nos. 2,541,274 and 2,541,230. Other exemplified compounds can be synthesized in the same manner as described above. As the binder or protective colloid that can be used in the emulsion layer or other hydrophilic colloid layers of the photographic light-sensitive material of the present invention, mainly gelatin is used.
For example, gelatin derivatives, albumin, proteins such as casein, ethyl cellulose, cellulose derivatives such as carboxymethyl cellulose, sugar derivatives such as starch derivatives, polyvinyl alcohol, polyacrylic acid, polyacrylamide, mono- or copolymers such as polymethacrylic acid Such hydrophilic polymers can be used.

The emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or development processing, or stabilizing photographic performance. Can be added. Examples of the compound include azoles such as nitroindazoles, nitrobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazole (particularly,
-Phenyl-5-mercaptotetrazole), mercaptotriazines, thioketone compounds, azaindenes, for example, triazaindenes and tetraazaindenes (particularly, 4-hydroxy-1,3,3a, 7-tetrazaindene) ), Pentaazaindenes, benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and many other compounds conventionally known as antifoggants or stabilizers. Of these, particularly preferred are benzotriazoles and nitroindazoles. These compounds may be contained in a processing solution used for the development processing. In the emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention,
Hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, and the like can be contained as color fog inhibitors.

The emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention may contain an inorganic or organic hardener. Examples of the hardener include a chromium salt (such as chrome alum), an N-methylol compound, a dioxane derivative, and an active vinyl compound (for example, 1,2,5-triacryloyl-hexahydro-s-triazine,
3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (eg, 2,4-dichloro-6-hydroxy-s-triazine, etc.), and mucohalic acids (eg, mucochloric acid, mucophenoxycyclolic acid, etc.). These hardeners can be used alone or in combination. Emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention, coating aid, antistatic,
Surfactants can be contained for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic properties (for example, acceleration of development, high contrast, sensitization, etc.). Examples of the surfactant include saponin, alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglyceride, alkylphenol polyglyceride, etc.), fatty acid esters of polyhydric alcohol, and sugars. Nonionic surfactants such as alkyl esters, anions having an acidic group such as carboxy group, sulfo group, sulfate group, phosphate group such as alkyl carboxylate, alkyl sulfate, alkyl phosphate, etc. Amphoteric surfactants, amino acids, aminoalkylsulfonic acids, amphoteric surfactants such as aminoalkylsulfuric acid or phosphate esters, aliphatic or aromatic quaternary ammonium salts, or heterocyclic quaternary ammonium salts Etc. It can be exemplified emissions surfactant.

The emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention may contain a dispersion of a water-soluble or poorly-soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, (meth) acrylamide, vinyl ester, glycidin (meth) acrylate, acrylonitrile, styrene, etc., alone or in combination, or acrylic acid, methacrylic acid, It can be used in combination with a polymer having a combination of α, β-unsaturated dicarboxylic acid, styrenesulfonic acid and the like as a monomer component. Other hydrophilic colloid layers other than the silver halide emulsion layer in the present invention include a surface protective layer, a filter layer, an antihalation layer, and an antistatic layer. A hydrophilic colloid layer such as a surface protective layer may contain a matting agent for the purpose of preventing adhesion and improving the surface condition. As matting agents, US Pat. Nos. 2,701,245 and 2,992,101
No. 4,142,894, No. 4,396,70
Fine particles such as polymethyl methacrylate homopolymers, copolymers of methyl methacrylate and methacrylic acid, starch, silica, and magnesium oxide described in the specifications of No. 6 can be used. The surface protective layer includes a silicone compound described in each of U.S. Pat. Nos. 3,489,576 and 4,047,958.
No. 23139, colloidal silica, paraffin wax, higher fatty acid esters and the like can be added.

The photographic light-sensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, U.S. Patent Nos. 3,533,794 and 4,236,013
Benzotriazoles substituted with an aryl group described in U.S. Pat. No. 4,195,999 described in Japanese Patent Publication No. 51-6540 and European Patent No. 57,160. Butadiene described, U.S. Pat. Nos. 3,705,805 and 3,70
7,375, cinnamic acid esters described in the specifications of US Pat. No. 3,215,230 and British Patent No. 1,321,355, benzophenones described in the specifications of US Pat. Polymer compounds having an ultraviolet absorbing group described in the specifications of 3,761,272 and 4,431,726 can be used. U.S. Pat. Nos. 3,499,762 and 3,700,455
UV-absorbing optical brighteners described in the above-mentioned specifications may be used. The photographic material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes,
Hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes are included. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

In the photographic light-sensitive material of the present invention, formalin scavengers can be used in the emulsion layer and other hydrophilic colloid layers, and they can be used alone or in combination of two or more. As a formalin scavenger, for example,
Urea-based compounds described in Japanese Patent Application No. 9-312843 can be exemplified.

In the photographic light-sensitive material of the present invention, an anti-fading agent can be used in the emulsion layer and other hydrophilic colloid layers, and the anti-fading agent can be used alone or in combination of two or more. Examples of the discoloration inhibitor include, for example, JP-A-59-12
Phenols or phenyl ether compounds described in JP-A-5732, metal complexes described in JP-A-60-97353, hindered amines or hindered phenol compounds described in JP-A-62-115157, Examples thereof include metal complexes described in Japanese Unexamined Patent Publication No. 61-140941. In the emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as plasticizers. Further, a fluorescent whitening agent, a development accelerator, a pH adjuster, a thickener, an antistatic agent and the like can be added to the emulsion layer and other hydrophilic colloid layers.

The support used in the photographic light-sensitive material of the present invention may be a film made of a synthetic polymer such as cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, polycarbonate, etc., baryta paper, or α-olefin binder. Paper (eg, polyethylene, polypropylene) or the like, or synthetic paper or the like can be used. The support may be colored using a dye or a pigment. When such a support is used for a reflective material, it is preferable to add a white pigment to the support or the laminate layer. Examples of the white pigment include titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white, alumina white, and titanium phosphate. In particular, titanium dioxide, barium sulfate, and zinc oxide are useful. The surface of these supports is
In general, an undercoating treatment is performed to improve the adhesion to a photographic emulsion. The surface of the support may be subjected to a treatment such as corona discharge or ultraviolet irradiation before or after the undercoating treatment. When these supports are used for a reflective material, a hydrophilic colloid layer containing a white pigment at a high density is further provided between the support and the emulsion layer to improve whiteness and sharpness of a photographic image. Can be. In the photographic light-sensitive material of the present invention, when a synthetic resin film kneaded with a white pigment is used, in addition to the improvement of smoothness, gloss, and sharpness, a photographic image excellent in saturation, depiction of a dark portion, and the like can be obtained. . In this case, polyethylene terephthalate and cellulose acetate are particularly useful as synthetic resin films, and barium sulfate and titanium oxide are particularly useful as white pigments.

The silver halide photographic light-sensitive material of the present invention can form a black-and-white image by exposing from a black-and-white negative film or from a color negative film. The color developer that can be used in the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine developing agent. As a developing agent, 4-
Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline and the like. Color developers include carbonates, pH buffers such as borates and phosphates, bromides,
Antifoggants such as iodides and organic antifoggants can be included. If necessary, a water softener, a sulfite of an alkali metal, a development accelerator such as diethylene glycol, polyethylene glycol, a quaternary ammonium salt, an amine, a competing coupler, a fogging agent such as sodium boron hydride, 1-phenyl Auxiliary developing agents such as -3-pyrazolidone, viscosity-imparting agents, US Pat. No. 4,082,7
It may contain a polycarboxylic acid-based chelating agent described in JP-A No. 23, an antioxidant described in West German Patent Application No. 2,622,950, and the like. The fact that benzyl alcohol is not substantially contained in the developer means that even if benzyl alcohol is contained in the developer, it is not more than 5 ml / l. More preferably, it does not contain benzyl alcohol.

The silver halide photographic light-sensitive material of the present invention is usually subjected to bleaching after color development. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitroso compounds are used. For example, ferricyanide, dichromate, an organic acid salt of iron (III) or cobalt (III), for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3
-Aminopolycarboxylic acids such as -diamino-2-propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid, persulfates, manganates, nitrosophenols and the like can be used. Of these, sodium ethylene (III) ethylenediaminetetraacetate and ammonium (III) ethylenediaminetetraacetate are particularly useful. The iron (III) complex salt of ethylenediaminetetraacetate is useful both in an independent bleaching solution and in a single-bath bleach-fixing solution. After the color development or the bleach-fixing process, a washing process or a stabilizing process alternative to washing is performed.

In the case of continuous development, color development is 18 °
It can be carried out at any temperature between C and 55 ° C. Preferably, it is performed at 30 ° C. or higher, particularly preferably at 35 ° C. or higher. The time required for development is in the range of about 20 seconds to about 1 minute 30 seconds, and particularly preferably 40 seconds to 50 seconds. The liquid replenishment rate is in the range of 30 ml to 300 ml, preferably in the range of 40 ml to 170 ml per square meter of the processing area.
Bleaching and fixing can be carried out at any temperature between 18 ° C. and 50 ° C., preferably 30 ° C. or higher. When the temperature is 35 ° C. or more, the processing time can be reduced to 1 minute or less, and the replenishment rate of the solution is 30 ml to 220 m per square meter of the processing area.
1 can be reduced. After color development or bleach-fixing, the solution can be processed within 2 minutes using a stabilizing bath instead of washing, with the replenishing rate of 200 ml to 400 ml per square meter of the processing area.

The colored dye deteriorates and fades due to mold during storage, in addition to being deteriorated by light, heat or humidity. The cyan dye is particularly susceptible to deterioration by mold, and it is preferable to use a fungicide. A specific example of a fungicide is disclosed in
Examples thereof include 2-thiazolylbenzimidazoles described in JP-A-7-157244. The fungicide may be incorporated in the silver halide photographic material,
It may be added from the outside in the development processing step, and can be added in any step as long as it coexists with the processed photosensitive material.

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DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments. Example 1 Preparation of Emulsion A-100 45.0 g of lime-processed gelatin was added to 1,500 ml of distilled water, dissolved at 40 ° C., adjusted to pH 3.5 with sulfuric acid, 4.5 g of sodium chloride and N , N'-dimethylimidazolidin-2-thione, 0.05 g, was added and the temperature was raised to 65.0 ° C. Subsequently, 35.7 g of silver nitrate
Was dissolved in 250 ml of distilled water, and sodium chloride 1
A solution obtained by dissolving 2.3 g in 250 ml of distilled water was added and mixed with the above solution at 65.0 ° C. over 20 minutes with vigorous stirring (liquid 1). Next, a solution prepared by dissolving 187.5 g of silver nitrate in 500 ml of distilled water and 64.5 g of sodium chloride.
g was dissolved in 500 ml of distilled water, and the mixture was added to solution 1 at 65.0 ° C. with vigorous stirring over 25 minutes and mixed (solution 2). Next, a solution prepared by dissolving 26.8 g of silver nitrate in 60 ml of distilled water, 9.2 g of sodium chloride and 7.4 × 10 ^−5.
A solution prepared by dissolving moles of K ₃ Fe (CN) ₆ in 60 ml of distilled water was added to and mixed with a vigorously stirred solution 2 of 65.0 ° C. over 5 minutes (solution 3). Liquid 3 was desalted and washed with water at 40 ° to obtain a silver chloride cubic emulsion having a side length of 0.65 μm. Next, 2,000 ml of distilled water was added to this emulsion,
25.0 g of lime-processed gelatin was added, and the pAg was adjusted to 7.9 with sodium chloride and sodium hydroxide.
Was adjusted to 6.5, and then cooled and set. The silver chloride emulsion thus obtained was designated as A-100.

Preparation of Emulsion A-101 Emulsion A-100 was heated to 55 ° C. and dissolved, and 1.0 × 10 ^-4 mol of sensitizing dye I-1 per mol of silver was added.
1.3 × 10 ^-4 mol of I-1 and 4.0 × 10 ^-5 mol of sensitizing dye III-1 were added, and the mixture was stirred for 20 minutes, and then monodispersed ultrafine particles having an average particle size of 0.05 μm. The silver bromide emulsion was added with 0.5 mol% as silver halide and stirred for 20 minutes, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer to the silver halide emulsion. 50 mg was added per mole. The emulsion thus obtained was designated as A-101. Preparation of Emulsion A-102 In the preparation of Emulsion A-101, a monodispersed ultrafine silver bromide emulsion was added, and the mixture was stirred for 20 minutes, and triethylthiourea was added in an amount of 1.3 × 10 ⁻⁵ mol per mol of silver halide. Emulsion A-1 except that the mixture was stirred for 60 minutes and sulfur sensitized.
Emulsion A-102 was prepared in the same manner as in Emulsion 01. Preparation of Emulsion A-103 In the preparation of Emulsion A-102, the monodisperse ultrafine silver bromide emulsion added after the addition of the sensitizing dye was replaced with 3 × 10 ⁻⁸ mol of iridium hexachloride (IV) per mol of silver bromide. Emulsion A-103 was prepared in the same manner as Emulsion A-102, except that the composition contained potassium acid.

Preparation of Emulsion A-104 In the preparation of Emulsion A-102, the monodispersed ultrafine silver bromide emulsion added after the addition of the sensitizing dye was replaced with 2 × 10 ^-6 mol of iridium hexachloride per mol of silver bromide. Emulsion A-104 was prepared in the same manner as Emulsion A-102, except that the composition contained potassium (IV) acid. Preparation of Emulsion A-105 In the preparation of Emulsion A-102, the monodisperse ultrafine silver bromide emulsion added after the addition of the sensitizing dye was replaced with 3 × 10 ^-5 mol of iridium (IV) hexachloride per mol of silver bromide. Emulsion A-105 was prepared in the same manner as Emulsion A-102, except that the composition contained potassium acid. Preparation of Emulsion A-106 In the preparation of Emulsion A-102, the monodisperse ultrafine silver bromide emulsion added after the addition of the sensitizing dye was replaced with 2 × 10 ^-4 mol of iridium (IV) hexachloride per mol of silver bromide. Emulsion A-106 was prepared in the same manner as Emulsion A-102, except that the composition contained potassium acid.

Preparation of Emulsion A-107 In the preparation of Emulsion A-102, the monodispersed ultrafine silver bromide emulsion added after the addition of the sensitizing dye was mixed with 2 × 10 ^-3 mol of iridium hexachloride per mol of silver bromide. Emulsion A-107 was prepared in the same manner as Emulsion A-102, except that the composition contained potassium (IV) acid. Preparation of Emulsion A-108 In the preparation of Emulsion A-101, the monodisperse ultrafine silver bromide emulsion added after the addition of the sensitizing dye was replaced with 3 × 10 ^-8 mol of iridium (IV) hexachloride per mol of silver bromide. Emulsion A-108 was prepared in the same manner as Emulsion A-101, except that the composition contained potassium acid. Preparation of Emulsion A-109 In the preparation of Emulsion A-101, the monodisperse ultrafine silver bromide emulsion added after the addition of the sensitizing dye was replaced with 2 × 10 ^-6 mol of iridium (IV) hexachloride per mol of silver bromide. Emulsion A-109 was prepared in the same manner as Emulsion A-101, except that the composition contained potassium acid.

Preparation of Emulsion A-110 In the preparation of Emulsion A-101, the monodispersed ultrafine silver bromide emulsion added after the addition of the sensitizing dye was mixed with 3 × 10 ^-5 mol of iridium hexachloride per mol of silver bromide. Emulsion A-110 was prepared in the same manner as Emulsion A-101, except that the composition contained potassium (IV) acid. Preparation of Emulsion A-111 In the preparation of Emulsion A-101, the monodispersed ultrafine silver bromide emulsion added after the addition of the sensitizing dye was replaced with 2 × 10 ^-4 mol of iridium (IV) hexachloride per mol of silver bromide. Emulsion A-111 was prepared in the same manner as Emulsion A-101, except that the composition contained potassium acid. Preparation of Emulsion A-112 In the preparation of Emulsion A-101, the monodisperse ultrafine silver bromide emulsion added after the addition of the sensitizing dye was replaced with 2 × 10 ⁻³ mol of iridium hexachloride (IV) per mol of silver bromide. Emulsion A-112 was prepared in the same manner as Emulsion A-101, except that the composition contained potassium acid. Preparation of Emulsion A-113 In the preparation of Emulsion A-110, sensitizing dyes I-3 and I
Emulsion A-11 except for changing to I-20 and IV-10
Emulsion A-113 was prepared in the same manner as in Preparation Example No. 0.

A coupler dispersion was prepared as follows. After dissolving the coupler in di-n-butyl phthalate and ethyl acetate, it was added to an aqueous gelatin solution in the presence of a surfactant, and finely dispersed using an ultrasonic homogenizer. The silver halide emulsion and the coupler dispersion were mixed, and three layers were simultaneously coated on a polyethylene-coated paper so as to have the following layer structure. The silver halide emulsions used are shown in Table 1. In addition, 2,4-dichloro-6-hydroxy- is used as a hardener.
The s-triazine sodium salt was used to make up 2% by weight of the gelatin used. Top protective layer Gelatin 1.0 g / m ² UV absorbing layer UV absorber A 0.15 g / m ² UV absorber B 0.20 g / m ² High boiling point solvent 0.2 g / m ² Gelatin 0.6 g / m ²

Silver halide emulsion layer Silver halide emulsion Silver 0.7 g / m^Two Coupler (Y-8) 0.425 g / m^Two Coupler (M-10) 0.126 g / m^Two Coupler (C-13) 0.225 g / m^Two Coupler (C-1) 0.190 g / m^Two High boiling point solvent 1g / m^Two Gelatin 1.5g / m^Two Anti-irradiation dye A 0.02 g / m^Two Anti-irradiation dye B 0.01 g / m^Two  Anti-irradiation dye C 0.01 g / m^Two Support polyethylene coated paper

The other additives are as follows. High boiling point solvent di-n-butyl phthalate

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Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

[Table 1]

The thus-prepared sample was exposed through an optical wedge using a sensitometer for sensitometry (light source color temperature: 3200 K) for an exposure time of 0.2 second, and was subjected to the following color development, bleach-fixing, and water washing alternative stabilization. And dried. Processing process Processing temperature Processing time Color development 35 ° C 45 seconds Bleaching and fixing 35 ° C 45 seconds Washing alternative stability 35 ° C 90 seconds

Color developer 4-amino-3-methyl-N-ethyl-N- (β-methylsulfonamidoethyl) aniline sesquisulfate monohydrate 6.1 g triethanolamine 8.2 g nitrilotriacetic acid 1 0.5 g 1-hydroxyethylidene-1,1'-diphosphonic acid (60% aqueous solution) 1.6 g potassium hydroxide 4.2 g Tinopearl SFP 0.8 g potassium carbonate 0.9 g N, N-diethylhydroxylamine 4.0 g water The pH was adjusted to 10.1 by adding 10% sulfuric acid or a 20% aqueous potassium hydroxide solution to 1 l. In addition,
Tinopearl SFP is a fluorescent whitening agent manufactured by Ciba Geigy Aktien Gesellschaft.

Bleaching and fixing solution Sodium ferric ethylenediaminetetraacetate monohydrate 48.0 g Disodium ethylenediaminetetraacetate dihydrate 24.0 g Ammonium thiosulfate (70% aqueous solution) 148 ml Sodium bisulfite (anhydrous) 15.0 g Water And adjusted to pH 6.10 with 25% aqueous ammonia or 90% acetic acid.

Water-washing alternative stabilizer methanol 4.0 ml p-hydroxybenzoic acid-n-butyl ester 0.01 g thiabendazole 0.10 g ethylene glycol 6.0 ml Add water to make 1 liter. pH was 7.45.

The image of the optical wedge thus obtained was measured for the black density using a Macbeth RD918 densitometer, and the sensitivity, gradation and maximum density were measured from the characteristic curve. The sensitivity is the reciprocal of the exposure required to give a density 0.6 higher than the fog density, and is expressed as a relative value with the sensitivity of Sample 1 being 100. The gradation is 0.5 logE from the exposure amount for which the sensitivity was determined.
The density and the sensitivity with respect to the increased exposure amount were represented by a difference between the obtained densities. Table 2 shows the obtained results.

[0100]

[Table 2]

Next, the sample was subjected to a xenon pulsar MP-30.
Exposure was performed through an optical wedge using xenon flash light with an emission time of 10 ^-6 seconds using 0, processed in the above color development, bleach-fix and wash-alternative stability and dried. The image of the optical wedge thus obtained was measured for black density using a Macbeth RD918 densitometer, and the sensitivity, gradation, and maximum density were measured from the characteristic curve. The sensitivity was represented by a relative value with the sensitivity of Sample 1 being 100. Table 3 shows the obtained results.

[0102]

[Table 3]

From the results shown in Tables 2 and 3, Samples 2, 3, 4, 5, 6, and 7 using the chemically sensitized emulsion had lower sensitivities in high illuminance exposure than low illuminance exposure, It can be seen that the maximum density is extremely reduced. Sample 1 using an emulsion which did not use iridium and did not undergo chemical sensitization.
Indicates that the gradation, sensitivity, and maximum density are low in both the low illuminance exposure and the high illuminance exposure. The amount of iridium is 1.0 × 10 ^{−6 to} 1.0 × 10 ⁻⁸ per mole of silver halide.
Samples 9, 10, 11, and 13 of the present invention in the range of
Whether exposed at low or high illuminance, it has high sensitivity, little change in gradation and maximum density, shows favorable photographic characteristics, and can be used for both low and high illuminance exposure. it can. Samples 8 and 12 of the present invention in which the amount of iridium is out of the above range have inferior characteristics as compared with the samples 9 to 11 and 13 of the present invention, but have excellent characteristics as compared with comparative samples. You can see that.

[0104]

The silver halide photographic light-sensitive material of the present invention comprises:
It can be applied to low light exposure and high light exposure,
It is possible to obtain a black-and-white image of a dye image having a small change in density between low-illumination exposure and high-illumination exposure.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/20 G03C 1/20 5/29 5/29

Claims (6)

[Claims] 1. A silver halide emulsion layer comprising a silver halide emulsion layer having a silver chloride content of at least 95 mol% on a support.
In a silver halide photographic material having at least one silver halide emulsion layer containing a yellow coupler, a magenta coupler and a cyan coupler, the silver halide grains of the silver halide emulsion mainly consist of silver bromide on the surface. A silver halide photographic material having a localized layer, wherein the localized layer contains iridium and silver halide grains are not chemically sensitized. 2. The amount of iridium contained in silver halide grains of a silver halide emulsion is from 1.0 × 10 ^{-6 to} 1.0 × 10 ^-8 mol per mol of silver halide. 1
The silver halide photographic light-sensitive material as described above. 3. A silver halide emulsion comprising at least one compound represented by formula (I), at least one compound represented by formula (II), a compound represented by formula (III) or 2. The silver halide photographic light-sensitive material according to claim 1, comprising at least one compound represented by the general formula (IV). Embedded image In the formula, R ₁ and R ₂ represent an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 6 carbon atoms, and an aralkyl group, and Z ₁ and Z ₂ form a benzene ring and a naphthalene ring. represents a non-metallic atomic group necessary for, X ₁ ^- represents an anion group. P ₁ represents 1 or 2, and when P ₁ is 1, an internal salt is formed. Embedded image Wherein R ₃ and R ₄ are an alkyl group having 1 to 6 carbon atoms,
A ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an aryl group, and Y ₁ and Y ₂ represent a sulfur atom, an oxygen atom, selenium atom, an N-R _5, R ₅ is from 1 to 3 carbon atoms
Represents an alkyl group. Z ₃ and Z ₄ represents a nonmetallic atomic group necessary for forming a benzene ring, a naphthalene ring, X ₂ ^- represents an anion group. P ₂ represents 1 or 2, and when P ₂ is 1, an internal salt is formed. Embedded image Embedded image Wherein R ₆ , R ₇ , R ₈ and R ₉ are an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 6 carbon atoms,
A ₂ represents an aralkyl group, and A ₂ represents a hydrogen atom,
Represents an alkyl group or an aryl group. Z ₅ , Z ₆ , Z ₇ and Z ₈ represent a group of non-metallic atoms necessary for forming a benzene ring and a naphthalene ring, and Z ₉ represents a group of non-metallic atoms necessary for forming a 6-membered ring. X ₃ ^- and X ₄ ^- represents an anion group. P ₃ and P ₄ represent 1 or 2, and when P ₃ and P ₄ are 1, an inner salt is formed. 4. A silver halide emulsion layer comprising a silver halide emulsion layer having a silver chloride content of at least 95 mol% on a support.
An image forming method comprising: developing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a yellow coupler, a magenta coupler and a cyan coupler with a color developer containing substantially no benzyl alcohol, The silver halide grains of the silver halide emulsion have a localized layer mainly composed of silver bromide on the surface, the localized layer contains iridium, and the silver halide grains are not chemically sensitized. An image forming method comprising: 5. The image forming method according to claim 4, wherein the amount of iridium contained in the silver halide grains of the silver halide emulsion is from 10 ^-6 to 10 ^-8 mol per mol of silver halide. 6. A silver halide emulsion comprising at least one compound represented by formula (I), at least one compound represented by formula (II), a compound represented by formula (III) or The image forming method according to claim 4, comprising at least one compound represented by formula (IV). Embedded image In the formula, R ₁ and R ₂ represent an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 6 carbon atoms, and an aralkyl group, and Z ₁ and Z ₂ form a benzene ring and a naphthalene ring. represents a non-metallic atomic group necessary for, X ₁ ^- represents an anion group. P ₁ represents 1 or 2, and when P ₁ is 1, an internal salt is formed. Embedded image Wherein R ₃ and R ₄ are an alkyl group having 1 to 6 carbon atoms,
A ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an aryl group, and Y ₁ and Y ₂ represent a sulfur atom, an oxygen atom, selenium atom, an N-R _5, R ₅ is from 1 to 3 carbon atoms
Represents an alkyl group. Z ₃ and Z ₄ represents a nonmetallic atomic group necessary for forming a benzene ring, a naphthalene ring, X ₂ ^- represents an anion group. P ₂ represents 1 or 2, and when P ₂ is 1, an internal salt is formed. Embedded image Embedded image Wherein R ₆ , R ₇ , R ₈ and R ₉ are an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 6 carbon atoms,
A ₂ represents an aralkyl group, and A ₂ represents a hydrogen atom,
Represents an alkyl group or an aryl group. Z ₅ , Z ₆ , Z ₇ and Z ₈ represent a group of non-metallic atoms necessary for forming a benzene ring and a naphthalene ring, and Z ₉ represents a group of non-metallic atoms necessary for forming a 6-membered ring. X ₃ ^- and X ₄ ^- represents an anion group. P ₃ and P ₄ represent 1 or 2, and when P ₃ and P ₄ are 1, an inner salt is formed.