JP2002174872A - Silver halide emulsion and silver halide color photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide emulsion free of high illuminance failure due to (ultra)high illuminance exposure such as laser scanning exposure, having high sensitivity, giving contrasty gradation, excellent also in latent image stability after exposure and capable of stably forming a high contrast image, and to provide a silver halide color photosensitive material. SOLUTION: The silver halide emulsion contains silver halide grains doped with a six-coordination complex having at least one H2O as a ligand and Ir as a central metal at parts having >=90 mol% silver chloride content and doped with a six-coordination complex having Cl, Br or I as a ligand and Ir as a central metal at parts having >=40 mol% silver bromide content. The silver halide color photographic sensitive material comprises the silver halide emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion and a silver halide color photographic light-sensitive material using the same. More specifically, the present invention does not cause high illuminance failure even in digital exposure such as laser scanning exposure. The present invention relates to a silver halide emulsion from which a high-contrast image can be obtained, and a silver halide color photographic material using the same.

[0002]

2. Description of the Related Art In recent years, in the field of color printing using color photographic paper, the spread of digitization has been remarkable. For example, a digital exposure method using laser scanning exposure has been carried out from a processed color negative film to a color printer. It shows a dramatic increase in the penetration rate compared to the analog exposure method in which printing is performed directly. Such a digital exposure method is capable of performing image processing, and has a feature that high image quality can be obtained by the image processing, and plays an extremely important role in improving the quality of color prints using color photographic paper.
Also, with the rapid spread of electronic recording media such as digital cameras, the ability to easily obtain high-quality color prints from such electronic recording media is also an important factor, which is expected to bring about a dramatic spread.

On the other hand, as a color printing method, technologies such as an ink jet method, a sublimation method, and a color xerography have advanced respectively, and are being recognized as a color printing method, for example, for declaring photographic quality. Among them, the digital exposure method using color photographic paper is characterized by high image quality,
Due to high productivity and high image robustness, it is desired to further enhance these features, that is, to provide higher quality photographs more easily and at lower cost.

As a silver halide emulsion used for color photographic paper, a silver halide emulsion having a high silver chloride content has been used mainly due to a demand for rapid processing to enhance productivity. Such a silver halide emulsion having a high silver chloride content generally tends to cause low sensitivity softening (hereinafter, referred to as "high illuminance failure") at high illuminance exposure, and various techniques for improving this point have been disclosed. ing.

[0005] For example, a technique of doping iridium to improve the high illuminance failure of a silver chloride emulsion is known.
However, iridium-doped silver chloride emulsions
It is known that a latent image is sensitized within a short time after exposure. For example, in Japanese Patent Publication No. Hei 7-34103, a localized phase (site) having a high silver bromide content is provided, and iridium is added thereto. It is disclosed that doping can solve the problem of latent image sensitization. The silver halide emulsion prepared by this method can provide high sensitivity and high contrast even at relatively high illuminance exposure of about 1/100 second, and does not cause a problem of latent image sensitization.
When trying to maintain high sensitivity up to 1 μs ultra-high illuminance exposure required by a digital exposure method using laser scanning exposure, a problem that hard gradation was difficult to obtain became clear. U.S. Pat. No. 5,691,119 discloses a method for preparing an emulsion comprising silver halide grains having a localized phase (site) having a high silver bromide content, whereby the gradation under high illuminance is hardened. However, there is a drawback that the effect is not sufficient and the performance is not stabilized by repeated preparation.

[0006] US Patent Nos. 5,783,373 and 5,783,378 disclose a method of reducing high-illuminance failure and achieving high contrast by using at least three types of dopants. . However, a high contrast is obtained because a dopant having a desensitizing high contrast effect is used, and is incompatible with high sensitivity in principle.

In US Pat. Nos. 5,726,005 and 5,736,310, an emulsion containing a grain having a maximum of I concentration on the surface of a high silver chloride emulsion provides high sensitivity and high illuminance failure. It is disclosed that less emulsion can be obtained. Certainly, although higher sensitivity was obtained with higher illuminance exposure, it was found that the gradation was very soft and not suitable for digital exposure in which the dynamic range of the light amount was limited.

[0008]

As described above, even in (ultra) high illuminance exposure (digital exposure) by laser scanning exposure, high sensitivity can be obtained without high illuminance failure, and latent image sensitization can be achieved. A silver halide color photographic light-sensitive material (silver halide emulsion) capable of forming few images with high gradation
Is not yet provided.

An object of the present invention is to solve the above conventional problems and achieve the following objects. That is, the present invention provides a high-sensitivity hard tone gradation without high illuminance failure at the time of (ultra) high illuminance exposure (digital exposure) such as laser scanning exposure, and a halogenated image with less latent image sensitization. It is intended to provide a silver emulsion. In addition, the present invention can provide a high-sensitivity, hard gradation without accompanying high illuminance failure due to (ultra) high illuminance exposure (digital exposure) such as laser scanning exposure, and also provides a latent image stability after exposure. It is an object of the present invention to provide a silver halide color photographic light-sensitive material capable of stably forming an excellent and high-contrast image.

[0010]

Means for solving the above problems are as follows. That is, <1> a six-coordination complex having iridium (Ir) as a central metal and having at least one H ₂ O as a ligand,
A six-coordinate complex doped with iridium (Ir) having Cl, Br or I as a ligand and having a central metal of a silver halide grain having a silver chloride content of 90 mol% or more in the silver halide grain is converted into a odor of the silver halide grain. A silver halide emulsion comprising silver halide grains doped at a site having a silver halide content of 40 mol% or more.

<2> The halogenation according to <1>, wherein the portion having a silver bromide content of 40 mol% or more in the silver halide grains is formed by dissolving and depositing silver halide fine grains. It is a silver emulsion. <3> The halogen according to <1> or <2>, wherein the silver halide grains are silver chloroiodobromide grains having a silver iodide content of 0.02 mol% or more and 1 mol% or less. It is a silver halide emulsion.

<4> On a support, at least one silver halide emulsion layer containing a yellow dye-forming coupler, at least one silver halide emulsion layer containing a magenta dye-forming coupler, and at least one layer containing a cyan dye-forming coupler In a silver halide color photographic light-sensitive material having a light-sensitive emulsion layer including a silver halide emulsion layer, the light-sensitive emulsion layer comprises the silver halide emulsion of any one of the above items <1> to <3>; At least one of the emulsion layers contains a hexacoordination complex having at least one iridium (Ir) having H ₂ O as a ligand as a central metal at a site having a silver chloride content of 90 mol% or more in silver halide grains. A hexacoordinate complex having iridium (Ir) as a central metal, which is doped and has Cl, Br or I as a ligand, forms a silver bromide containing silver bromide. A silver halide color photographic light-sensitive material comprising silver halide grains doped at a portion having a content of 40 mol% or more.

<5> The above-mentioned item <4>, wherein the portion having a silver bromide content of 40 mol% or more in the silver halide grains is a silver halide grain formed by dissolving and depositing silver halide fine grains. And the silver halide color photographic light-sensitive materials described in <1. <6> The halogen according to <4> or <5>, wherein the silver halide grains are silver chloroiodobromide grains having a silver iodide content of 0.02 mol% or more and 1 mol% or less. It is a silver halide color photographic light-sensitive material.

[0014]

DETAILED DESCRIPTION OF THE INVENTION In the silver halide emulsion of the present invention, at least one iridium (hereinafter may be abbreviated as "Ir") hexacoordinate complex having at least one H ₂ O as a ligand is halogenated. An Ir6 coordination complex having a silver chloride content of 90 mol% or more in a silver grain and having Cl, Br or I as a ligand is added to a site where the silver bromide content of the silver halide grain is 40 mol% or more. Includes doped silver halide grains. Further, the silver halide color photographic light-sensitive material of the present invention has a photosensitive emulsion layer comprising the silver halide emulsion of the present invention on a support. In the present invention, the photosensitive emulsion layer includes a layer containing at least one layer each containing a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, and a cyan dye-forming coupler-containing silver halide emulsion layer. Say. Hereinafter, the silver halide emulsion of the present invention will be described in detail, and the silver halide color photographic light-sensitive material of the present invention will be described in detail through the description.

[Silver Halide Emulsion] The silver halide emulsion of the present invention is preferably a cubic or tetradecahedral crystal grain having substantially {100} faces (these grains are rounded at the apex of the grain and higher in the order of Planes) or octahedral crystal grains, or 50% or more of the total projected area is {100}
It is preferable to be composed of tabular grains having an aspect ratio of 2 or more and composed of {111} faces. The aspect ratio refers to a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of a particle. In the present invention, cubic or tabular grains having a {100} plane as a principal plane or tabular grains having a {111} plane as a principal plane are preferably applied.

The silver halide emulsion of the present invention (hereinafter sometimes simply referred to as "emulsion") comprises silver halide grains containing at least silver chloride and silver bromide, and comprises silver chloroiodide or salt. Silver iodobromide is suitably used, and silver chloroiodobromide is particularly preferred. The silver chloride content in the emulsion is 90
It must be at least mol%. The silver chloride content is preferably 95 mol% or more, more preferably 97 mol% or more, from the viewpoint of rapid processing.

The silver iodide content is 0.0
The content is preferably from 2 to 1 mol%, more preferably from 0.05 to 0.50 mol%, and more preferably from 0.07 to 0.40 mol%, from the viewpoint of further increasing sensitivity and increasing contrast during high-illuminance exposure. Is more preferred. Such silver iodide is preferably present near the surface of the silver halide grains.

As a method for introducing iodide ions for incorporating silver iodide into the silver halide emulsion of the present invention, an iodide salt solution may be added alone, or a silver salt solution and a high chloride An iodide salt solution may be added together with the addition of the salt solution. In the latter case, the iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of the iodide salt and the high chloride salt. The iodide salt is added in the form of a soluble salt, such as an alkali or alkaline earth iodide salt. Alternatively, iodide can be introduced by cleaving iodide ions from organic molecules, as described in US Pat. No. 5,389,508. Also, fine silver iodide grains can be used as another iodide ion source.

The addition of the iodide salt solution may be carried out intensively at one stage of grain formation, or may be carried out over a certain period of time. The position where iodide ions are introduced into the high chloride salt in the emulsion is limited in order to obtain an emulsion having high sensitivity and low fogging. As the introduction of iodide ions is made deeper into the emulsion grains, the increase in sensitivity is smaller. Therefore, the introduction of iodide ions by the addition of an iodide salt solution is preferably performed outside 50% of the particle volume, more preferably outside 70% of the particle volume.
Most preferably, it is performed outside 80%. Furthermore, the introduction of iodide ions by the addition of the iodide salt solution is preferably terminated within 98% of the particle volume.
Most preferably, it ends within%. By terminating the addition of the iodide salt solution slightly inside from the grain surface, it is possible to obtain an emulsion having higher sensitivity and lower fogging.

The distribution of the iodide ion concentration in the silver halide grains in the depth direction in the grains is determined by etching.
/ TOF-SIMS (Time of Flight-Secondary Ion M
assSpectrometry) method, for example, TR manufactured by Phi Evans
It can be measured using IFT type II TOF-SIMS. TOF
The SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” edited by The Surface Science Society of Japan (Maruzen Co., Ltd., 1999).

When the emulsion grains are analyzed by the etching / TOF-SIMS method, even if the addition of the iodide salt solution is completed inside the grains, it can be analyzed that iodide ions are exuding toward the grain surface. . In the silver halide emulsion of the present invention, it is preferable that iodide ions have a maximum concentration on the grain surface and that the iodide ion concentration is attenuated inward by analysis by etching / TOF-SIMS.

In the silver halide emulsion of the present invention, it is preferable to contain silver bromide from the viewpoint of high sensitivity and high contrast at high illuminance exposure. In this case, the silver bromide content is as follows:
It is preferably from 0.1 to 7 mol%, more preferably from 0.5 to 5 mol%. Such silver bromide is preferably formed as a localized phase having a higher silver bromide content than the surroundings inside or on the surface of the silver halide grains. The localized phase is
It may be formed in a layer so as to surround the inside of or on the surface of the halogenated particle, or may be formed epitaxially at a corner of the surface of the halogenated particle. Further, when the silver halide grains are cubic or tabular grains having a {100} plane as a main surface, the silver halide grains having a main surface of {10}
A localized phase having a high silver bromide content may be formed so as to cover the 0 ° plane. Here, the local concentration of the silver bromide in the localized phase is preferably 10 mol% or more, and is preferably 20 to 80 mol%.
Mole% is more preferred, and 40 to 80 mol% is most preferred.

The silver halide emulsion of the present invention contains iridium (Ir). Ir is introduced in the form of an iridium compound. Among them, in particular, Ir can be uniformly incorporated into silver halide crystals, and thus has six ligands, and a six-coordination complex having iridium (Ir) as a central metal is used. preferable. Specifically, it is constituted by the following two modes.

First, as a first form of Ir used in the present invention, a 6-coordinate iridium complex having Cl, Br or I as a ligand and having Ir as a central metal (6-coordinate complex).
At a site where the silver bromide content of the silver halide grains is 40 mol% or more (that is, a localized phase; hereinafter, sometimes referred to as a “silver halide site”). The silver bromide content of the silver halide grains doped with the six-coordination complex,
If the amount is less than 40 mol%, the latent image sensitization may increase.

Among the above, the silver bromide content in the silver halide site (local phase) containing (doping) the hexacoordinate complex is preferably 50 mol% or more, and more preferably 60 mol%. It is preferable that it is above. The silver halide portion having a silver bromide content of 40 mol% or more may be formed by adding an Ag solution and a halogen solution in opposite directions, but is preferably added in the form of silver halide fine particles. Is good. Thus, the silver halide sites having a silver bromide content of 40 mol% or more are formed by dissolving and depositing the silver halide fine particles. At this time, the iridium complex may be added separately from the fine particles, but is more preferably contained in the fine particles in advance.

In the above-mentioned six-coordinate iridium complex (six-coordinate complex), all six ligands are Cl, Br or I
A six-coordination complex having Ir as a central metal is preferably
In particular, a six-coordination complex having Ir as a central metal in which all six ligands are Cl is more preferable.

In the following, all six ligands are Cl, Br
Alternatively, specific examples of a six-coordination complex having Ir as a central metal are described. However, the present invention is not limited to these. That is, [IrCl ₆ ] ^2- (1), [IrCl ₆ ] ^3- (2), [IrBr ₆ ] ^2- (3), [IrBr ₆ ] ^3- (4), [IrI ₆ ] ^3- … (5),

Second, as a second form of Ir used in the present invention, a six-coordination complex having at least one H ₂ O as a ligand and having Ir as a central metal is a compound having a silver chloride content of silver halide grains. 90% by mole or more is doped. When the silver chloride content of the silver halide grains doped with the hexacoordinate complex is less than 90 mol%, the gradation tends to be soft.

Above all, it has at least one H ₂ O as a ligand and the remaining ligands are Cl, Br or I
A six-coordinate complex having Ir as a central metal is preferable, and a six-coordinate complex having Ir as a central metal having at least one H ₂ O as a ligand and all remaining ligands being Cl is more preferable.

In the following, at least one H ₂ O is used as a ligand, and the remaining ligands are Cl, Br or I
Specific examples of the six-coordination complex having Ir as a central metal will be described. However, the present invention is not limited to these. _{That, [Ir (H 2 O)} Cl 5] 2- ... (6), [Ir (H 2 O) 2 Cl 4] - ... (7), [Ir (H 2 O) Br 5] 2- ... ( _{8), [Ir (H 2} O) 2 Br 4] - ... (9),

The above-mentioned six-coordinate complex (metal complex) is an anion, and when forming a salt with a cation, its counter cation is preferably one which is easily dissolved in water. Specifically, sodium ion, potassium ion, rubidium ion,
Alkali metal ions such as cesium ions and lithium ions, ammonium ions, and alkyl ammonium ions are preferred. These metal complexes should be used by dissolving them in a mixed solvent of water and a suitable organic solvent that can be mixed with water (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.). Can be.

In the first and second embodiments, the doping amount of the hexacoordination complex of Ir in the doping is 1 × 10 ^-10 to 1 × 10 ^-3 mol per mol of silver halide. Preferably, it is more preferably from 1 × 10 ⁻⁸ to 1 × 10 ⁻⁵ mol.

As means for analyzing the components of silver halide grains containing the above-mentioned six-coordinate iridium complex (six-coordinate complex),
ICP-mass-spectroscopy while dissolving silver halide
And a method of analyzing by detecting halogen and Ir.

The iridium complex may be added directly to the reaction solution when forming silver halide grains, or may be added to an aqueous halide solution for forming silver halide grains, or to another solution. It is preferable to incorporate into the silver halide grains by adding to the solution. It is also preferable to physically ripen the fine particles in which the iridium complex has been incorporated in advance and incorporate them into silver halide grains.
Further, these methods can be combined and contained in silver halide grains.

When the iridium complex is incorporated into silver halide grains, it may be uniformly present inside the grains, as described in JP-A-4-208936 and JP-A-2-1252.
No. 45 and JP-A-3-18837, it is also preferable that the compound be present only on the particle surface layer, and that the compound be present only inside the particle and have no complex on the particle surface. Is also preferred. Further, as disclosed in U.S. Patent Nos. 5,252,451 and 5,256,530, the particle surface phase is improved by physical ripening with fine particles having an iridium complex incorporated therein. Quality is also preferred. Further, these methods may be used in combination, and a plurality of kinds of complexes may be incorporated in one silver halide grain.

In the present invention, metal ions other than iridium may be doped into the inside and / or the surface of the silver halide grains. As other metal ions, transition metal ions are preferable, and among them, iron, ruthenium, osmium, lead, cadmium, and zinc are more preferable. More preferably, the other metal ion is used as a hexacoordinate octahedral complex with a ligand.

In the hexacoordinate octahedral complex, when an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, suboxide Nitrate ion, water, ammonia, nitrosyl ion, thionitrosyl ion is preferable, and it is also preferable to use the iron, ruthenium, osmium, lead, cadmium, and zinc by coordinating any metal ion. It is also preferable to use them in one complex molecule.

Further, an organic compound may be used as a ligand,
Examples of the organic compound include a chain compound having 5 or less carbon atoms in a main chain and / or a 5- or 6-membered heterocyclic compound. Further, as a preferable organic compound, a compound having a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom as a coordinating atom to a metal in the molecule, and among them, furan, thiophene, oxazole, isoxazole, thiazole, and isothiazole , Imidazole,
Most preferred are pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and preferred examples are compounds in which these compounds are used as a basic skeleton and further substituents are introduced.

The combination of the other metal ion and the ligand is preferably a combination of an iron ion, a ruthenium ion and a cyanide ion. In the present invention, it is preferable to use iridium in combination with these compounds. In these compounds, the cyanide ion preferably occupies the majority of the coordination number to the central metal, iron or ruthenium, and the remaining coordination sites are thiocyan, ammonia, water, nitrosyl ion, dimethylsulfoxide, pyridine , Pyrazine and 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron complex or a hexacyanoruthenium complex.

In the case of a hexacoordinate octahedral complex having a cyanide ion as a ligand, the amount of the complex may be from 1 × 10 ⁻⁸ to 1 mol per mol of silver halide during formation of silver halide grains.
1 × 10 ⁻² mol is preferred, and 1 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol is most preferred.

In the case of a hexacoordinated octahedral complex having ruthenium and osmium as central metals, it is also preferable to use a nitrosyl ion, a thionitrosyl ion, or a water molecule and a chloride ion together as a ligand. Above all, it is more preferable to form a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex, and it is also preferable to form a hexachloro complex. In the case of these six-coordinate octahedral complexes, the amount added is 1 × 10 ⁻¹⁰ to 1 × 1 per mol of silver during grain formation.
It is preferably 0 ^{-6, and} more preferably 1 × 10 ^-9 to 1 × 10 ^-6 mol.

Average grain size of silver halide grains in the silver halide emulsion of the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain, and the number average is calculated)
Is preferably 0.1 to 2 μm. The average particle size distribution is preferably a variation coefficient (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, more preferably 15% or less, and so-called monodispersion of 10% or less. Are particularly preferred. At this time, from the viewpoint of obtaining a wide latitude, it is also preferable to use the emulsion in the monodispersed state by blending it in the same layer, or to perform multilayer coating.

In the silver halide emulsion of the present invention, the gold
You may feel. The gold sensitization is usually performed by adding a gold sensitizer.
The emulsion is heated at a high temperature (preferably 40 ° C. or higher) for a certain period of time.
It is performed by stirring. Addition amount of the gold sensitizer
Depends on various conditions, but as a guide,
1 × 10 per mole of silver logenide^-71 x 10 or more ^-Four
Molar or less is preferred.

Examples of the gold sensitizer include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like. Examples thereof include colloidal gold sulfide and gold sensitizers having a gold complex stability constant of 21 to 35, and not only one kind but also a plurality of kinds may be used in combination.

In addition to the gold sensitization, other chemical sensitizations can be used in combination. As a chemical sensitization method that can be used in combination, sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization other than gold, reduction sensitization, or the like can be used. Compounds used for chemical sensitization are described in JP-A-62-2.
No. 15,272, from the lower right column on page 18 to the upper right column on page 22, are preferably used.

In the silver halide emulsion of the present invention, various compounds are used for the purpose of preventing fogging during the production process, storage or photographic processing of the silver halide color photographic light-sensitive material, or stabilizing photographic performance. Alternatively, a precursor thereof can be added. Specific examples of various compounds or precursors thereof are described in
No. 15272, pp. 39 to 72 are preferably used. Further, a 5-arylamino-1,2,3,4-thiatriazole compound (the aryl residue has at least one electron-withdrawing group) described in EP0447647 is also preferably used.

For the purpose of improving the storage stability of the silver halide emulsion, a hydroxamic acid derivative described in JP-A-11-109576; an amino acid at both ends adjacent to a carbonyl group described in JP-A-11-327094, Cyclic ketones having a double bond substituted with a group or a hydroxyl group (especially those represented by the general formula (S1), and the compounds described in paragraphs [0036] to [0071] are described in the specification of the present application. Can be taken in.);
No. 011, sulfo-substituted catechol and hydroquinones (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-
Benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,
4,5-trihydroxybenzenesulfonic acid and salts thereof); described in U.S. Pat. No. 5,556,741;
Hydroxylamines represented by the general formula (A) (U.S. Pat. No. 5,556,741, column 4, lines 56 to 11)
The description in column 22, line preferably applies to this application and is incorporated as part of the specification of this application. ); JP-A-11-1
Water-soluble reducing agents represented by general formulas (I) to (III) described in No. 02045 can be added.

In the silver halide emulsion of the present invention, in the silver halide color photographic light-sensitive material of the present invention described later, the silver halide emulsion forming each layer constituting the photosensitive emulsion layer is spectrally dispersed in a desired light wavelength range. For the purpose of imparting sensitivity, spectral sensitization is performed. In each layer constituting the photosensitive emulsion layer of a silver halide color photographic light-sensitive material, blue, green, spectral sensitizing dyes used for spectral sensitization in the red region, for example, FM
By Harmer Heterocyclic compounds-Cyanine dyes and r
elated compounds (John Wiley & Sons [New York, Lond
on], published in 1964). Specific examples of compounds and spectral sensitization are described in JP-A-62-2
The description in the upper right column on page 22 to page 38 of JP 15272 can be suitably applied. Further, particularly as a red-sensitive spectral sensitizing dye used for silver halide grains having a high silver chloride content,
From the viewpoint of stability, strength of adsorption, temperature dependence of exposure, etc.
The spectral sensitizing dyes described in JP-A-3-123340 are very preferred.

The amount of the spectral sensitizing dye to be added can be selected from a wide range depending on the case, and is particularly preferably from 0.5 × 10 ^{-6 to} 1.0 × 10 ^-2 mol per mol of silver halide.
1.0 × 10 ^{−6 to} 5.0 × 10 ⁻³ mol is more preferable.

[Silver halide color photographic light-sensitive material] The silver halide color photographic light-sensitive material of the present invention comprises the above-described silver halide emulsion of the present invention, and comprises at least one layer of a yellow dye on a support. A light-sensitive emulsion layer comprising a coupler-containing silver halide emulsion layer, at least one magenta dye-forming coupler-containing silver halide emulsion layer, and at least one cyan dye-forming coupler-containing silver halide emulsion layer. And at least one of the photosensitive emulsion layers contains silver halide grains doped with the above-mentioned hexacoordinate iridium complex. The silver halide grains doped with the hexacoordinate iridium complex described above contain at least one H
A hexacoordinate iridium complex having ₂ O as a ligand is doped at a site where the silver chloride content of the silver halide grains is 90 mol% or more, and a hexacoordinate iridium complex having Cl, Br or I as a ligand is formed. The silver halide grains are doped at a site (localized phase) where the silver bromide content is 40 mol% or more.

For the silver halide color photographic light-sensitive material of the present invention (hereinafter sometimes simply referred to as "photographic light-sensitive material"), conventionally known photographic materials and additives can be used. Hereinafter, description will be made in order. For example, as a support constituting the photographic light-sensitive material, a transmission type support and a reflection type support are exemplified. Examples of the transmission type support include transparent films such as cellulose nitrate film and polyethylene terephthalate, and 2,6-naphthalenedicarboxylic acid (ND
Preferred examples thereof include polyesters of CA) and ethylene glycol (EG), and polyesters of NDCA, terephthalic acid and EG provided with an information recording layer such as a magnetic layer. As the reflective support, a plurality of water-resistant resin layers such as a polyethylene layer and a polyester layer are laminated, and at least one of the water-resistant resin layers (laminate layer) contains a white pigment such as titanium oxide. A support and the like are preferred.

Among the above-mentioned reflective supports, fine pores are formed on a paper substrate on which a layer comprising a silver halide emulsion (hereinafter referred to as a "silver halide emulsion layer") is provided. Those having a polyolefin layer are preferred. The polyolefin layer may be composed of multiple layers, in this case, the polyolefin layer adjacent to the gelatin layer on the side having the silver halide emulsion layer has no micropores (for example, polypropylene, polyethylene, etc.), It is more preferable that the polyolefin layer on the side close to the paper substrate has micropores (for example, polypropylene, polyethylene, etc.).

The polyolefin layer is located between a paper substrate and a photographic component layer such as a silver halide emulsion layer, and the density of the one or more polyolefin layers is 0.4%.
0 to 1.0 g / ml is preferable, and 0.50 to 0.70 g
/ Ml is more preferred. The layer thickness of the one or more polyolefin layers is preferably from 10 to 100 μm, more preferably from 15 to 70 μm. Further, the ratio of the thickness of the polyolefin layer (p) to the thickness of the paper substrate (b) (p / b)
Is preferably 0.05 to 0.2, and 0.1 to 0.2.
15 is more preferred.

From the viewpoint of increasing the rigidity of the reflection support, it is preferable to provide a polyolefin layer on the opposite side (back side) of the paper substrate from the side on which the photographic component layer is provided. in this case,
The surface of the back polyolefin layer is preferably matte polyethylene or polypropylene, more preferably polypropylene. The layer thickness of the polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further preferably the density is 0.7 to 1.1 g / ml.

In the above-mentioned reflection support, preferred embodiments relating to a polyolefin layer provided on a paper substrate are described in JP-A-10-333277 and JP-A-10-33327.
No. 8, No. 11-52513, No. 11-65024,
Examples are described in EP0880065 and EP0888066.

The water-resistant resin layer preferably contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in a hydrophilic colloid layer of a photographic light-sensitive material. Preferred examples of the fluorescent whitening agent include benzoxazole-based, coumarin-based, and pyrazoline-based ones. Among them, benzoxazolylnaphthalene-based and benzooxazolylstilbene-based fluorescent whitening agents are more preferred. The amount of the optical brightener used is not particularly limited, but is preferably 1 to 100 mg /
m ² . The mixing ratio when mixed with a water-resistant resin such as polyethylene or polyester is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass, based on the amount (mass) of the resin. More preferred.

The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

In the present invention, as a support constituting the photographic light-sensitive material, a white pigment-based support for a display or a white pigment is provided on the surface of a support on which a silver halide emulsion layer is provided. A support provided with a layer may be used.

For the purpose of improving sharpness, it is preferable to coat an antihalation layer on the side of the support on which the silver halide emulsion layer is provided or on the side opposite to the side (back side). In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.

For the purpose of improving the sharpness of an image, etc., a hydrophilic colloid layer is coated on the hydrophilic colloid layer in EP 0,337,4.
No. 90A2, pp. 27-76, a dye capable of being decolorized by processing (a water-soluble dye; particularly, an oxonol dye) is used so that the optical reflection density at 680 nm of a photographic material becomes 0.70 or more. 12% by mass or more (more preferably 14% by mass or more) of titanium oxide surface-treated with a divalent or tetravalent alcohol (for example, trimethylolethane) or the like is added to the water-resistant resin layer of the support. Is preferred.

For the purpose of preventing irradiation and halation, and improving safelight safety, etc., the hydrophilic colloid layer can be decolorized by the treatment described in pages 27 to 76 of EP0333790A2. It is preferable to add a dye (a water-soluble dye; among them, an oxonol dye and a cyanine dye). European Patent EP08
The dyes described in JP 19977 can also be suitably added. Among these water-soluble dyes, there are those that increase color separation and safelight safety when the amount used is increased, and as dyes that can be used without deteriorating color separation,
Water-soluble dyes described in JP-A-5-127324, JP-A-5-127325 and JP-A-5-216185 are preferred.

In place of the hydrophilic colloid layer containing the water-soluble dye, or in combination with the hydrophilic colloid layer containing the water-soluble dye, a colored layer that can be decolorized by treatment can be provided. The colored layer which can be decolorized by the treatment may be directly under the silver halide emulsion layer, or may be arranged so as to be in contact with an intermediate layer containing a processed color mixture inhibitor such as gelatin or hydroquinone. The colored layer is preferably provided as a lower layer (support side) of a silver halide emulsion layer that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to arbitrarily select only some of them. Further, it is also possible to provide a colored layer which is colored corresponding to a plurality of primary color gamuts.

As the optical reflection density of the colored layer, the wavelength range used for exposure (40% in ordinary printer exposure) is used.
In the visible light region of 0 to 700 nm, or the light source wavelength of the scanning exposure used in the scanning exposure), the optical density value at the wavelength showing the highest optical density is preferably 0.2 or more and 3.0 or less. 5 or more and 2.5 or less are more preferable, and 0.8 or more and 2.0 or less are especially preferable.

For forming the colored layer, a conventionally known method can be applied. For example, Japanese Patent Application Laid-Open No. 2-28224
No. 4, page 3 in the upper right column to dyes described in page 8 and JP-A-3-7.
No. 931, page 3, upper right column to page 11, lower left column, etc., such as a method in which solid fine particle dispersion is contained in a hydrophilic colloid layer, a method in which an anionic dye is mordanted to a cationic polymer, and a method in which a dye is used. A method in which fine particles such as silver halide are adsorbed and fixed in a layer;
No. 44 using colloidal silver.

In the above, a method for dispersing the fine powder of the dye in a solid state is described in, for example, JP-A-2-308244.
No. 4, pages 13 to 13 describe a method for incorporating a fine powder dye which is substantially water-insoluble at least at pH 6 or lower, but is substantially water-soluble at least at pH 8 or higher. In the above, as a method for mordanting an anionic dye to a cationic polymer, for example,
Reference can be made to the description on pages 18 to 26 of -84637.
In the above, methods for preparing colloidal silver as a light absorber include those described in U.S. Patent Nos. 2,688,601 and 3,4.
No. 59,563. Among the above methods, a method of containing the fine powder dye, a method of using colloidal silver, and the like are preferable.

The silver halide color photographic light-sensitive material of the present invention is used as a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper and the like, and among them, it is preferable to use it as a color photographic paper. The color photographic paper according to the present invention comprises a silver halide emulsion layer containing a yellow dye-forming coupler (yellow color-forming property) and a magenta dye-forming coupler (magenta color-forming property).
It has at least one silver halide emulsion layer and at least one silver halide emulsion layer containing a cyan dye-forming coupler (cyan color-forming property). Generally, these silver halide emulsion layers are formed in order from the support side to yellow color formation. And a magenta-color-forming silver halide emulsion layer and a cyan-color-forming silver halide emulsion layer.

However, the present invention is not necessarily limited to the above structure, and a different layer structure may be adopted. That is, the silver halide emulsion layer (yellow coupler-containing layer) containing the yellow dye-forming coupler (yellow coupler) may be arranged at any position on the support, but the yellow coupler-containing layer is In the case of containing silver tabular grains, it is preferably provided at a position more distant from the support than at least one of the magenta coupler-containing silver halide emulsion layer and the cyan coupler-containing silver halide emulsion layer. Further, from the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color by the sensitizing dye, the yellow-coupler-containing silver halide emulsion layer is located farthest from the support than the other silver halide emulsion layers. Preferably, it is coated. Further, from the viewpoint of reducing Blix discoloration, the cyan coupler-containing silver halide emulsion layer is preferably the central layer of the other silver halide emulsion layers. The silver halide emulsion layer is preferably the lowermost layer.

The color-forming silver halide emulsion layers for yellow, magenta and cyan may be composed of two or three layers. For example, Japanese Patent Application Laid-Open No. 4-75055, 9
As described in JP-A-114035, JP-A-10-246940 and U.S. Pat. No. 5,576,159, a coupler layer containing no silver halide emulsion is provided adjacent to the silver halide emulsion layer, and a color-forming layer is formed. It is also preferable to do so.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) used in the present invention, and the processing methods and processing applied for processing this photographic light-sensitive material As an additive, JP-A-62-21
5272, JP-A-2-33144, European Patent EP
Those described in U.S. Pat. No. 0,355,660 A2, particularly those described in European Patent EP 0,355,660 A2 can be preferably applied. Further, JP-A-5-34
No. 889, No. 4-359249, No. 4-313375
Nos. 4-270344, 5-66527, and 4
-34548, 4-145433, 2-854
Nos. 1-158431, 2-90145 and 3
Also preferred are silver halide color photographic light-sensitive materials described in, for example, JP-A-194539, JP-A-2-93641, and European Patent Publication No. 0520457A2, and a processing method thereof.

In the present invention, the above-mentioned reflective support,
Silver halide emulsion, different metal ion species doped in silver halide grains, storage stabilizer of silver halide emulsion, antifoggant, chemical sensitization (sensitizer), spectral sensitization (spectral sensitization) Agents), cyan couplers, magenta couplers, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (anti-stain and anti-fading agents), dyes (colored layers), gelatin species, layer composition of photographic light-sensitive materials, photographs Coating pH of photosensitive material
Regarding the above, those described in the patents in Table 1 below can be particularly preferably applied.

[0071]

[Table 1]

The cyan, magenta and yellow couplers used in the present invention include those described in
215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144, page 3 upper right column 1
Line 4 to the last line of the upper left column of page 18 and the sixth line of the upper right column of page 30
Page 35, lower right column, line 11, EP 0355,660A2, page 4, lines 15 to 27, page 30, line 30 to page 28, last line 45, page 29 to line 31, page 47, 23 Lines-63
The couplers described on page 50, line 50, are also useful. In addition, WO
General formula (II) or (III) described in -98/33760
And a compound represented by formula (D) described in JP-A-10-221825 can be suitably added.

Hereinafter, a more specific description will be given. Preferable examples of the cyan coupler usable in the present invention include pyrrolotriazole couplers.
The couplers represented by the general formula (I) or (II) described in No. 3324, the couplers represented by the general formula (I) described in JP-A-6-347960, and the exemplary couplers described in these patents can be used. Particularly preferred. Also, phenolic,
A naphthol-based cyan coupler is also preferable, and examples thereof include a cyan coupler represented by the general formula (ADF) described in JP-A-10-333297. Other cyan couplers other than those described above include pyrroloazole-type cyan couplers described in European Patents EP0488248 and EP0491197A1, and US Pat. No. 5,888,7.
2,5-diacylaminophenol couplers described in U.S. Patent Nos. 4,873,183 and 4,91
Pyrazoloazole type cyan couplers having an electron-withdrawing group and a hydrogen bonding group at the 6-position described in JP-A-6,051, especially JP-A-8-171185, JP-A-8-31360, and JP-A-8-31360
Pyrazoloazole-type cyan couplers having a carbamoyl group at the 6-position described in JP-A-339060 are also preferable.

Further, diphenylimidazole cyan couplers described in JP-A-2-33144 and 3-hydroxypyridine cyan couplers described in European Patent EP 0 333 185 A2 (including couplers (42) listed as specific examples) (Equivalent to 2-equivalent coupler having a chlorine leaving group to 4-equivalent coupler, coupler (6) and coupler (9)), and JP-A-64-3226.
No. 0, the cyclic active methylene-based cyan couplers (among others, coupler examples 3, 8 listed as specific examples,
34 is particularly preferred), EP 0 456 226 A
Pyrrolopyrazole-type cyan couplers described in the specification of JP-A No. 1 and pyrroleimidazole-type cyan couplers described in EP 0484909 are also exemplified.

Among the above-mentioned cyan couplers, pyrroloazole-based cyan couplers are preferable.
Particularly preferred are pyrroloazole-based cyan couplers represented by the general formula (I) described in No. 2138, and include the exemplified cyan couplers (1) to (47) described in paragraphs [0012] to [0059] of the patent. , As applied to the present application, and is preferably incorporated as a part of the specification of the present application.

Examples of the magenta couplers usable in the present invention include 5-pyrazolone magenta couplers and pyrazoloazole magenta couplers described in the publicly known documents in Table 1 above. Among them, hue, image stability, and color development In terms of properties and the like, secondary or
A pyrazolotriazole coupler in which a secondary alkyl group is directly bonded to the 2-, 3- or 6-position of the pyrazolotriazole ring; a pyrazoloazole coupler containing a sulfonamide group in the molecule described in JP-A-61-65246; JP-A-61-
No. 147254, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group; pyrazolo compounds having an alkoxy group or an aryloxy group at the 6-position described in European Patent Nos. 226,849A and 294,785A. Azole couplers are preferred.

Among the above magenta couplers, Japanese Unexamined Patent Publication No.
Particularly preferred are pyrazoloazole couplers represented by the general formula (MI) described in No. 122984, and paragraph numbers [0009] to [0026] of the patent are applied to the present application as they are, and a part of the specification of the present application. Captured as In addition to this, European Patent Nos. 854384 and 844640.
Pyrazoloazole couplers having a sterically hindered group at both the 3- and 6-positions described in (1) are also preferably used.

The yellow couplers usable in the present invention include, in addition to the compounds listed in Table 1 above, European coupler EP
No. 4,447,969 A1, 3 to 3 in the acyl group.
Acylacetamide type yellow coupler having a 5-membered cyclic structure; Malondianilide type yellow coupler having a cyclic structure described in European Patent EP 0 482 552 A1;
No. 53871A1, No. 953872A1, No. 95
3873A1, 953874A1, 953
875A1 and the like, pyrrole-2 or 3-yl or indol-2 or 3-ylcarbonylacetic acid anilide-based couplers; acylacetamide type having a dioxane structure described in US Pat. No. 5,118,599 Yellow couplers are preferred. Among them, an acylacetamide-type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide-type yellow coupler in which one of the anilides forms an indoline ring are particularly preferable. The cyan, magenta or yellow couplers described above may be used alone or in a combination of two or more.

Each of the couplers can be prepared by loading a loadable latex polymer (for example, US Pat. No. 4,20) in the presence (or absence) of the high boiling organic solvent described in Table 1 above.
3,716) or dissolved together with a water-insoluble and organic solvent-soluble polymer to emulsify and disperse in a hydrophilic colloid aqueous solution. Examples of the water-insoluble and organic solvent-soluble polymer include columns 7 to 15 of U.S. Pat. No. 4,857,449 and pages 12 to 30 of WO 88/00723.
Homopolymers or copolymers described on the page are preferable, methacrylate-based or acrylamide-based polymers are more preferable, and acrylamide-based polymers are particularly preferable in terms of color image stability and the like.

In the present invention, known color mixing inhibitors can be used. As the color mixing inhibitor, those described in the following patents are preferable. For example, JP-A-5-33
High molecular weight redox compound described in No. 3501, WO
No. 98/33760, U.S. Pat. No. 4,923,787, etc .;
And white couplers described in JP-A-10-282615, German Patent No. 19629142A1, and the like. In particular, the pH of the developer is increased,
In the case of speeding up the development, German Patent No. 196187
86A1, EP 839623 A1, EP 842975 A1, German Patent 19806846 A1
It is also preferable to use the redox compounds described in US Pat.

In the present invention, as an ultraviolet absorber,
It is preferable to use a compound having a triazine skeleton having a high molar extinction coefficient, for example, JP-A-46-3335.
No. 55-152776, JP-A-5-1970074
Nos. 5-232630, 5-307232, 6-211813, 8-53427, and 8-23
No. 4364, No. 8-239368, No. 9-31067
No., No. 10-115598, No. 10-147577
No. 10-182621, German Patent No. 197397
No. 97A, European Patent No. 711804A and Japanese Patent Publication No.
No. 5,291,291 and the like. These are a color-forming silver halide emulsion layer (photosensitive layer)
And / or preferably added to the non-photosensitive layer.

The silver halide color photographic light-sensitive material of the present invention may contain a binder or a protective colloid.
Gelatin is advantageous as the binder or protective colloid, but other hydrophilic colloids can be used alone or together with gelatin. In the gelatin, iron,
The concentration of heavy metals contained as impurities such as copper, zinc, and manganese is preferably 5 ppm or less, more preferably 3 ppm or less. The amount of calcium contained in the photographic material is preferably 20 mg.
/ M ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

In the present invention, a fungicidal / fungicidal agent described in JP-A-63-271247 is added for the purpose of preventing various fungi and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image. Is preferred. The coating pH of the photographic material is preferably from 4.0 to 7.0, preferably from 4.0 to 7.0.
6.5 is more preferred.

Improvement of coating stability in a photographic light-sensitive material,
A surfactant can be added to the photographic light-sensitive material from the viewpoint of preventing static electricity generation and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. Among them, a fluorine atom-containing surfactant is preferable. The fluorine atom-containing surfactant may be used alone, or may be used in combination with another conventionally known surfactant, and is preferably used in combination with another conventionally known surfactant.

The addition amount of the surfactant in the photographic light-sensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , preferably 1 × 10 ^−4.
１1 × 10 ⁻¹ g / m ² , more preferably 1 × 10 ^{-3 −1}
× 10 ^-2 g / m ² is most preferred.

The silver halide color photographic light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a usual negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. For the cathode ray tube used for image exposure, various light emitters that emit light in a spectral region are used as necessary. For example, one or more of a red light emitter, a green light emitter, and a blue light emitter are used. Used as a mixture. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular,
A cathode ray tube which emits white light by mixing these light emitters is often used.

When the photographic light-sensitive material has a plurality of silver halide emulsion layers (photosensitive layers) having different spectral sensitivity distributions and the cathode tube also has a phosphor which emits light in a plurality of spectral regions, The color may be exposed at a time, that is, a plurality of color image signals may be input to the cathode ray tube to emit light from the tube surface. A method of sequentially inputting image signals for each color to sequentially emit light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure) may be employed. However, since a high-resolution cathode ray tube can be used, it is preferable for high image quality.

In the silver halide color photographic light-sensitive material of the present invention, a gas laser, a light-emitting diode, a semiconductor laser, a semiconductor laser, a solid-state laser using a semiconductor laser as an excitation light source, and a non-linear optical crystal are combined. A digital scanning exposure method using monochromatic high-density light such as a harmonic emission light source (SHG) is preferable. Among them, from the viewpoint of making the system compact and inexpensive, a semiconductor laser, a semiconductor laser or a solid-state laser and a nonlinear optical crystal are preferred. The second harmonic generation light source (SHG) combining the above is preferable. In particular, from the viewpoint of designing a device that is compact, inexpensive, and has a long life and excellent stability, a semiconductor laser is preferable, and a semiconductor laser is preferably used as at least one of the exposure light sources.

When using such a scanning exposure light source,
The maximum wavelength of the spectral sensitivity of the silver halide color photographic light-sensitive material of the present invention can be arbitrarily set depending on the wavelength of the scanning exposure light source to be used. An SHG light source obtained by combining a solid-state laser using a semiconductor laser as an excitation light source or a semiconductor laser and a nonlinear optical crystal can halve the laser oscillation wavelength, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photographic material is normal blue,
It is possible to have the wavelengths in three wavelength regions of green and red.
The exposure time in such scanning exposure is set to a pixel density of 4
If the pixel size in the case of 00 dpi is defined as the exposure time, the exposure time is preferably 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less.

The preferred scanning exposure method applicable to the present invention is described in detail in the patent publication shown in Table 1 above. In order to process the silver halide color photographic light-sensitive material of the present invention, JP-A-2-207250-26
Line 1 in the lower right column of the page to line 9 in the upper right column of the page 34, and
No. 97355, page 5, upper left column, line 17 to page 18, lower right column 2
The processing materials and processing methods described in the 0th line can be preferably applied. As the preservative used in the developer, compounds described in the patent publications shown in Table 1 are preferably used.

The silver halide color photographic light-sensitive material of the present invention can be applied as a material having rapid processing suitability. The exposed photographic light-sensitive material is subjected to conventional color development processing, but for the purpose of rapid processing, after color development,
It is preferable to perform bleach-fix processing.

When rapid processing is performed, the color development time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more, and particularly preferably 30 seconds or less and 6 seconds or more. Here, the color development time refers to the time from when the photosensitive material enters the color developing solution to when it enters the bleach-fixing solution in the next processing step. For example, when processing is performed by an automatic developing machine or the like, the time during which the photographic light-sensitive material is immersed in the color developing solution (so-called in-solution time) and the time when the photographic light-sensitive material leaves the color developing solution and is used in the next processing The sum of the time during which the paper is conveyed through the air toward the bleach-fix bath (so-called air time) is referred to as the color development time.

The bleach-fixing time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more.
It is particularly preferable that the time is 6 seconds or less. Here, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until it enters the next washing or stabilizing bath. The washing or stabilizing time is preferably 150 seconds or less, and 130 seconds or less.
Seconds or more are more preferred. Here, the term “washing or stabilizing time” refers to the time during which the photosensitive material is in the washing or stabilizing solution and is in the solution for the drying step (so-called in-solution time).

After exposure of the photographic light-sensitive material, a conventional method of developing with a developing solution containing an alkali agent and a developing agent, an alkali solution containing a developing agent in the photographic light-sensitive material and containing no developing agent can be used. In addition to a wet method such as a method of developing with an activator solution such as a method described above, a thermal developing method without using a processing solution can be used. In particular, since the activator method does not contain a developing agent in the processing solution, it is easy to manage and handle the processing solution, and is a preferable method from the viewpoint of environmental conservation because it has a small load when processing the waste liquid. In the activator method, as a developing agent or a precursor thereof incorporated in a photosensitive material, for example, JP-A-8-234388
And the hydrazine-type compounds described in JP-A Nos. 9-152686, 9-152693, 9-212814 and 9-160193.

Further, the amount of silver applied to the photographic material is reduced,
A developing method of performing image amplification processing (intensification processing) using hydrogen peroxide is also preferably used. In particular, it is preferable to use this method for the activator method. Specifically, an image forming method using an activator solution containing hydrogen peroxide described in JP-A-8-297354 and JP-A-9-152699 is preferably used. In the activator method, after processing with an activator solution, usually a desilvering process is performed, but in an image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted, and a simple method such as washing or stabilizing can be performed. Further, in a method of reading image information from a photographic photosensitive material with a scanner or the like, even when a photographic photosensitive material having a high silver content such as a photographic photosensitive material is used,
A processing mode that does not require desilvering processing can be adopted.

As the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, Research Disclosure Item 36544
(September 1994) pp. 536-541, JP-A-8
-234388 can be used.

When the photosensitive material of the present invention is exposed to a printer, the band stop filter described in US Pat. No. 4,880,726 may be used from the viewpoint of eliminating color mixing and significantly improving color reproducibility. preferable. In the present invention, as described in European Patent Nos. EP0789270A1 and EP0789480A1, before applying image information, a yellow microdot pattern may be pre-exposed in advance to control copying.

The silver halide color photographic light-sensitive material of the present invention can be suitably used in combination with an exposure and development system described in the following known materials. An automatic printing and developing system described in JP-A-10-333253; a photosensitive material transporting device described in JP-A-2000-10206; a recording system including an image reading device described in JP-A-11-21512; -88619 and JP-A-10-202
Exposure system consisting of a color image recording method described in Japanese Patent Application No. 950 ・ Digital photo print system including a remote diagnostic method described in Japanese Patent Application Laid-Open No. H10-210206 system

As described above, the silver halide grains have a K content of 90 mol% or more in the silver halide grains.
₂ [Ir (H ₂ O) Cl ₅ ] is doped and the Br content of silver halide grains is 40 mol% or more.
₂ [IrCl ₆ ] is doped, so that even in the case of short-time exposure such as 1 μsec and ultra-high illuminance such as laser scanning exposure, a high-sensitivity hard gradation can be obtained, and The latent image after exposure can be stabilized, and imaging can be performed stably.

[0100]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of Emulsion A) Lime-treated gelatin 3% aqueous solution 1000
ml and adjusted to pH 3.3 and pCl 1.7.
An aqueous solution containing 2.12 mol of silver and 2.2 parts of sodium chloride
At 68 ° C with vigorous stirring
The addition was mixed. After desalination at 40 ° C, lime treatment
Add 168 g of gelatin to pH 5.7 and pCl 1.8
It was adjusted. The obtained particles have a side length of 0.6 μm and a variation coefficient of 1
It was a 1% cubic silver chloride emulsion. Continue melting at 40 ° C
And dissolve sodium thiosulfonate in silver halide
2 × 10 per le^-FiveMole addition, average particle size 0.05μm
Silver bromide 70 mol% silver chloride 30 mol% fine grain emulsion (fine
Grain emulsion A) was added to give a silver content of 1%. That
Then, sodium thiosulfate pentahydrate was added to 1 mole of silver halide.
2 × 10 per ^-6Moles, the following compound S-2 as a gold sensitizer
Of 1.2 × 10 per mol of silver halide^-Five6 moles
Aged at 0 ° C. for 40 minutes.

After the temperature was lowered to 40 ° C., the following sensitizing dye A was used in an amount of 2 × 10 ⁻⁴ mol per mol of silver halide, and the following sensitizing dye B was used in an amount of 1 × 10 ⁻⁴ mol per mol of silver halide; −
5-mercaptotetrazole was used in an amount of 2 × 10 ^-4 mol per mol of silver halide, 1- (5-methylureidophenyl)
-5-mercaptotetrazole was added in an amount of 2 × 10 ^-4 mol per mol of silver halide, and potassium bromide was added in an amount of 2 × 10 ^-3 mol per mol of silver halide.

[0103]

Embedded image

[0104]

Embedded image

(Preparation of Emulsion B) When the addition of silver nitrate to Emulsion A was completed at 90%, an aqueous solution of potassium iodide was vigorously mixed while the amount of I was 0.25 per mol of the completed silver halide. Emulsions were prepared which differed only in molar addition. The resulting particles have a side length of 0.6μ
m, a cubic silver chloroiodobromide emulsion having a variation coefficient of 11%.

(Preparation of Emulsion C)
From 70% to 85% of the addition of _Two
[IrCl₆] Add aqueous solution to finished silver halide 1
2 × 10 Ir amount per mole^-8Added to make it mole
Emulsions were prepared which differed only in that: Obtained particles have side length
Cubic silver chloroiodobromide emulsion with 0.6 μm, coefficient of variation 11%
there were.

(Preparation of Emulsion D)
From 70% to 85% of the addition of _Two
[IrCl₆] Add aqueous solution to finished silver halide 1
5 × 10 Ir amount per mole^-8Added to make it mole
Emulsions were prepared which differed only in that: Obtained particles have side length
Cubic silver chloroiodobromide emulsion with 0.6 μm, coefficient of variation 11%
there were.

(Preparation of Emulsion E) In Emulsion D, a fine grain emulsion comprising 70 mol% of silver bromide and 30 mol% of silver chloride and doped with K ₂ [IrCl ₆ ] in place of fine grain emulsion A (average grain size) 0.05 μm) is changed to K ₂ [Ir
[Cl ₆ ] was prepared so that the amount was 2 × 10 ⁻⁸ mol per mol of silver halide. The resulting grains were cubic silver chloroiodobromide emulsions having a side length of 0.6 μm and a variation coefficient of 11%.

(Preparation of Emulsion F) In Emulsion D, a fine grain emulsion comprising 70 mol% of silver bromide and 30 mol% of silver chloride and doped with K ₂ [IrCl ₆ ] instead of fine grain emulsion A (average grain size) 0.05 μm) is changed to K ₂ [Ir
[Cl ₆ ] was prepared so that the amount was 5 × 10 ⁻⁸ mol per mol of silver halide. The resulting grains were cubic silver chloroiodobromide emulsions having a side length of 0.6 μm and a variation coefficient of 11%.

(Preparation of Emulsion G) In Emulsion D, a fine grain emulsion comprising 70 mol% of silver bromide and 30 mol% of silver chloride and doped with K ₂ [IrCl ₆ ] instead of fine grain emulsion A (average grain size) 0.05 μm) is changed to K ₂ [Ir
[Cl ₆ ] was prepared so that the amount was 2 × 10 ⁻⁷ mol per mol of silver halide. The resulting grains were cubic silver chloroiodobromide emulsions having a side length of 0.6 μm and a variation coefficient of 11%.

(Preparation of Emulsion H)
From 70% to 85% of the addition of _Two
[IrCl₆] Add aqueous solution to finished silver halide 1
1 × 10 Ir amount per mole^-7Added to make it mole
Emulsions were prepared which differed only in that: Obtained particles have side length
Cubic silver chloroiodobromide emulsion with 0.6 μm, coefficient of variation 11%
there were.

(Preparation of Emulsion I)
From 70% to 85% of the addition of _Two
[Ir (H_TwoO) Cl_Five] Add the aqueous solution to the finished halogen
Ir content per mole of silver halide is 2 × 10^-7To be mole
Emulsions were prepared that differed only in the addition. Obtained particles
Is a cubic silver chloroiodobromide having a side length of 0.6 μm and a variation coefficient of 11%
It was an emulsion.

(Preparation of Emulsion J)
From 70% to 85% of the addition of _Two
[Ir (H_TwoO) Cl_Five] Add the aqueous solution to the finished halogen
Ir content of 5 × 10^-7To be mole
Emulsions were prepared that differed only in the addition. Obtained particles
Is a cubic silver chloroiodobromide having a side length of 0.6 μm and a variation coefficient of 11%
It was an emulsion.

(Preparation of Emulsion K) In Emulsion J, a fine grain emulsion comprising 70 mol% of silver bromide and 30 mol% of silver chloride and doped with K ₂ [IrCl ₆ ] instead of fine grain emulsion A (average grain size) 0.05 μm) is changed to K ₂ [Ir
[Cl ₆ ] was prepared so that the amount was 5 × 10 ⁻⁹ mol per mol of silver halide. The resulting grains were cubic silver chloroiodobromide emulsions having a side length of 0.6 μm and a variation coefficient of 11%.

(Preparation of Emulsion L) In Emulsion J, a fine grain emulsion comprising 70 mol% of silver bromide and 30 mol% of silver chloride and doped with K ₂ [IrCl ₆ ] instead of fine grain emulsion A (average grain size) 0.05 μm) is changed to K ₂ [Ir
[Cl ₆ ] was prepared so that the amount was 2 × 10 ⁻⁸ mol per mol of silver halide. The resulting grains were cubic silver chloroiodobromide emulsions having a side length of 0.6 μm and a variation coefficient of 11%.

(Preparation of Emulsion M) In Emulsion J, a fine grain emulsion comprising 70 mol% of silver bromide and 30 mol% of silver chloride and doped with K ₂ [IrCl ₆ ] instead of fine grain emulsion A (average grain size) 0.05 μm) is changed to K ₂ [Ir
[Cl ₆ ] was prepared so that the amount was 5 × 10 ⁻⁸ mol per mol of silver halide. The resulting grains were cubic silver chloroiodobromide emulsions having a side length of 0.6 μm and a variation coefficient of 11%.

(Preparation of Emulsion N) In Emulsion J, a fine grain emulsion comprising 70 mol% of silver bromide and 30 mol% of silver chloride and doped with K ₂ [IrCl ₆ ] instead of fine grain emulsion A (average grain size) 0.05 μm) is changed to K ₂ [Ir
[Cl ₆ ] was prepared so that the amount was 1 × 10 ^-7 mol per mol of silver halide. The resulting grains were cubic silver chloroiodobromide emulsions having a side length of 0.6 μm and a variation coefficient of 11%.

(Preparation of Emulsion O) In Emulsion J, a fine grain emulsion comprising 70 mol% of silver bromide and 30 mol% of silver chloride and doped with K ₂ [IrCl ₆ ] instead of fine grain emulsion A (average grain size) 0.05 μm) is changed to K ₂ [Ir
Cl _6] weight was prepared only different emulsions it was added to a silver halide per mole 5 × 10 ^-7 mol. The resulting grains were cubic silver chloroiodobromide emulsions having a side length of 0.6 μm and a variation coefficient of 11%.

(Preparation of Emulsion P) In Emulsion J, a fine grain emulsion comprising 70 mol% of silver bromide and 30 mol% of silver chloride and doped with K ₂ [IrCl ₆ ] instead of fine grain emulsion A (average grain size) 0.05 μm) is changed to K ₂ [Ir
Cl _6] weight was prepared only different emulsions it was added to a silver halide per mole 2 × 10 ^-6 mol. The resulting grains were cubic silver chloroiodobromide emulsions having a side length of 0.6 μm and a variation coefficient of 11%.

(Preparation of Emulsion Q) Emulsion N was composed of 70 mol% of silver bromide and 30 mol% of silver chloride, and K ₂ [Ir
Cl ₆ ] -doped fine grain emulsion (average grain size 0.05
μm) instead of silver bromide 3 having an average particle size of 0.08 μm.
0 mol% silver chloride 70 mol%, and K ₂ [IrC
1 ₆ ], except that a fine grain emulsion doped with [ ₆ ] was used. The resulting grains were cubic silver chloroiodobromide emulsions having a side length of 0.6 μm and a variation coefficient of 11%.

(Preparation of Emulsion R) Emulsion N was composed of 70 mol% of silver bromide and 30 mol% of silver chloride and had a K ₂ [Ir
Cl ₆ ] -doped fine grain emulsion (average grain size 0.05
μm) instead of silver bromide 5 having an average particle size of 0.08 μm.
0 mol% silver chloride 50 mol%, and K ₂ [IrC
1 ₆ ], except that a fine grain emulsion doped with [ ₆ ] was used. The resulting grains were cubic silver chloroiodobromide emulsions having a side length of 0.6 μm and a variation coefficient of 11%.

(Preparation of Emulsion S) Emulsion N was composed of 70 mol% of silver bromide and 30 mol% of silver chloride, and K ₂ [Ir
Cl ₆ ] -doped fine grain emulsion (average grain size 0.05
μm) instead of silver bromide 1 having an average particle size of 0.05 μm.
An emulsion was prepared which differed only in that a fine grain emulsion consisting of 00 mol% and doped with K ₂ [IrCl ₆ ] was used.
The resulting grains were cubic silver chloroiodobromide emulsions having a side length of 0.6 μm and a variation coefficient of 11%.

(Preparation of emulsion T)
From 70% to 85% of the addition of _Two
[Ir (H_TwoO) Cl_Five] Add the aqueous solution to the finished halogen
The amount of Ir is 1 × 10^-6To be mole
Emulsions were prepared that differed only in the addition. Obtained particles
Is a cubic silver chloroiodobromide having a side length of 0.6 μm and a variation coefficient of 11%
It was an emulsion.

(Preparation of Emulsion U)
From 70% to 85% of the addition of _Two
[Ir (H_TwoO) Cl_Five] Add the aqueous solution to the finished halogen
Ir content of 5 × 10^-6To be mole
Emulsions were prepared that differed only in the addition. Obtained particles
Is a cubic silver chloroiodobromide having a side length of 0.6 μm and a variation coefficient of 11%
It was an emulsion.

(Preparation of Emulsion V) In Emulsion J, the amount of the aqueous solution of K ₂ [Ir (H ₂ O) Cl ₅ ] to be added at the time of adding silver nitrate was adjusted so that the Ir amount was 2 × 1
Instead of the amount equal to 0 ^-5 mol, and, in place of the fine grain emulsion A, bromide 70 consists mole% silver chloride 30 mol%, and K ₂ [IrCl _6] doped fine grain emulsion (average grain size 0 the _{.05μm), K 2 [IrCl 6} ] amount in this case was prepared only different emulsions it was added to a silver halide per mole 5 × 10 ^-8 mol. The resulting grains were cubic silver chloroiodobromide emulsions having a side length of 0.6 μm and a variation coefficient of 11%.

The emulsions prepared as described above are shown in Table 2 below.

[Table 2]

(Preparation of Sample Sample): A silver halide color photographic light-sensitive material A corona discharge treatment was applied to one surface of a support having both sides coated with polyethylene resin, and then dodecylbenzenesulfonic acid A gelatin undercoat layer containing sodium was provided, and a photographic component layer of the following first to seventh layers was further coated on the gelatin undercoat layer to prepare a sample sample of a silver halide color photographic light-sensitive material. . The coating solution for each photographic constituent layer was prepared as follows.

-Preparation of Coating Solution for First Layer- 57 g of the following yellow coupler (ExY), 7 g of the following color image stabilizer (Cpd-1), and the following color image stabilizer (Cpd-2)
4 g, the following color image stabilizer (Cpd-3) 7 g, the following color image stabilizer (Cpd-8) 2 g, and the following solvent (Solv-1) 2
Dissolve in 1 g and 80 ml of ethyl acetate and dissolve this solution in 23.5 containing 4 g of sodium dodecylbenzenesulfonate.
The emulsion was emulsified and dispersed in 220 g of a mass% aqueous solution of gelatin with a high-speed stirring emulsifier (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, the emulsified dispersion A and the chemically sensitized emulsion A were mixed and dissolved to prepare a coating solution for forming a first layer (first layer coating solution) so as to have a composition described below. Incidentally, the emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solution for forming the second to seventh layers (second layer to
The seventh layer coating solution) was prepared in the same manner as the first layer coating solution. As the gelatin hardener for each layer, the following 1-oxy-
3,5-dichloro-s-triazine sodium salt (H-
1), (H-2) and (H-3) in a total amount of 100 mg / m ²
Using. In addition, the following Ab-1, Ab-2, Ab-
3, and Ab-4, each in a total amount of 15.0 mg / m
^{2, 60.0mg / m 2, 5.0mg} / m 2 and 10.0
mg / m ² .

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[0131]

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The silver chlorobromide emulsions used for forming the third layer (green-sensitive emulsion layer) and the fifth layer (red-sensitive emulsion layer) used the following spectral sensitizing dyes, respectively.

Third layer (green-sensitive emulsion layer)

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(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for the emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMole of sensitizing dye F per mole of silver halide.
2.0 × 10^-FourMol, small sa
2.8 × 10^-FourMole was added. )

Fifth layer (red-sensitive emulsion layer)

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(Sensitizing dyes G and H were used in an amount of 8.0 × 10 8
^-5 mol and 10.7 × 10 ^-5 mol were added to the small size emulsion. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide. )

[0137]

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Also, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 1.0 × 10 ^-3 mol and 5 × 5 mol per mol of silver halide, respectively. 0.9 × 10 ^-4 mol was added.
Further, the second layer, the fourth layer, the sixth layer and the seventh layer are also provided with 0.2 mg / m ² , 0.2 mg / m ² and 0.6 mg / m ² respectively.
² and 0.1 mg / m ² . Further, 4-hydroxy-6 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
-Methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol, 2 mol
× 10 ^-4 mol was added. To the red-sensitive emulsion layer, 0.05 g / m ² of a copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200000 to 400,000) was added. Also, disodium catechol-3,5-disulfonate was added to the second layer, the fourth layer and the sixth layer at 6 mg / m ² , 6 mg / m ² and 18 mg / m ² respectively.
m ² . To prevent irradiation, the following dyes were added (in parentheses, the coating amount is shown).

[0139]

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-Layer Structure- The structure of each layer is shown below. The number is the coating amount (g / m ² )
Represents The silver halide emulsion represents a coating amount in terms of silver. <Support> ・ Polyethylene resin laminated paper (the polyethylene resin on the side forming the first layer is a white pigment (TiO ₂ ; content: 16% by mass, ZnO; content: 4% by mass), a fluorescent whitening agent (4, 4'-bis (5-methylbenzoxazolyl) stilbene; content 0.03% by mass),
Blue dye (including ultramarine blue)

<First Layer (Blue-Sensitive Emulsion Layer)> Emulsion a (Selected from emulsions A to V in Table 2; see Table 3 below) 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 colors Image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv) -1) 0.21

<Second layer (color mixture preventing layer)> Gelatin 0.99 Color mixture inhibitor (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0 .13 color image stabilizer (Cpd-7) 0.01 solvent (Solv-1) 0.06 solvent (Solv-2) 0.22

<Third Layer (Green-Sensitive Emulsion Layer)> Silver chlorobromide emulsion b 0.14 (gold-sulfur sensitized cubic, large-size emulsion with average grain size of 0.45 μm and small-size emulsion with 0.35 μm) (A silver molar ratio) of 0.10 and 0.08, respectively, and each size emulsion contained 0.15 mol% of silver iodide in the vicinity of the surface of the grains, and the 0.4 mol% of silver halide was locally contained on the surface of the grains.) Gelatin 1.36 Magenta coupler (ExM) 0.15 Ultraviolet absorber (UV-A) 0.14 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 0.002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 03 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.11 Solvent (Solv-4) 0.22 Solvent (Solv-5) 0.20

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention layer (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion c 0.12 (cube sensitized with gold and sulfur, a large emulsion having an average grain size of 0.40 μm and a small emulsion having a mean grain size of 0.30 μm A 5: 5 mixture (silver molar ratio), the coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively.Each size emulsion and each size emulsion contained 0.1 mol% of silver iodide near the grain surface. Gelatin 1.11 Cyan Coupler (ExC-2) 0.13 Cyan Coupler (ExC-3) 0.03 Color Image Stabilizer (Cpd- 1) 0.05 Color image stabilizer (Cpd-6) 0.06 Color image stabilizer (Cpd-7) 0.02 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 color image stabilizer (Cpd-14) 0.01 color image stabilizer ( Cpd-15) 0.12 Color image stabilizer (Cpd-16) 0.03 Color image stabilizer (Cpd-17) 0.09 Color image stabilizer (Cpd-18) 0.07 Solvent (Solv-5) 0 .15 Solvent (Solv-8) 0.05

Sixth layer (ultraviolet absorbing layer) Gelatin 0.46 Ultraviolet absorbing agent (UV-B) 0.45 Compound (S1-4) 0.0015 Solvent (Solv-7) 0.25

Seventh layer (protective layer) Gelatin 1.00 Acrylic modified copolymer of polyvinyl alcohol 0.04 (degree of modification 17%) Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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Sample 1 obtained as described above
(See Table 3).
Samples 2 to 22 shown in Table 3 below were prepared in the same manner as described above, except that the emulsions B to V shown in Table 3 were used.

The following experiment was conducted in order to examine the photographic characteristics of the sample samples obtained as described above. Each sample was subjected to sensitometric gradation exposure using a high-illumination exposure sensitometer (HIE type, manufactured by Yamashita Denso Co., Ltd.). An SP-1 filter manufactured by Fuji Photo Film Co., Ltd. was attached, and exposure was performed at a high illuminance of 10 ^-4 seconds. After the exposure, the following color development processing A was performed.

[Treatment A] The sample was 127 mm
After processing into a roll of width and imagewise exposing using a mini-lab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., continuous processing (running) until replenishing twice the capacity of the color developing tank in the processing process under the following processing conditions Test). The color developing process using the running liquid is referred to as process A. Processing Step Temperature Time Replenishment amount * Color development 38.5 ° C 45 seconds 45 ml Bleaching and fixing 38.0 ° C 45 seconds 35 ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds - rinse (3) ** 38.0 ℃ 20 seconds - rinsing (4) ** 38.0 ℃ 30 seconds 121 ml * photographic material 1 m ² per replenishment amount ** Fuji photo Film Co., Ltd. rinse cleaning system RC50D Install in rinse (3), take out rinse liquid from rinse (3), and send to reverse osmosis membrane module (RC50D) by pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane-based surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8 g 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g -Potassium bromide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescence 2.5 g 5.0 g Brightening agent (Hakkol FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 8 0.5 g 11.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 15.7 g potassium carbonate 26 3g 26.3g Add water 1000ml 1000ml pH (adjusted with potassium hydroxide and sulfuric acid at 25 ° C)

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 700 ml 600 ml iron (III) ammonium ethylenediaminetetraacetate 47.0 g 94.0 g 1.4 g 2.8 g m-carboxybenzenesulfinic acid 8.3 g 16.5 g nitric acid (67%) 16.5 g 33.0 g imidazole 14.6 g 29.2 g ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml ammonium sulfite 16.0 g 32.0 g ammonium bisulfite 23.1 g 46.2 g Water was added to add 1000 ml 1000 ml pH (adjusted at 25 ° C./acetic acid and ammonia) 6.0 6.0

[Rinse Solution] [Tank Solution] [Replenisher] 0.02 g 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity 5 μS / cm or less) 1000 ml 1000 ml pH 6.5 6.5

The yellow color density of each of the processed samples was measured, and the exposure high illuminance sensitivity for 10 ^-4 seconds was determined. The sensitivity was defined as the reciprocal of the exposure amount giving a color density higher than the minimum color density by 1.0, and was expressed as a relative value when the sensitivity of Sample 1 coated with Emulsion A was 100. The gradation (contrast) was determined from the slope of the straight line between the sensitivity point and the sensitivity point at the density of 1.5. Further, gradation exposure for sensitometry was given by 0.1 second exposure using a light meter for medium illumination exposure (FW type, manufactured by Fuji Photo Film Co., Ltd.). A change (difference) in the density of the area corresponding to the exposure amount giving a density of 1.5 at the time of 30 seconds after the exposure after 60 minutes from the exposure was obtained as an index indicating the latent image stability. . Therefore, it can be said that the smaller the numerical value is, the smaller the change amount is and the more excellent the latent image stability is. The above results are shown in Table 3 below.

[0165]

[Table 3]

As is clear from the results in Table 3, the halo
K is added to the silver halide particles at a site where the silver chloride content is 90 mol% or more.
_Two[Ir (H_TwoO) Cl_FiveIs doped and K_Two[Ir
Cl ₆Has a Br content of 40 mol of silver halide grains.
% Silver halide emulsion
In the sample of the present invention, high illuminance sensitivity is increased
Thus, an image having a high gradation was obtained. At the same time, the latent image
The qualification was also very good. On the other hand, the sample
High sensitivity and high contrast as long as the latent image stability is excellent
Is not enough.
Latent image stability could not be obtained.

Example 2 A sample having a reduced thickness was prepared by changing the layer structure as described below, and the same experiment as in Example 1 was performed on this sample. Results are in Example 1.
In the same manner as above, even when the sample sample having been thinned was subjected to ultra-rapid processing, the high illuminance sensitivity was increased, and the gradation could be hardened. At the same time, the latent image stability was very good.

(Preparation of Sample Sample): Silver halide color photographic light-sensitive material <First layer (blue-sensitive emulsion layer)> Emulsion a (selected from emulsions A to V in Table 2; see Table 3) 24 Gelatin 1.25 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 colors Image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21

Second layer (color mixture preventing layer) Gelatin 0.60 Color mixture inhibitor (Cpd-19) 0.09 Color image stabilizer (Cpd-5) 0.007 Color image stabilizer (Cpd-7) 0.007 UV absorber (UV-C) 0.05 Solvent (Solv-5) 0.11

Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion b (the same emulsion as in Example 1) 0.14 gelatin 0.73 magenta coupler (ExM) 0.15 ultraviolet absorber (UV-A) 0 0.05 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-7) 0.008 Color image stabilizer (Cpd-8) 0.07 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.009 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.06 Solvent (Solv-4) 0.11 Solvent (Solv-5) 0. 06

Fourth layer (color mixture prevention layer) Gelatin 0.48 Color mixture prevention layer (Cpd-4) 0.07 Color image stabilizer (Cpd-5) 0.006 Color image stabilizer (Cpd-7) 0.006 UV absorber (UV-C) 0.04 Solvent (Solv-5) 0.09

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion c (the same emulsion as in Example 1) 0.12 gelatin 0.59 cyan coupler (ExC-2) 0.13 cyan coupler (ExC-3) 0.03 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-15) 0.19 Color image stabilizer (Cpd-18) 04 UV absorber (UV-7) 0.02 Solvent (Solv-5) 0.09

Sixth layer (ultraviolet absorbing layer) Gelatin 0.32 Ultraviolet absorber (UV-C) 0.42 Solvent (Solv-7) 0.08 Seventh layer (protective layer) Gelatin 0.70 Acrylic of polyvinyl alcohol Modified copolymer (degree of modification 17%) 0.04 Liquid paraffin 0.01 Surfactant (Cpd-13) 0.01 Polydimethylsiloxane 0.01 Silicon dioxide 0.003

Each of the produced sample samples was exposed in the same manner as in the experiment of Example 1, and the color developing process was performed ultra-rapidly according to the following developing process B.

[Process B] An experiment in which each sample sample obtained above was processed into a roll having a width of 127 mm, and a minilab printer processor PP350 manufactured by Fuji Photo Film Co., Ltd. was modified so that the processing time and processing temperature could be changed. Using a processing apparatus, the sample sample was imagewise exposed from a negative film having an average density, and the volume of the color developing replenisher used in the following processing step was 0.1% of the volume of the color developing tank.
The continuous processing (running test) was performed until the value became 5 times. The color developing process using this running liquid is referred to as process B.

Processing Step Temperature Time Replenishment amount * Color development 45.0 ° C. 15 seconds 45 ml Bleaching and fixing 40.0 ° C. 15 seconds 35 ml Rinse (1) 40.0 ° C. 8 seconds-Rinse (2) 40.0 ° C. 8 sec - rinse (3) ** 40.0 ° C. 8 seconds - rinse (4) ** 38.0 ° C. 8 seconds 121 ml drying 80 ° C. 15 seconds (Note) * photographic material 1 m ² per replenishment amount ** Fuji A rinse screening system RC50D manufactured by Photo Film Co., Ltd. is attached to the rinse (3), and the rinse liquid is taken out of the rinse (3) and sent to a reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse (4), and the concentrated liquid is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day. The rinsing was of a four-tank countercurrent type from (1) to (4).

The composition of each processing solution is as follows. [Color developing solution] [Tank solution] [Replenisher] Water 800 mL 600 mL Fluorescent brightener (FL-1) 5.0 g 8.5 g Triisopropanolamine 8.8 g 8.8 g Sodium p-toluenesulfonate 20.0 g 20 0.0 g ethylenediaminetetraacetic acid 4.0 g 4.0 g sodium sulfite 0.10 g 0.50 g potassium chloride 10.0 g-sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.50 g 0.50 g disodium-N, N-bis (sulfonatoethyl) hydroxylamine 8.5 g 14.5 g 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline / 3/2 sulfate monohydrate 10 0.0g 22.0g Potassium carbonate 26.3g 26.3g Water was added to make the total amount 1000mL 10. 00 mL pH (adjusted at 25 ° C with sulfuric acid and KOH) 0.35 12.6

[Bleach-fix solution] [Tank solution] [Replenisher] Water 800 mL 800 mL Ammonium thiosulfate (750 g / mL) 107 mL 214 mL Succinic acid 29.5 g 59.0 g Ethylene (III) ammonium ethylenediaminetetraacetate 47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4 g 2.8 g Nitric acid (67%) 17.5 g 35.0 g Imidazole 14.6 g 29.2 g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Water was added and the whole amount was added. 1000 mL 1000 mL pH (adjusted at 25 ° C. with nitric acid and aqueous ammonia) 6.00 6.00

[Rinse liquid] [Tank liquid] [Replenisher] Dechlorinated sodium isocyanurate 0.02 g 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL pH (25 ° C.) 6.5 6. 5

[0180]

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Example 3 Using the sample samples of Example 2, an image was formed by laser scanning exposure.
As a laser light source, a semiconductor laser GaAlAs
A semiconductor laser GaAlAs obtained by converting the wavelength of a YAG solid-state laser (oscillation wavelength 946 nm) (oscillation wavelength 946 nm) using an excitation light source (oscillation wavelength 808.5 nm) with an SHG crystal of LiNbO ₃ having an inversion domain structure,
(Oscillation wavelength: 808.7 nm) as excitation light source YVO ₄
A wavelength of 532 nm obtained by converting a solid-state laser (oscillation wavelength: 1064 nm) using an SHG crystal of LiNbO ₃ having an inversion domain structure, and AlGaInP (oscillation wavelength: about 680 nm: Type No.
0) was used.

Each of the laser beams of the three colors is moved by a polygon mirror in a direction perpendicular to the scanning direction, so that the laser light can be sequentially scanned and exposed on the sample. Fluctuations in light intensity due to the temperature of the semiconductor laser are suppressed by using a Peltier element to keep the temperature constant. The effective beam diameter is 80 μm and the scanning pitch is 42.3 μm
(600 dpi), and the average exposure time per pixel was 1.7 × 10 ⁻⁷ seconds. After the exposure, when the same color development processing B as in Example 2 was performed, the same result as that of the high illuminance exposure in Example 2 was obtained, and the silver halide particles had a silver chloride content of 90 mol% or more in the site. K ₂ [Ir (H ₂ O) C
l ₅ ] and K ₂ [IrCl ₆ ] was used in a sample containing a silver halide emulsion doped with silver halide grains having a Br content of 40 mol% or more. Was increased in sensitivity and the gradation was hard. Moreover, the latent image stability was very good. From the above, it was found that the method was also suitable for image formation using laser scanning exposure.

[Example 4] Instead of the UV absorbers UV-A and UV-B used in Examples 1 to 3, only UV-4 containing as a part of the mixed composition among them UV of the same mass was used. -8
The following UV-A 'and UV-B', each of which was replaced with the corresponding UV-A and UV-B, respectively, except that the same mass was used to prepare sample samples in the same manner as in Examples 1 to 3. Experiments, evaluations, etc. were performed. UV-A ': UV-1 / UV-2 / UV-3 / UV-8 = 4/2/2/3 mixture (mass ratio) UV-B': UV-1 / UV-2 / UV-3 / UV-8 / UV-5 / UV-6 = 9/3/3/4/5/3
As a result, the same results as in Examples 1 to 3 were confirmed.

[0184]

According to the present invention, laser scanning exposure
It is possible to provide a silver halide emulsion which does not suffer from high illuminance failure at the time of (ultra) high illuminance exposure (digital exposure), can obtain a high-contrast color development gradation with high sensitivity, and has little latent image sensitization. In addition, high sensitivity and hard gradation can be obtained without high illuminance failure due to (ultra) high illuminance exposure (digital exposure) such as laser scanning exposure, etc. A silver halide color photographic light-sensitive material capable of stably forming a high image can be provided.

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Claims (6)

[Claims] 1. A hexacoordination complex having iridium (Ir) as a central metal and having at least one H ₂ O as a ligand is doped into a portion of a silver halide grain having a silver chloride content of 90 mol% or more, Silver halide grains in which a hexacoordination complex having iridium (Ir) as a central metal and having Cl, Br or I as a ligand is doped at a site where the silver bromide content of the silver halide grains is 40 mol% or more A silver halide emulsion comprising: 2. The silver halide emulsion according to claim 1, wherein the portion having a silver bromide content of 40 mol% or more in the silver halide grains is formed by dissolving and depositing silver halide fine grains. . 3. The silver halide grains having a silver iodide content of 0.1%.
The silver halide emulsion according to claim 1 or 2, wherein the silver halide grains are from 02 mol% to 1 mol% inclusive. 4. A support comprising at least one silver halide emulsion layer containing a yellow dye-forming coupler, at least one silver halide emulsion layer containing a magenta dye-forming coupler and at least one halogen containing a cyan dye-forming coupler. A silver halide color photographic material having a photosensitive emulsion layer including a silver halide emulsion layer, wherein at least one of the photosensitive emulsion layers contains iridium (Ir) having at least one H ₂ O as a ligand as a central metal. Is doped at a site having a silver chloride content of 90 mol% or more of silver halide grains, and C
Iridium having l, Br or I as a ligand (I
A silver halide color photograph, characterized in that the six-coordination complex having r) as a central metal contains silver halide grains doped at a site where the silver bromide content of the silver halide grains is at least 40 mol%. Photosensitive material. 5. The silver halide grain according to claim 4, wherein the portion having a silver bromide content of 40 mol% or more in the silver halide grain is a silver halide grain formed by dissolving and depositing silver halide fine grains. The silver halide color photographic light-sensitive material described in the above. 6. The silver halide grains having a silver iodide content of 0.1%.
6. The silver halide color photographic light-sensitive material according to claim 4, wherein the silver chloroiodobromide grains comprise from 02 mol% to 1 mol%.