JP2003295373A - Silver halide emulsion and silver halide photosensitive material obtained by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide emulsion from which a silver halide photosensitive material is obtained, the material having suitability to digital exposure such as laser scanning exposure and suitability to rapid processing, having high sensitivity and excellent in exposure temperature dependence and to provide a silver halide photosensitive material (particularly a silver halide photographic sensitive material) obtained by using the same. <P>SOLUTION: In the silver halide emulsion comprising silver halide grains having ≥90 mol% silver chloride content, ≥80% of the total projected area of the silver halide grains is occupied by tabular grains having an average aspect ratio of ≥2 and <0.3 μm average thickness, the coefficient of variation in equivalent spherical diameter of all the grains is ≤20%, and a hexacoordination iridium complex having at least one non-halogen or non- cyanogen as a ligand to Ir as a central metal is contained. <P>COPYRIGHT: (C)2004,JPO

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 more specifically, it provides a highly sensitive and hard gradation even in digital exposure such as laser scanning exposure, is stable to an exposure environment, and is quick. The present invention relates to a silver halide emulsion capable of obtaining a silver halide light-sensitive material having processability, and a silver halide light-sensitive material using the same.

[0002]

2. Description of the Related Art In recent years, digitalization has been remarkably permeated even in the field of color printing using color photographic paper. For example, the digital exposure method by laser scanning exposure can be applied to a color printer from a processed color negative film which has been conventionally used. Compared to the analog exposure method that directly prints, it shows a dramatic increase in the penetration rate. Such a digital exposure method is characterized in that a high image quality can be obtained by performing image processing, and plays an extremely important role in improving the quality of color prints using color printing paper. Further, with the rapid spread of digital cameras, it is also an important factor that color prints of high image quality can be easily obtained from these electronic recording media, and it is considered that this will lead to a further dramatic spread.

On the other hand, as the color printing method, techniques such as an ink jet method, a sublimation method, and a color xerography have made progress, and the color printing method is being recognized as a color printing method. Among these, the characteristics of the digital exposure method using color photographic paper are high image quality, high productivity, and high image fastness, and by further increasing these, it is possible to easily produce higher quality photographs. It is desired to provide it at a lower cost.

As a silver halide emulsion used for color photographic paper, a silver halide emulsion having a high silver chloride content is used mainly because of the demand for rapid processability for enhancing productivity. At present, a processing is generally performed in which a light-sensitive material containing a high silver chloride emulsion is processed with a color development time of 45 seconds and a total processing time is about 4 minutes. (For example, color processing CP-45X manufactured by Fuji Photo Film Co., Ltd.). However, other color systems (eg electrostatic transfer system, thermal transfer system,
It is hard to say that the processing system for high silver chloride color print materials is satisfactorily quicker than the processing time for inkjet printing), and the total processing time for high silver chloride color print materials is further accelerated (ultra-quick processing). Is desired.

To increase the developing speed of color photographic paper,
It is well known in the art that reducing the size of the high silver chloride grains of the silver halide emulsion to be used is one of the means, but the sensitivity is also reduced. It is also well known in the art to adopt a flat plate shape as one means for achieving a highly sensitive and small size. On the other hand, such a silver halide emulsion having a high silver chloride content is generally liable to cause low softness in high-intensity exposure such as laser scanning exposure and rapid processing, and various techniques for improving this point have been proposed. It is disclosed.

Although the gradation can be corrected in the digital exposure photosensitive material, from the viewpoint of color fringing and cost, it is required to have a gradation as hard as possible. Further, the emulsion grains are required to have a monodisperse grain size.

On the other hand, when the exposure condition is set in the morning in the minilab exposure apparatus, there is a problem that the exposure temperature becomes high during the subsequent use and the exposure condition is deviated. Some exposure apparatuses have a function of correcting the exposure temperature dependency of the light-sensitive material, but they are not perfect, and in particular when the gradation is hard, the deviation becomes large, which is likely to cause a problem. Especially in the case of a high contrast emulsion, it is important that the exposure temperature dependency is small.

[0008]

In view of these problems, the present inventors have made a detailed study and found that such high silver chloride tabular grains can be exposed to high illuminance for a short time after exposure (30
It has been newly found that the exposure temperature dependence in (seconds) is a serious problem. It is a surprising fact that high silver chloride tabular grains have not been disclosed so far and that the exposure temperature dependence in such a high illuminance and short time latent image becomes large.

By the way, it is known to dope iridium in order to improve the high illumination failure of silver chloride emulsions. For example, in Japanese Patent Laid-Open No. 7-72569, {100}
For a tabular silver chloride grain whose main plane is [Ir (t
Although it has been disclosed that the use of (hiazole) Cl ₅ ] ²⁻ improves both the low illuminance failure and the high illuminance failure with a high feeling, it does not describe the exposure temperature dependency.

An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, an object of the present invention is to provide a silver halide emulsion which has a digital exposure suitability such as laser scanning exposure and a rapid processing suitability, and is capable of obtaining a silver halide light-sensitive material having high sensitivity and excellent exposure temperature dependency, And to provide a silver halide light-sensitive material (especially silver halide photographic light-sensitive material) using the same.

[0011]

The present inventors have found that the following means can be used to effectively solve the above problems. That is, the present invention provides: (1) In a silver halide emulsion containing silver halide grains having a silver chloride content of 90 mol% or more, 80% or more of the projected area of the silver halide grains has an average aspect ratio of 2 or more and an average aspect ratio of 2 or more. Six-coordinate with tabular grains having a thickness of less than 0.3 μm, variation coefficient of spherical equivalent diameter of all grains being 20% or less, and having Ir as a central metal having at least one non-halogen or non-cyan ligand as a ligand. A silver halide emulsion containing an iridium complex.

(2) In a silver halide emulsion containing silver halide grains having a silver chloride content of 90 mol% or more, 80% or more of the projected area of the silver halide grains has an average aspect ratio of 2 or more and an average thickness of 0. A 6-coordinate iridium complex having Ir as the central metal, which is a tabular grain having a size of less than 3 μm, has a variation coefficient of equivalent spherical diameter of all grains of 20% or less, and has at least one non-halogen or non-cyan as a ligand. A silver halide emulsion comprising at least one and at least one hexacoordinate iridium complex having 6 chlorines as ligands.

(3) The silver halide emulsion according to the above (1) or (2), characterized in that the tabular grains of the silver halide grains have {111} faces as main planes.

(4) The silver halide emulsion as described in any one of (1) to (3) above, wherein the hexacoordinate iridium complex is contained in the silver bromide-containing phase. .

(5) Any one of (1) to (4) above
A silver halide light-sensitive material containing the silver halide emulsion described in the item 1.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Silver Halide Emulsion] The silver halide emulsion of the present invention comprises silver halide grains described below. The silver halide grains will be described.

The silver halide grains are required to have tabular grains accounting for 80% or more of the projected area of all grains. Here, all grains mean "all silver halide grain grains" contained in a silver halide emulsion. The tabular grains have two parallel main planes facing each other and have an average aspect ratio of 2 or more. Here, the aspect ratio is a value obtained by dividing the diameter (a) of a circle corresponding to the projected area of tabular grains by the thickness (b) of tabular grains. The larger the aspect ratio, the flatter the shape becomes. In the present invention, an average aspect ratio of 5
100 is preferable, more preferably 7.0 to 100, and further preferably 10.0 to 100. Here, the average aspect ratio means the average value of the aspect ratios of all tabular grains in the emulsion. The projected diameter of a tabular grain (diameter of circle equivalent to projected area (a)) refers to the diameter of a circle having an area equal to the projected area when the principal plane is placed in parallel with the substrate surface and observed from the vertical direction. . In the present invention, a “circle equivalent diameter” or a “projected area equivalent diameter” is used in the same meaning as the “projected diameter”. The equivalent circle diameter of the tabular grains is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm.
m, particularly preferably 0.2 to 2.0 μm. Also,
Those particle size distributions have a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20% or less,
It is preferably monodisperse with a content of 15% or less.
At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating.

The tabular grain thickness (b) refers to the distance between the two principal planes of the tabular grain, and the average thickness means the average value of the thicknesses (b) of all the tabular grains. In the present invention, the average thickness is less than 0.3 μm, but 0.01 to 0.30.
μm is preferable, and 0.02 to 0.20 is more preferable.
μm, particularly preferably 0.05 to 0.15 μm.
The thickness (b) of the tabular grains was measured by vapor-depositing metal from the oblique direction of the grains together with a reference latex, measuring the shadow length on an electron micrograph, and referring to the shadow length of latex. It can be easily calculated.

The tabular grains in the silver halide grains are
{111} plane or {100} plane (preferably {111} plane
Tabular grains (hereinafter referred to as {11
1) tabular grains and {100} tabular grains). Here, the main plane is a set of parallel planes perpendicular to the thickness direction of tabular grains.

First, the {111} tabular grains will be described. A method of adding an additive (crystal phase controlling agent) at the time of grain formation in order to form {111} tabular grains is known,
It can be suitably used. Hereinafter, examples of the crystal habit controlling agent will be shown.

[0021]   Patent number Crystal habit control agent Inventor ・ U.S. Pat. No. 4,400,463 Azaindenes Muscasky                                 + Thioether Peptizer- -U.S. Pat. No. 4,783,398 No. 2-4-dithiazolidinone -U.S. Pat. No. 4,713,323 Aminopyrazolopyrimidine Mascasky -U.S. Pat. No. 4,983,508 Bispyridinium salt Ishiguro, etc. US Pat. No. 5,185,239 Triaminopyrimidine muscaski -U.S. Pat. No. 5,178,997 7-azaindole type compound Mascasky ・ US Pat. No. 5,178,998 Xanthine Mascasky ・ Japanese Patent Laid-Open No. 64-70741 Dye Nishikawa et al. ・ JP-A-3-212639 Aminothioether Ishiguro ・ JP-A-4-283742 Thiourea derivative Ishiguro ・ JP-A-4-335632 Triazolium salt Ishiguro ・ JP-A-2-32, bispyridinium salt, Ishiguro, etc. ・ JP-A-8-227117, monopyridinium salt, Ozeki, etc.

Among various crystal habit controlling agents as described above,
Compounds described in JP-A-2-32 (Compound Example 1
To 42) are preferable, and the crystal habit controlling agents 1 to 29 described in JP-A-8-227117 are particularly preferable. However, the present invention is not limited to these.

The {111} tabular grains are obtained by forming two parallel twin planes. The formation of the twin plane depends on the temperature, the dispersion medium (gelatin), the halogen concentration, the addition rate of silver, the halogen, etc., so these conditions must be set appropriately. When the crystal habit controlling agent is present during nucleation, the gelatin concentration is preferably 0.1% to 10%. The silver chloride concentration is 0.01 mol / liter or more, preferably 0.03 mol / liter or more.

In order to make tabular grains monodisperse,
It is disclosed in JP-A-8-184931 that it is preferable not to use a crystal habit controlling agent for nucleation. When the crystal habit controlling agent is not used during nucleation, the gelatin concentration is preferably 0.03% to 10%, more preferably 0.0
It is 5% to 1.0%. Silver chloride concentration is 0.001 mol /
It is preferably from 1 to 1 mol / liter, more preferably from 0.003 mol / liter to 0.1 mol / liter. The nucleation temperature can be selected from 2 ° C to 90 ° C, but is preferably 5 ° C to 80 ° C, more preferably 5 ° C to 5 ° C.
0 degreeC is preferable and 15 degreeC-45 degreeC is especially preferable.

As the type of gelatin used for nucleation, alkali-processed gelatin is usually used, but other modified gelatin such as oxidation-processed gelatin, amber gelatin, phthalated gelatin and trimellitic gelatin may also be used. it can. The molecular weight of gelatin is usually
Gelatin having a molecular weight of 10,000 or more can be used, but in order to monodisperse tabular grains, gelatin having a molecular weight of 60,000 or more is preferable, and high molecular weight gelatin having 100,000 or more is more preferable. Gelatin concentration for nucleation is 0.03%
-10% is preferable, and more preferably 0.05% -1.
It is 0%.

Although nuclei of tabular grains are formed in the initial nucleation step, a large number of nuclei other than tabular grains are contained in the reaction vessel immediately after nucleation. Therefore, it is necessary to have a technique of performing ripening after nucleation so that only tabular grains remain and the others disappear. When normal Ostwald ripening is performed, tabular grain nuclei are also dissolved and disappeared, so that tabular grain nuclei are reduced and the size of the resulting tabular grains may be increased. In order to prevent this, a crystal habit controlling agent is added. At this time, it is preferable to use a modified gelatin such as phthalated gelatin, amber gelatin or trimellitic gelatin in combination because the effect of the crystal habit controlling agent can be enhanced and the dissolution of tabular grains can be prevented. The pAg during aging is particularly important and is preferably 50 to 140 mV, and particularly preferably 60 to 120 mV with respect to the silver-silver chloride electrode.

The formed nuclei are grown in the presence of a crystal habit controlling agent by physical ripening and addition of a silver salt and a halide. The chloride concentration during growth is preferably 5 mol / liter or less,
It is more preferably 0.05 to 1 mol / liter. The temperature during grain growth can be selected in the range of 10 ° C to 95 ° C, but is preferably in the range of 30 ° C to 80 ° C. The total amount of crystal habit modifier used is 6 × per mol of silver halide in the finished emulsion.
It is preferably 10 ^-5 mol or more, particularly 3 × 10 ^-4 mol to 6 ×
10 ^-2 mol is preferred. The crystal habit controlling agent may be added at any time from the nucleation of silver halide grains to the physical ripening or grain growth. The formation of {111} planes starts after the addition. The crystal habit controlling agent may be added in advance in the reactor, but in the case of forming small-sized tabular grains, it is preferable to add it in the reaction vessel along with grain growth to increase its concentration.

Next, the {100} tabular grains will be described. The {100} tabular grains are tabular grains having the {100} plane as the main plane, and when the tabular grains having the {100} plane as the main plane are classified by shape, the following six can be listed. (1) The shape of the principal plane is a right-angled parallelogram, and the aspect ratio = side ratio (long side length / short side length) in one tabular grain.
Is 1 to 10, preferably 1 to 3, and more preferably 1 to 2.
(2) Particles in which one or more, preferably 1 to 3 of the four corners of the right-angled parallelogram are non-equivalently omitted,
That is, [(maximum missing area / minimum missing area) =
Particles having K1 of 2 to ∞], (3) particles equivalently missing the four corners (particles having K1 smaller than 2), (4) 5 to 100% of the area of the edge surface of the missing part. , Preferably 20-
100% of the grains are {111} faces, (5) grains in which at least two opposite sides of the four edge sides forming the contour of the projected shape of the tabular grains are outwardly convex curves,
(6) Particles in which one or more, preferably 1 to 3 of the four corners of the right parallelogram are missing in the right parallelogram.
In addition, the area of the edge surface of the tabular grain is 1 to 10
There can be mentioned grains having 0%, preferably 5 to 50% of {n10} planes. Here, n = 1 to 5, preferably 1.

The {100} tabular grains can be formed by adding and mixing an aqueous silver salt solution and an aqueous halide salt solution in a dispersion medium such as an aqueous gelatin solution while stirring. For example, in JP-A-6-301129, JP-A-6-347929, JP-A-9-34045, and JP-A-9-96881, silver iodide or iodide ion, or silver bromide or bromide ion is used. There is disclosed a method in which a crystal defect, which is caused to exist, causes strain in a nucleus due to a difference in crystal lattice size from silver chloride, and imparts anisotropic growth property such as screw dislocation. When the screw dislocation is introduced, the formation of two-dimensional nuclei on that surface is not rate-determining under low supersaturation conditions, so that crystallization proceeds on this surface and tabular grains are formed by introducing the screw dislocation. . Here, the low supersaturation condition indicates preferably 35% or less, more preferably 2 to 20% at the time of critical addition. Although it was not confirmed that the crystal defect was a screw dislocation,
It is considered that there is a high possibility that it is a screw dislocation because the direction in which the dislocations are introduced or the grains are given anisotropic growth. In order to make the {100} tabular grains thinner, it is preferable to retain the introduced dislocations.
No. 954 and No. 9-189977. Alkali-processed gelatin is usually used as the type of gelatin used for nucleation, but modified gelatin such as oxidation-processed gelatin, amber gelatin, phthalated gelatin, and trimellitated gelatin may also be used. In order to make the {100} tabular grains thinner, it is usually preferable to use gelatin having a molecular weight of 10,000 or more.

Further, in JP-A-6-347928, imidazoles and 3,5-diaminotriazoles are used, and polyvinyl alcohols disclosed in JP-A-8-339044 are used. 10
It is also possible to use a method of forming a {100} tabular grain by adding a 0} plane formation accelerator. However, the present invention is not limited to these.

As the silver halide grains containing tabular grains as described above, silver halide grains having a silver chloride content of 90 mol% or more (preferably silver chloroiodobromide grains) are used. From the viewpoint of rapid processability, the silver chloride content is 9
Silver halide grains having 7 mol% or more (preferably silver chloroiodobromide grains) are preferable, and silver halide grains having a silver chloride content of 98 mol% or more (preferably silver chloroiodobromide grains) are more preferable. Among such silver halide grains, the content of iodide ions contained in the silver halide grains is preferably 0.01 to 1.0 mol%, more preferably 0.05 to 0.80 per mol of total silver. Mol%, most preferably 0.
Those having a silver iodochloride phase containing 05 to 0.60 mol% of iodide ions are preferable because high sensitivity can be obtained and the suitability for exposure to high illuminance is excellent.

The silver halide grains (preferably silver chloroiodobromide grains) preferably have a so-called core / shell structure composed of a core portion and a shell portion surrounding the core portion. It is preferable that 90 mol% or more of the core portion is silver chloride. The core part may further be composed of two or more parts having different halogen compositions. The shell portion is preferably 50% or less of the total particle volume, and particularly preferably 40% or less. In that case, the iodide ion content of the shell part is 0.01 to 8.
0 mol%, more preferably 0.05 to 6.0 mol%, most preferably 0.25 to 4.0 mol%, and the iodide ion content of the core part is 1/10 of the value of the shell part. The following are preferred.

The silver halide grains preferably have a silver iodide-containing phase (silver iodide localized phase). In particular, tabular grains preferably have a silver iodide-containing phase (silver iodide localized phase) that decays inward (depth) from the main plane. At this time, the iodide is preferably introduced (supplied) continuously along with the addition of the silver salt solution and the high chloride salt solution. The direction from the main plane to the inside (depth) refers to the direction perpendicular to the main plane. Further, the introduction of this iodide causes a smaller increase in sensitivity as it is more inside the emulsion grains.
The iodide salt solution is preferably added to the outside of 50% of the grain volume, more preferably to the outside of 70%, and most preferably to the outside of 80%. The silver potential at the time of introducing iodide is preferably 40 to 200 mV, more preferably 50 to 160 mV, and 60 to 140 mV.
V is particularly preferred. At this time, it is preferable to introduce the iodide while increasing the silver potential, and the potential increase rate is preferably 1.05 to 3.75 times the initial silver potential at the time of introducing the iodide, and 1.1. Is more preferably 2.4 to 2.4 times, most preferably 1.2 to 1.8 times. Further, it is preferable to form the iodide while increasing the supply rate thereof. The supply rate was 1.
It is preferably from 02 to 5.4 times, more preferably from 1.1 to 4.2 times, and most preferably from 1.2 to 3.5.
Double. The addition of the iodide salt solution may be terminated during grain formation (inside the total grain volume), preferably 90 to 100% of the grain volume, and more preferably 96 to 100%.
It is 100%. The iodide to be added may be added separately from the high chloride salt solution or as a mixed solution of the iodide salt and the high chloride salt. The iodide is added in the form of a soluble salt such as an alkali or alkaline earth iodide salt, or the iodide ion is cleaved from the organic molecule described in US Pat. No. 5,389,508. It is also possible to introduce iodide in the above step, but it is preferable to make the attenuation profile of the iodide ion concentration between grains uniform, and it is particularly preferable to use fine silver iodide grains as the iodide ion source. At this time, the fine silver iodide grain size is 0.2 to 0.00.
1 μm is preferable, and 0.1 to 0.002 is more preferable.
μm, most preferably 0.05 to 0.004 μm.

Here, the distribution of the iodide ion concentration from the main plane of the tabular grains to the inside (depth) direction can be measured by the following method. Generally, the distribution of iodide ion concentration from the grain surface to the depth (inner) direction is
TOF-SIMS (Time of Flight-S)
elementary Ion Mass Spectro
For example, TRIFT II type TOF-SIMS manufactured by Phi Evans can be used for measurement. The TOF-SIMS method is specifically described in "Surface Analysis Technology Selection Manual, Secondary Ion Mass Spectroscopy" edited by The Surface Science Society of Japan, Maruzen Co., Ltd. (issued in 1999). The surface of the particles is etched with gallium ions in the TOF-SIMS device, and the TOF-SIM is etched after the etching.
Iodide ions are detected by mass spectrometry of the pole surface by the S method. The etching rate is obtained in advance, and the depth position is determined by converting the time required for etching into the etching depth. Etching measurement sample and TO
By repeating the F-SIMS measurement, the concentration distribution of iodide ions in the depth (inner) direction from the grain surface can be evaluated. In the preparation of the measurement sample, when the tabular grains are diluted and adjusted to such an extent that they do not overlap, the tabular grains are oriented and the principal plane can be measured mainly. The distribution of concentration can be evaluated. At this time, the depth resolution of the etching / TOF-SIMS method is about several nm. Short region of the etching time, with the etching of organic origin such as gelatin remaining on the particle surface ¹³
The secondary ionic strength of CH ⁻ decreases. Secondary ions such as chloride ions and iodide ions derived from silver halide grains are detected only after the organic substances such as gelatin are removed by etching. Therefore, this point is the outermost surface of the tabular grains,
The distribution of the iodide ion concentration in the depth direction can be evaluated from the starting point.

The iodide ion concentration on the main plane of the tabular grains is preferably 1 mol% or more, more preferably 1.5 mol% or more, and particularly preferably 2 mol% or more with respect to the silver ion concentration on the main plane. . What is the iodide ion concentration on the main plane? ESCA (Electron Spec
Roscopy for Chemical Anal
ysys) method. For example Ulvac P
Using ESCA5300 manufactured by hi, in order to prevent damage to the sample due to thermal radiation from the irradiated X-ray or X-ray source, the sample was measured by repeatedly performing cumulative measurement while cooling the sample with liquid nitrogen. At this time, the value obtained when the photoelectrons emitted from the sample surface by X-ray irradiation were detected at an extraction angle of 90 ° with respect to the sample surface was used.

The silver halide grains preferably have a higher silver bromide content in the shell portion than in the core portion. The one having a silver bromide-containing phase (silver bromide localized phase) having a silver bromide content of 0.2 to 5 mol%, more preferably 0.5 to 3 mol% based on the total silver mol has high sensitivity. It is particularly preferable because it can be obtained and the photographic performance can be stabilized. This silver bromide-containing phase (silver bromide localized phase) can take a band-like continuous phase localized in the outermost layer of the fringe portion connecting the side surfaces of the tabular grains, in addition to the conventional epitaxial phase. The silver bromide content of this silver bromide-containing phase (silver bromide localized phase) is 5 to 100%, more preferably 10 to 100%, most preferably 20 to 1%.
It is 00%. The silver bromide content of the silver bromide localized phase is 10 to 10.
The range of 60 mol% is preferable, and the range of 20 to 50 mol% is the most preferable.

It is necessary that the silver halide grains contain at least one non-halogen or non-cyan hexacoordinate iridium complex having Ir as a central metal and having a ligand as a ligand. The non-halogen or non-cyan ligand is a ligand other than halogen and cyano, and specific examples of the hexacoordinate iridium complex include H ₂ O, OH, O and OC.
A hexacoordinated iridium complex having Ir as the central metal and having N, thiazole or substituted thiazole as a ligand is preferable, and at least one H ₂ O, OH, O, OCN,
A hexacoordinated iridium complex in which thiazole or substituted thiazole is used as a ligand and the remaining ligand is Cl, Br, or I and Ir is a central metal is more preferable. Further, a hexacoordinated complex having 1 or 2 5-methylthiazole as a ligand and the rest of the ligands consisting of Cl, Br or I and having Ir as a central metal is most preferable.

In the following, at least one H ₂ O, OH,
Specific examples of the hexacoordinated iridium complex having O, OCN, thiazole or substituted thiazole as a ligand and the rest of the ligands consisting of Cl, Br or I and Ir as a central metal are given below. Not limited.

[Ir (H ₂ O) Cl ₅ ] ^2- [Ir (H ₂ O) ₂ Cl ₄ ] ^- [Ir (H ₂ O) Br ₅ ] ^2- [Ir (H ₂ O) ₂ Br ₄ ] _{^{- [Ir (OH) Cl 5}} ] 3- [Ir (OH) 2 Cl 4] 3- [Ir (OH) Br 5] 3- [Ir (OH) 2 Br 4] 3- [Ir (O) Cl 5 ] ^4- [Ir (O) ₂ Cl ₄ ] ^5- [Ir (O) Br ₅ ] ^4- [Ir (O) ₂ Br ₄ ] ^5- [Ir (OCN) Cl ₅ ] ^3- [Ir (OCN) ^{_{Br 5] 3- [Ir (thiazole}} ) Cl 5] 2- [Ir (thiazole) 2 Cl 4] - [Ir (thiazole) Br 5] 2- [Ir (thiazole) 2 Br 4] - [Ir (5- Methylthiazole) Cl ₅ ]
^2- [Ir (5-methylthiazole) ₂ Cl ₄ ]
^- [Ir (5-methylthiazole) Br ₅ ]
^2- [Ir (5-methylthiazole) ₂ Br ₄ ]
^-

The silver halide grains comprise at least one non-halogen or non-cyan (preferably (H ₂ O, OH, O,
OCN, thiazole or substituted thiazole) as a ligand, a six-coordinate iridium complex having Ir as the central metal and a six-coordinate iridium complex having all six ligands as Cl as the central metal are used in combination.
It is preferable from the viewpoint of further enhancing the effect of the present invention. Further, as the hexacoordinate iridium complex having Ir as a central metal and having at least one non-halogen or non-cyan ligand, at least one H ₂ O, OH, O, OCN,
A hexacoordinated iridium complex having thiazole or substituted thiazole as a ligand and the rest of the ligands consisting of Cl, Br, or I with Ir as the central metal is preferable, but it is particularly preferable to use two kinds of them in combination.

The iridium complex (metal complex) is an anion, and when it forms a salt with a cation, it is preferable that it is easily dissolved in water as its counter cation. Specifically, sodium ion, potassium ion, rubidium ion,
Alkali metal ions such as cesium ion and lithium ion, ammonium ion, and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a suitable organic solvent that can be mixed with water (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.) before use. You can One of these iridium complexes is added per mole of silver during grain formation.
× preferably be 1 × 10 ^-3 mol per mol of the 10 ^-10 moles, and most preferably 1 × 10 ^-5 mol per mol of 1 × 10 ^-8 mol.

The iridium complex is added directly to the reaction solution at the time of silver halide grain formation, or is added to an aqueous solution of a halide for forming silver halide grains, or to a solution other than the above, to prepare a grain formation reaction solution. Is preferably incorporated into the silver halide grain.
Further, it is also preferable to physically ripen fine particles in which an iridium complex has been incorporated into the grains and incorporate them into the silver halide grains. Further, these methods may be combined and contained in the silver halide grains.

In order to incorporate the iridium complex into the silver halide grain, the iridium complex may be uniformly present inside the grain, but it is disclosed in JP-A-4-208936 and JP-A-2-125.
As disclosed in JP-A No. 245 and JP-A-3-188437, it is also preferable that the layer is present only in the particle surface layer, and the complex is present only inside the particle and a layer not containing the complex is added to the particle surface. Is also preferable. Also, US Pat. No. 5,252,451 and US Pat.
As disclosed in 6,530, it is also preferable to physically ripen the fine particles having the complex incorporated in the particles to modify the surface phase of the particles. Further, these methods can be used in combination, and plural kinds of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the iridium complex is contained is not particularly limited, but 6
The hexacoordinated iridium complex having Ir as the central metal in which all the individual ligands are Cl is preferably contained in the silver bromide-containing phase (silver bromide concentration maximum part).

The silver halide grains include other iridium complexes (for example, all 6 ligants are halogen or cyan, and all 6 ligants are not Cl).
Besides the iridium complex, other metal ions can be doped inside and / or on the surface of the silver halide grain. A transition metal ion is preferable as the metal ion used in addition to the iridium complex, and among them, iron, ruthenium,
It is preferably osmium, lead, cadmium or zinc. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand.
When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyanate, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol ion It is preferable to use a nitrosyl ion, and the above iron,
It is also preferable to use it by coordinating with any metal ion of ruthenium, osmium, lead, cadmium, or zinc, and it is also preferable to use plural kinds of ligands in one complex molecule. Further, an organic compound can be used as the ligand, and preferred organic compounds include a chain compound having a main chain having 5 or less carbon atoms and / or a 5-membered or 6-membered heterocyclic compound. . More preferable organic compound is a compound having a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom in the molecule as a coordination atom to a metal, and most preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazan, pyran, pyridine, pyridazine, pyrimidine,
A compound which is pyrazine and further has a substituent introduced into them as a basic skeleton is also preferable.

Here, the combination of the metal ion and the ligand is preferably the combination of iron ion and ruthenium ion and the cyanide ion. In the present invention, it is preferable to use iridium and these compounds in combination. In these compounds, the cyanide ion preferably accounts for the majority of the coordination numbers with respect to the central metal, iron or ruthenium, and the remaining coordination sites are thiocyan, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine and pyrazine. , Or 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron or hexacyanoruthenium complex. Complexes having these cyanide ions as ligands are used in an amount of 1 per 1 mol of silver during grain formation.
It is preferable to add ^{x10 -8} mol to ^{1x10 -2} mol, and most preferable to add ^{1x10 -6} mol to ^{5x10 -4} mol. When ruthenium and osmium are the central metals, it is also preferable to use nitrosyl ion, thionitrosyl ion, or water molecule and chloride ion together as ligands. 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. It is preferable to add 1 × 10 ⁻¹⁰ to 1 × 10 ⁻⁶ mol, and more preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁶ mol of these complexes per 1 mol of silver during grain formation. Is.

It is necessary that the variation coefficient of the spherical equivalent diameter of all grains in the silver halide grains be 20% or less. Here, the sphere-equivalent diameter means the average grain size of silver halide grains (the grain size is defined as the diameter of a circle equivalent to the projected area of grains, and the number average thereof is taken), and it is 0.1 μm.
˜2 μm is preferred. That is, the coefficient of variation of the sphere equivalent diameter is
The coefficient of variation of those particle size distributions is shown and means the standard deviation of the particle size distribution divided by the average particle size. The silver halide grains are preferably so-called monodisperse grains having a variation coefficient of the equivalent spherical diameter of preferably 15% or less, more preferably 10% or less. At this time, it is also preferable to use the above monodisperse particles (emulsion) by blending them in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating.

The silver halide emulsion of the present invention may contain silver halide grains other than the above-defined silver halide grains.

Next, the silver halide emulsion will be described. The sustained electron release time of the silver halide emulsion of the present invention is 10
It is preferably between ^-5 and 10 seconds. Here, the term "electron sustained release time" refers to the time until a photoelectron generated in a silver halide crystal is trapped in an electron trap in the crystal and exposed again when the silver halide emulsion is exposed to light. . If the electronic controlled release time is shorter than 10 ^-5 seconds, it is difficult to obtain a high-sensitivity and high-contrast gradation in high-illuminance exposure. Cause The electron sustained release time is more preferably 10 ⁻⁴ to 10 seconds, most preferably 10 ⁻³ to 1 second.

Here, the electron sustained release time can be measured by the double pulse photoconductivity method. A microwave photoconductivity method or a radio wave photoconductivity method is used to perform a first short-time exposure and then a second fixed short-time exposure. Electrons are trapped in the electron trap in the silver halide crystal by the first exposure, and when the second exposure is given immediately after that, the electron trap is clogged and the second photoconduction signal becomes large. If the two exposure intervals are set sufficiently and the electrons trapped in the electron trap have already been emitted in the first exposure, the photoconduction signal of the second emission returns to the original magnitude. When the exposure interval dependency of the second photoconductive signal intensity is taken by changing the exposure interval of two times, it can be measured that the second photoconductive signal intensity decreases with the exposure interval. This represents the sustained release time of photoelectrons from the electron trap. Sustained electron release may continue to occur for a certain period of time after exposure, but from 10 ^-5 seconds to 1
It is preferred that sustained release is observed during 0 seconds. Sustained release is preferably observed between 10 ^-4 and 10 seconds.
More preferably, sustained release is observed between 0 ^-3 and 1 second.

The oxidation potential of the latent image of the silver halide emulsion of the present invention is preferably nobler than 70 mV, and 100 m
More preferably, it is noble than V. The oxidation potential of the latent image being nobler than 70 mV means that the latent image has relatively strong oxidation resistance. Oxidation potential of latent image is based on Photographic Sensitivity- (Photo
graphic Sensitivity, Oxford
d University Press, Tadaak
i Tani 1995) 103, page 103 and the like. Specifically, the silver halide emulsion coating is subjected to gradation exposure for 0.1 seconds,
Before development, the latent image is bleached by immersing it in a redox bath of various potentials.

The silver halide emulsion of the present invention is usually chemically sensitized. In the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used. Of these, gold-sensitized ones are particularly preferable. By performing gold sensitization, it is possible to further reduce fluctuations in photographic performance when scanning and exposing with laser light or the like.

In order to perform gold sensitization on the silver halide emulsion of the present invention, various inorganic gold compounds, gold (I) complexes having inorganic ligands and gold (I) compounds having organic ligands are used. can do. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and examples of the gold (I) complex having an inorganic ligand include a gold dithiocyanate compound such as potassium gold (I) dithiocyanate and gold (I) 3 dithiosulfate. Compounds such as sodium dithiosulfate compounds such as sodium can be used.

The silver halide emulsion of the present invention is colloidal.
Gold sulfide or gold complex stability constant log β₂Is 21 or more
And it is preferable that it is gold sensitized with a gold sensitizer of 35 or less.
Good The research method for producing colloidal gold sulfide is
Closure (Research Disclosur)
e, 37154), Solid State Ionics
(Solid State Ionics) No. 79
Vol. 60-66, 1995, Compt. Ren
d. Hebt. Seans Acad. Sci. S
ect. B Vol. 263, p. 1328, published in 1966
Have been described. Various sizes as colloidal gold sulfide
It is possible to use those with a particle size of 50 nm or less.
You can The amount added can vary widely depending on the case
Is 5 × 10 5 as gold atom per mol of silver halide.^-7
~ 5 x 10^-3Mol, preferably 5 × 10 ^-6~ 5 x 10^-Four
It is a mole. In the present invention, gold sensitization is further sensitized.
Methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization
Sensitivity or combination with precious metal sensitization using other than gold compounds
You may let me.

Below, the gold complex stability constant log β ₂ is 2
The gold sensitizer of 1 or more and 35 or less will be described. The complex stability constant log β ₂ of gold is measured by a comprehensive
Coordination Chemistry (Compreh
intensive Coordination Chemis
try, Chapter 55, p.864, 1987), Encyclopedia of Electrochemistry of.
The Elements (Encyclopedia of E
electrochemistry of the El
elements, Chapter IV-3, 1975), Journal of the Royal Chemical Society (Journal of the Roy).
al Netherlands Chemical S
(Vol. 101, 164, 1982), and the measurement methods described in the references thereof, and the measurement temperature is 25 ° C. and pH is potassium dihydrogen phosphate / disodium hydrogen phosphate buffer. The ionic strength was adjusted to 6.0 from the value of the gold potential under the condition of 0.1 M (KBr).
The value of gβ ₂ can be calculated. In this measurement method, the value of log β ₂ of thiocyanate ion is 20.5.
And the literature (Comprehensive Coordination Chemistry (Comprehensive Co
coordination Chemistry, 1987
Year, Chapter 55, page 864, Table 2)) described values, values close to 20 are obtained.

Gold complex stability constant log β in the present invention
The gold sensitizer in which ₂ is 21 or more and 35 or less is preferably represented by the following general formula (I). General formula ^{(I) {(L 1)} x (Au) y (L 2) z · Q q} p

In formula (I), L ¹ and L ² each independently represent a compound having a logβ ₂ value of 21 to 35. The compound contained in 22 to 31 is preferable, and the compound contained in 24 to 28 is more preferable.

L ¹ and L ² are, for example, compounds containing at least one unstable sulfur group capable of reacting with silver halide to form silver sulfide, hydantoin compounds, thioether compounds, mesoionic compounds, —SR ', A heterocyclic compound, a phosphine compound, an amino acid derivative, a sugar derivative, and a thiocyano group, which may be the same as or different from each other. Here, R'represents an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, a thiocarbamoyl group, or a sulfonyl group. Q represents a counter anion or counter cation necessary for neutralizing the charge of the compound, x and z represent an integer of 0 to 4, y and p represent 1 or 2, and q represents 0 including a decimal. ~
Represents a value of 1. However, neither x nor z is 0.

The compound represented by formula (I) is preferably a compound in which L ¹ and L ² contain at least one unstable sulfur group capable of reacting with silver halide to form silver sulfide. , Hydantoin compounds, thioether compounds, mesoionic compounds, -SR ', heterocyclic compounds,
Alternatively, it represents a phosphine compound, and x, y, and z each represent 1.

More preferably as the compound represented by the general formula (I), L ¹ and L ² contain at least one unstable sulfur group capable of reacting with silver halide to form silver sulfide. Compound, mesoionic compound, or -SR '
And x, y, z, and p each represent 1.

The gold compound represented by formula (I) will be described in more detail below. In the general formula (I), compounds having an unstable sulfur group capable of reacting with silver halides represented by L ¹ and L ² to produce silver sulfide include thioketones (for example, thioureas, Thioamides or rhodanines), thiophosphates, thiosulfates.

The compound containing at least one unstable sulfur group capable of reacting with silver halide to produce silver sulfide is preferably thioketones (preferably thioureas, thioamides, etc.), thiosulfate. Represents a class.

Next, examples of the hydantoin compound represented by L ¹ and L ² in the general formula (I) include unsubstituted hydantoin and N-methylhydantoin, and the thioether compound includes a thio group. Containing 1 to 8
They are substituted or unsubstituted linear or branched alkylene groups (eg, ethylene, triethylene, etc.), or chain or cyclic thioethers linked by a phenylene group (eg, bishydroxyethyl thioether, 3,6).
-Dithia-1,8-octanediol, 1,4,8,1
1-tetrathiacyclotetradecane etc.) and the like,
Examples of mesoionic compounds include mesoionic-3-mercapto-1,2,4-triazoles (for example, mesoionic-1,4,5-trimethyl-3-mercapto-
1,2,4-triazole etc.) and the like.

Next, in the general formula (I), L ¹ and L ² are -S.
When R'is represented, the aliphatic hydrocarbon group represented by R'is a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl). , N-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl,
2-ethylhexyl, 1,5-dimethylhexyl, n-
Decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, hydroxyethyl, hydroxypropyl, 2,
3-dihydroxypropyl, carboxymethyl, carboxyethyl, sodium sulfoethyl, diethylaminoethyl, diethylaminopropyl, butoxypropyl,
Ethoxyethoxyethyl, n-hexyloxypropyl, etc.), a substituted or unsubstituted cyclic alkyl group having 3 to 18 carbon atoms (for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, cyclododecyl, etc.), 2 to 2 carbon atoms. 16 alkenyl groups (eg, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups having 2 to 10 carbon atoms (eg, propargyl, 3
-Pentynyl, etc.), an aralkyl group having 6 to 16 carbon atoms (eg, benzyl, etc.) and the like, and the aryl group includes a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms and a naphthyl group (eg, unsubstituted phenyl). , Unsubstituted naphthyl, 3,5-dimethylphenyl, 4-butoxyphenyl, 4-dimethylaminophenyl, 2-carboxyphenyl and the like), and the heterocyclic group includes, for example, a substituted or unsubstituted nitrogen-containing hetero 5 Membered ring (for example, imidazolyl, 1,2,4-triazolyl, tetrazolyl,
Oxadiazolyl, thiadiazolyl, benzimidazolyl, purinyl, etc.), a substituted or unsubstituted nitrogen-containing hetero 6-membered ring (eg pyridyl, piperidyl, 1,3,5-
Triazino, 4,6-dimercapto-1,3,5-triazino, etc.), a furyl group, or a thienyl group, and the like, and examples of the acyl group include acetyl and benzoyl, and examples of the carbamoyl group include dimethylcarbamoyl. And the like. Examples of the thiocarbamoyl group include diethylthiocarbamoyl and the like, and examples of the sulfonyl group include a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms (eg, methanesulfonyl, ethanesulfonyl, etc.), carbon Examples of the substituted or unsubstituted phenylsulfonyl group of the formulas 6 to 16 (eg, phenylsulfonyl and the like) can be mentioned.

Further, as —SR ′ represented by L ¹ and L ² , R ′ is preferably an aryl group or a heterocyclic group, more preferably a heterocyclic group, and further preferably 5 or 6 membered. Is a nitrogen-containing heterocyclic group, most preferably a nitrogen-containing heterocyclic group substituted with a water-soluble group (eg, sulfo, carboxy, hydroxy, amino, etc.).

In the general formula (I), the heterocyclic compounds represented by L ¹ and L ² include substituted or unsubstituted nitrogen-containing hetero 5-membered rings (for example, pyrroles, imidazoles,
Pyrazoles, 1,2,3-triazoles, 1,2,
4-triazoles, tetrazoles, oxazoles, isoxazoles, isothiazoles, oxadiazoles, thiadiazoles, pyrrolidines, pyrrolines, imidazolidines, imidazolines, pyrazolidines, pyrazolines, hydantoins, etc.) And heterocycles containing the 5-membered ring (indoles, isoindoles, indolizines, indazoles, benzimidazoles, purines, benzotriazoles, carbazoles, tetraazaindenes, benzothiazoles,
Indolines, etc.), substituted or unsubstituted nitrogen-containing 6-membered heterocyclic ring (for example, pyridines, pyrazines, pyrimidines, pyridazines, triazines, thiadiazines,
Piperidine, piperazine, morpholine, etc.), and a heterocycle containing the 6-membered ring (eg, quinoline,
Isoquinolines, phthalazines, naphthyridines, quinoxalines, quinazolines, pteridines, phenaziridines, acridines, phenanthrolines, phenazines, etc.), substituted or unsubstituted furans, substituted or unsubstituted thiophenes, benzothia Zolium etc. are mentioned.

The heterocyclic compound represented by L ¹ and L ² is preferably an unsaturated nitrogen-containing hetero 5- or 6-membered ring, or a heterocycle containing the same, for example, pyrroles, Imidazoles, pyrazoles, 1,
2,4-triazoles, oxadiazoles, thiadiazoles, imidazolines, indoles, indolizines, indazoles, benzimidazoles, purines, benzotriazoles, carbazoles, tetraazaindenes, benzothiazoles , Pyridines, pyrazines, pyrimidines, pyridazines, triazines, quinolines, isoquinolines, phthalazines, and the like. Further, heterocyclic compounds known as antifoggants in the art (for example, indazoles , Benzimidazoles, benzotriazoles, tetraazaindenes, etc.) are preferred.

In the general formula (I), the phosphine compound represented by L ¹ and L ² includes an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heterocyclic group (for example, Pyridyl, etc.), a substituted or unsubstituted amino group (eg, dimethylamino, etc.), and / or an alkyloxy group (eg, methyloxy, ethyloxy, etc.) is substituted, and preferably represents 1 to 1 carbon atoms. 10
And the phosphines substituted with an aryl group having 6 to 12 carbon atoms (eg, triphenylphosphine, triethylphosphine, etc.) and the like.

Further, in the above-mentioned mesoionic compounds represented by L ¹ and L ² , —SR ′, and the heterocyclic compound, an unstable sulfur group capable of reacting with silver halide to produce silver sulfide is obtained. It is preferable that (for example, a thioureido group or the like) is substituted.

Further, the compounds represented by L ¹ and L ² in the above general formula (I) may further have a substituent as much as possible, and the substituent is, for example, a halogen atom (eg, ,
Fluorine atom, chlorine atom, bromine atom, etc.), aliphatic hydrocarbon group (eg, methyl, ethyl, isopropyl, n-propyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl, etc.), alkenyl group (eg, allyl, Two
-Butenyl, 3-pentenyl etc.), alkynyl group (eg propargyl, 3-pentynyl etc.), aralkyl group (eg benzyl, phenethyl etc.), aryl group (eg phenyl, naphthyl, 4-methylphenyl etc.),
Heterocyclic groups (eg, pyridyl, furyl, imidazolyl, piperidinyl, morpholyl, etc.), alkyloxy groups (eg, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, ethoxyethoxy, methoxyethoxy, etc.), aryloxy groups (eg, phenoxy) , 2-naphthyloxy, etc.), an amino group (eg, unsubstituted amino,
Dimethylamino, diethylamino, dipropylamino,
Dibutylamino, ethylamino, dibenzylamino, anilino, etc.), acylamino group (eg, acetylamino, benzoylamino, etc.), ureido group (eg, unsubstituted ureido, N-methylureido, N-phenylureido, etc.), thioureido group (For example, unsubstituted thioureido, N-methylthioureido, N-phenylthioureido, etc.), selenouride group (for example, unsubstituted selenouride, etc.), phosphine selenide group (diphenylphosphine selenide, etc.), telluroide group (for example, unsubstituted) Telluroide, etc.), urethane group (eg, methoxycarbonylamino, phenoxycarbonylamino, etc.), sulfonamide group (eg, methylsulfonamide, phenylsulfonamide, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl group) N, N-dimethylsulfamoyl, N-phenylsulfamoyl etc.), carbamoyl group (eg unsubstituted carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl etc.), sulfonyl group (eg methanesulfonyl, p -Toluenesulfonyl, etc.), a sulfinyl group (eg, methylsulfinyl,
Phenylsulfinyl etc.), alkyloxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl etc.), aryloxycarbonyl group (eg phenoxycarbonyl etc.), acyl group (eg acetyl, benzoyl, formyl, pivaloyl etc.), acyloxy group ( For example, acetoxy, benzoyloxy and the like), phosphoric acid amide group (for example, N, N-diethylphosphoric acid amide and the like), alkylthio group (for example, methylthio, ethylthio and the like), arylthio group (for example, phenylthio and the like),
Cyano group, sulfo group, thiosulfonic acid group, sulfinic acid group, carboxy group, hydroxy group, mercapto group, phosphono group, nitro group, sulfino group, ammonio group (eg, trimethylammonio, etc.), phosphonio group, hydrazino group, thiazolino Group, a silyloxy group (for example, t-
Butyldimethylsilyloxy, t-butyldiphenylsilyloxy) and the like. When there are two or more substituents, they may be the same or different.

Next, Q and q in the general formula (I) will be described. In the general formula (I), the counter anion represented by Q is a halogenium ion (for example, F ⁻ , Cl ⁻ ,
Br ⁻ , I ⁻ ), tetrafluoroborate ion (B
F ₄ ^-), hexafluorophosphate ion (P
F ₆ ^-), sulfate ion (SO ₄ ^2-), arylsulfonate ions (e.g., p- toluenesulfonate ion,
Naphthalene-2,5-disulfonate ion, etc.), carboxy ion (eg, acetate ion, trifluoroacetate ion, oxalate ion, benzoate ion, etc.) and the like, and the counter cation represented by Q is an alkali metal. Ion (eg, lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, etc.), alkaline earth metal ion (eg, magnesium ion, calcium ion, etc.), substituted or unsubstituted ammonium ion (eg, unsubstituted ammonium) Ion, triethylammonium, tetramethylammonium, etc.), a substituted or unsubstituted pyridinium ion (eg, unsubstituted pyridinium ion, 4-phenylpyridinium ion, etc.), and a proton. Further, q is the number of Q for neutralizing the charge of the compound, and represents a value of 0 to 1, and the value may be a decimal number.

Preferred as the counter anion represented by Q
Is a halogenium ion (eg Cl ^-, Br^-), Tet
Lafluoroborate ion, hexafluorophosphate
Counter cation represented by Q, which is a toion or a sulfate ion
As the alkali metal ion (for example, nato)
Lithium ion, potassium ion, rubidium ion, cell
Sium ion, etc.), substituted or unsubstituted ammonium
Ions (eg, unsubstituted ammonium ions, triethyl
Lumonium, tetramethylammonium etc.), or
It is a proton.

Specific examples (L- ^{1 to} L-17) of the compound represented by L ¹ or L ² are shown below, but the present invention is not limited thereto. In addition, the numerical value in parentheses shows a logβ ₂ value.

[0073]

[Chemical 1]

[0074]

[Chemical 2]

The compound represented by the general formula (I) can be prepared by a known method, for example, Inorganic and Nuclear Chemistry Letters (INORG.NUCL.
CHEM. LETTERSVOL. 10, 641 pages, 1
974), Transition Metal Chemistry (T
positionMet. Chem. Pages 1,248,
1976), Actor Crystallographica (Act)
a. Cryst. B32, p. 3321, 1976),
JP-A-8-69075, JP-B-45-8831, JP-A-915371A1 and JP-A-6-
No. 11788, No. 6-501789, No. 4-267249, and No. 9-118.
It can be synthesized with reference to Japanese Patent No. 685, etc.

Next, specific examples (S-1 to S-19) of the compound represented by the general formula (I) are shown, but the present invention is not limited thereto.

[0077]

[Chemical 3]

[0078]

[Chemical 4]

[0079]

[Chemical 5]

The gold sensitization in the present invention is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature (preferably 40 ° C. or higher) for a certain period of time. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 1 × 10 ⁻⁴ mol per mol of silver halide.

In the present invention, as the gold sensitizer, in addition to the above compounds, commonly used gold compounds (eg, chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, Tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichloro gold, etc.) can be used together.

The silver halide emulsion of the present invention can be used in combination with other chemical sensitization besides gold sensitization. As the chemical sensitization method that can be used in combination, sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization other than gold, or reduction sensitization can be used. As the compound used for the chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used.

The silver halide emulsion of the present invention contains various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. It can be added.
Specific examples of these compounds are described in JP-A-62-215272.
Those described on pages 39 to 72 of the publication are preferably used. Further, a 5-arylamino-1,2,3,4-thiatriazole compound described in EP 0447647 (wherein the aryl residue has at least one electron-withdrawing group) is also preferably used.

Further, in the present invention, in order to improve the storage stability of the silver halide emulsion, the hydroxamic acid derivative described in JP-A No. 11-109576 and JP-A No. 11-327.
Adjacent to the carbonyl group described in JP-A-094, a cyclic ketone having a double bond in which both ends are substituted with an amino group or a hydroxyl group (particularly represented by the general formula (S1), paragraphs 0036 to 0071 can be incorporated into the specification of the present application.), Sulfo-substituted catechols and hydroquinones described in JP-A No. 11-143011, such as 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, etc.),
General formula (A) of US Pat. No. 5,556,741
Hydroxylamines represented by (US Pat. No. 5,555
No. 6,741 column 4, line 56 to column 11, line 22 is preferably applied to the present application and incorporated as a part of the specification of the present application), JP-A-11-1
The water-soluble reducing agents represented by the general formulas (I) to (III) described in JP-A-02045 are preferably used in the present invention.

Further, the silver halide emulsion of the present invention can contain a spectral sensitizing dye for the purpose of imparting so-called spectral sensitivity, which exhibits photosensitivity in a desired light wavelength region.
Examples of the spectral sensitizing dye used for spectral sensitization in the blue, green and red regions include F.I. M. Harter by Heter
ocyclic compounds-Cyanine
dyes and related compound
ds (John Wiley & Sons [Ne
w York, London] 1964). Examples of specific compounds and the spectral sensitization method are described in the above-mentioned JP-A-62-21.
Those described on page 22, upper right column to page 38 of Japanese Patent No. 5272 are preferably used. Further, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dyes described in JP-A-3-123340 are stable, have strong adsorption, It is very preferable from the viewpoint of temperature dependence and the like.

The amount of these spectral sensitizing dyes added may be in a wide range depending on the case, and is 0.5 / mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range.

[Silver Halide Photosensitive Material] Next, the silver halide photosensitive material of the present invention will be described. The silver halide light-sensitive material of the present invention (hereinafter sometimes simply referred to as a light-sensitive material) contains the silver halide emulsion of the present invention. The silver halide light-sensitive material of the present invention is preferably applied to a silver halide photographic light-sensitive material. The silver halide light-sensitive material may be black and white or color, but is preferably a silver halide color photographic light-sensitive material. Be good.

The silver halide color photographic light-sensitive material preferably applied as the light-sensitive material of the present invention is a silver halide emulsion layer containing a yellow dye-forming coupler and a halogen containing a magenta dye-forming coupler on a support. In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer and at least one silver halide emulsion layer containing a cyan dye-forming coupler, at least one of the silver halide emulsion layers is a halogenated compound of the present invention. It is characterized by containing a silver emulsion. In the present invention, the silver halide emulsion layer containing the yellow dye-forming coupler as a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler as a magenta coloring layer, and the cyan dye-forming coupler. The silver halide emulsion layer thus prepared functions as a cyan coloring layer. The silver halide emulsions contained in the yellow color forming layer, the magenta color forming layer and the cyan color forming layer respectively have light in different wavelength regions (for example, light in blue region, green region and red region).
On the other hand, it is preferable to have photosensitivity.

The light-sensitive material of the present invention may have a hydrophilic colloid layer, an antihalation layer, an intermediate layer and a coloring layer, which will be described later, if desired, in addition to the yellow coloring layer, the magenta coloring layer and the cyan coloring layer. Good.

Conventionally known photographic materials and additives can be used in the light-sensitive material of the present invention. For example, a transmissive support or a reflective support can be used as the photographic support. As the transmissive support, a transparent film such as a cellulose nitrate film or polyethylene terephthalate, and further 2,6-naphthalenedicarboxylic acid (NDC)
Polyesters of A) and ethylene glycol (EG), polyesters of NDCA, terephthalic acid and EG, and the like provided with an information recording layer such as a magnetic layer are preferably used. In the present invention, a reflective support (or also referred to as a reflective support) is preferable, and as the reflective support, a plurality of polyethylene layers or polyester layers are laminated, and such a water resistant resin layer (laminate layer) is used. A reflective support containing a white pigment such as titanium oxide in at least one layer is preferred.

In the present invention, a more preferable reflective support is one having a polyolefin layer having fine pores on a paper base on which a silver halide emulsion layer is provided. The polyolefin layer may be composed of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no microvoids (eg polypropylene, polyethylene) and is on a paper substrate. It is more preferable to use a polyolefin (for example, polypropylene or polyethylene) having micropores on the near side. The density of these multi-layer or one-layer polyolefin layers located between the paper substrate and the photographic constituent layers is 0.40 to 40.
It is preferably 1.0 g / ml, and 0.50 to 0.
70 g / ml is more preferred. Further, the thickness of these multi-layer or one-layer polyolefin layers located between the paper base and the photographic constituent layers is preferably 10 to 100 μm, and 15 to
70 μm is more preferable. The ratio of the thickness of the polyolefin layer to the thickness of the paper substrate is preferably 0.05 to 0.2,
1 to 0.15 is more preferable.

It is also preferable to provide a polyolefin layer on the opposite side (back surface) to the photographic constituent layers of the above paper substrate from the viewpoint of increasing the rigidity of the reflective support. In this case, the polyolefin layer on the back surface has a matte surface. Preferred are polyethylene or polypropylene, with polypropylene being more preferred. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further has a density of 0.
It is preferably 7 to 1.1 g / ml. Regarding the preferred embodiment of the polyolefin layer provided on the paper substrate in the reflective support of the present invention, see JP-A-10-
No. 333277, No. 10-333278, No. 11-52513, No. 11-65024,
EP0880065 and EP0880066
The examples described in the specification are included.

Further, it is preferable to contain a fluorescent whitening agent in the water resistant resin layer. Also, a hydrophilic colloid layer containing the fluorescent whitening agent dispersed therein may be separately formed. As the fluorescent whitening agent, preferably, a benzoxazole-based, coumarin-based, or pyrazoline-based fluorescent whitening agent can be used, and more preferably, a benzoxazolylnaphthalene-based or benzoxazolyl-stilbene-based fluorescent whitening agent. The amount used is not particularly limited, but preferably 1 to 10
It is 0 mg / m ² . When mixed with a water resistant resin, the mixing ratio is preferably 0.0005 to 3 mass% with respect to the resin.
And more preferably 0.001 to 0.5 mass%.

The reflective type support may be a transmissive type support or the above-mentioned reflective type support coated with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a specular reflective or type II diffuse reflective metal surface.

The support used in the light-sensitive material of the present invention is a support in which a white polyester support or a layer containing a white pigment is provided on the support having a silver halide emulsion layer for display. The body may be used. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer-coated side or the back side of the support. Especially, the transmission density of the support is 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of.

In the light-sensitive material of the present invention, a hydrophilic colloid layer can be decolorized by the treatment described in European Patent EP 0,337,490A2, pages 27 to 76 for the purpose of improving the sharpness of an image. Dyes (among others, oxonol dyes) are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, and dihydric alcohols (e.g. 1 part of titanium oxide surface-treated with trimethylolethane)
It is preferable to contain 2 mass% or more (more preferably 14 mass% or more).

In the light-sensitive material of the present invention, a hydrophilic colloid layer is added to the European Patent EP0 for the purpose of preventing irradiation and halation and improving safety of safelight.
337490A2, pages 27-76,
Dyes that can be decolorized by treatment (including oxonol dyes,
Cyanine dye) is preferably added. Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes may deteriorate color separation and safelight safety when the amount used is increased. Examples of dyes that can be used without deteriorating the color separation include JP-A-5-127324 and JP-A-5-12
The water-soluble dyes described in JP 7325 and JP 5-216185 are preferable.

In the present invention, instead of the water-soluble dye,
Alternatively, a colored layer that can be decolorized by treatment with a water-soluble dye is used. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with the emulsion layer via an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to install a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is in the wavelength range used for exposure (400 nm for ordinary printer exposure).
It is preferable that the optical density value is 0.2 or more and 3.0 or less at a wavelength having the highest optical density in the visible light region of up to 700 nm, the wavelength of the scanning exposure light source used in the case of scanning exposure). It is more preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

A conventionally known method can be applied to form the colored layer. For example, the dyes described in JP-A-2-282244, from page 3, upper right column to page 8,
-7931 gazette, page 3, upper right column to page 11, lower left column, a method of incorporating a hydrophilic colloid layer in the form of a solid fine particle dispersion, a method of mordanting an anionic dye with a cationic polymer, a dye A method of adsorbing to a fine particle such as silver halide and fixing it in a layer, JP-A-1-239
A method using colloidal silver as described in Japanese Patent No. 544, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye that is substantially water-insoluble at least at pH 6 or less, but is substantially water-soluble at least at pH 8 or more is disclosed in Japanese Patent Laid-Open No. 2-308244, pages 4-13. Further, for example, a method of mordanting an anionic dye on a cationic polymer is described on pages 18 to 26 of JP-A-2-84637. For the preparation of colloidal silver as a light absorber, see US Pat. No. 2,688,
601 and 3,459,563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable.

The silver halide 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.
Color photographic paper is a yellow color-forming silver halide emulsion layer,
It is preferable to have at least one magenta color forming silver halide emulsion layer and at least one cyan color forming silver halide emulsion layer. In general, these silver halide emulsion layers are yellow color forming in order from the support. These are a silver halide emulsion layer, a magenta coloring silver halide emulsion layer, and a cyan coloring silver halide emulsion layer.

However, a layer structure different from this may be adopted. The silver halide emulsion layer containing the yellow coupler may be arranged at any position on the support, but when the yellow coupler-containing layer contains silver halide tabular grains, the magenta coupler-containing silver halide It is preferably coated at a position farther from the support than at least one of the 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 due to a sensitizing dye, the yellow coupler-containing silver halide emulsion layer is coated at a position farthest from the support as compared with other silver halide emulsion layers. It is preferably provided. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably a central layer of other silver halide emulsion layers, and from the viewpoint of reducing photofading, a cyan coupler-containing silver halide emulsion layer. Is preferably the bottom layer. Further, each of the yellow, magenta and cyan color forming layers may be composed of two layers or three layers. For example, JP-A-4-75055 and 9-1.
As described in 14035, 10-246940, US Pat. No. 5,576,159, etc.,
It is also preferable to provide a coupler layer containing no silver halide emulsion adjacent to the silver halide emulsion layer to form a color forming layer.

Silver halide emulsions and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied in the present invention, and processing methods and processing additives applied for processing the photographic material. As the agent, JP-A-62-21
Those described in JP-A-5272, JP-A-2-33144, and European Patent EP0,355,660A2, and particularly those described in European Patent EP0,355,660A2 are preferably used. . Furthermore, JP-A-5-34889 and 4-359249.
No. 4,313753, and No. 4-27034.
4, gazette 5-66527 gazette, and gazette 4-34548.
No. 4, 145,433, No. 2-854, No. 1,158,431, No. 2-90145, No. 3-19439, No. 2-93641, and European Patent Publication No. 0520457A2. The silver halide color photographic light-sensitive material and the processing method therefor described in the specification and the like are also preferable.

In particular, in the present invention, the above-mentioned reflection type support, silver halide emulsion, different metal ion species doped in silver halide grains, storage stabilizer for silver halide emulsion or antifoggant. , Chemical sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsion dispersion method, color image storability improving agent (anti-staining agent or anti-fading agent), As for the dye (colored layer), the type of gelatin, the layer structure of the photosensitive material and the coating pH of the photosensitive material, those described in each part of the patent shown in Table 1 below are particularly preferably applicable.

[0104]

[Table 1]

Other cyan, magenta and yellow couplers used in the present invention are described in JP-A-62 / 62.
-215272, page 91, upper right column, fourth line to 121
Page top left column, line 6, page 3 top right column, line 14 to page 18 top left column, end line, page 30 top right column, line 6 to page 35, bottom right column, line 11 of JP-A-2-33144 EP0355,660
Page 4, lines 15 to 27, page 5, lines 30 to 28, end line, page 45, lines 29 to 31, line 47, lines 23 to 63, line 50 of the A2 specification. The couplers described are also useful. In the present invention, compounds represented by the general formulas (II) and (III) of WO98 / 33760 and the general formula (D) of JP-A-10-221825 may be added, which is preferable.

As the cyan dye-forming coupler usable in the present invention (sometimes referred to simply as "cyan coupler"), a pyrrolotriazole-based coupler is preferably used. Or a coupler represented by (II) and JP-A-6-34796.
The couplers represented by formula (I) of JP-A No. 0, as well as the exemplified couplers described in these patents are particularly preferable. Phenol-based and naphthol-based cyan couplers are also preferable, and for example, a cyan coupler represented by the general formula (ADF) described in JP-A-10-333297 is preferable. As cyan couplers other than the above, European Patents EP0488248 and EP049119
Pyrroloazole-type cyan couplers described in 7A1 and 2,5-described in US Pat. No. 5,888,716.
Diacylaminophenol coupler, US Pat. No. 4,8
73,183 and 4,916,051 and a pyrazoloazole type cyan coupler having an electron-withdrawing group and a hydrogen bonding group at the 6-position, particularly JP-A-8-1
No. 71185, No. 8-311360, No. 8-
The pyrazoloazole type cyan coupler having a carbamoyl group at the 6-position described in JP-A-339060 is also preferable.

In addition to the diphenylimidazole type cyan coupler described in JP-A-2-33144, a 3-hydroxypyridine type cyan coupler described in European Patent EP 0333185A2 (the couplers listed as specific examples ( 42) A 4-equivalent coupler having a chlorine-releasing group to make it a 2-equivalent compound, or a coupler (6)
And (9) are particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (coupler examples 3, 8 and 3 listed as specific examples among them).
4 is particularly preferred), European Patent EP 0456226A1
, A pyrrolopyrazole-type cyan coupler described in
The pyrroloimidazole type cyan coupler described in European Patent EP 0484909 can also be used.

Among these cyan couplers, the pyrroloazole type cyan coupler represented by the general formula (I) described in JP-A No. 11-28138 is particularly preferable, and paragraphs 0012 to 0059 of the patent are described. Including the exemplified cyan couplers (1) to (47) are directly applied to the present application and are preferably incorporated as part of the specification of the present application.

The magenta dye-forming coupler used in the present invention (may be simply referred to as "magenta coupler")
As the 5-
Pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers are used. Among them, secondary or tertiary alkyl groups as described in JP-A-61-65245 in view of hue, image stability, color developability and the like. Is a pyrazolotriazole coupler directly linked to the 2, 3 or 6 position of the pyrazolotriazole ring, a pyrazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A-61-65246, Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254 and 6 as described in EP 226,849A and EP 294,785A. It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the position. Particularly, as a magenta coupler, JP-A-8-1
Pyrazoloazole couplers represented by General Formula (M-I) described in JP-A No. 22948 are preferable, and paragraph numbers 0009 to 0026 of the patent are directly applied to the present application and are incorporated as a part of the specification of the present application. In addition to this, a pyrazoloazole coupler having a steric hindrance group at both the 3-position and the 6-position described in European Patent Nos. 854384 and 884640 is also preferably used.

Also, a yellow dye-forming coupler (simply,
(In some cases, referred to as “yellow coupler”), in addition to the compounds listed in the above table, European Patent EP04479
No. 69A1, an acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure in the acyl group, a malondianilide type yellow coupler having a cyclic structure described in European Patent No. EP 0482552A1, European Patent No. 953870A1. Specification, No. 95387
1A1, No. 953872A1, No. 953873A1, No. 953874A1, No. 953875A1, etc. described in Pyrrole-2 or 3-yl or indole-2 or 3- Ilcarbonylacetic acid anilide coupler, US Pat. No. 5,
The acylacetamide type yellow coupler having a dioxane structure described in 118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

The coupler used in the present invention is a loadable latex polymer (for example, US Pat.
No. 3,716), or dissolved with a water-insoluble polymer soluble in an organic solvent, and then emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers which can be preferably used are described in US Pat. No. 4,857,449, No. 7
Columns to columns 15 and the homopolymers or copolymers described on pages 12 to 30 of International Publication WO88 / 00723 are mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, high molecular weight redox compounds described in JP-A-5-333501, WO98 /
No. 33760, U.S. Pat. No. 4,923,787, and other phenidone and hydrazine compounds, JP-A-5-249637 and JP-A-10-28261.
The white couplers described in Japanese Patent No. 5 and German Patent No. 19629142A1 can be used. Further, particularly when the pH of the developing solution is raised to accelerate the development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 84297.
It is also preferable to use the redox compounds described in Japanese Patent No. 5A1, German Patent 1980846A1 and French Patent No. 2760460A1.

In the present invention, it is preferable to use a compound having a triazine skeleton having a high molar extinction coefficient as the ultraviolet absorber. For example, the compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or the non-photosensitive layer. For example, JP-A-46-
3335 gazette, the same 55-152776 gazette, Unexamined-Japanese-Patent No. 5 197074, the same 5-232630 gazette,
No. 5-307232, No. 6-211813, No. 8-53427, No. 8-234364, No. 8-239368, No. 9-31067, No. 10-15898, and the same. 10-14757
7 gazette, the same 10-182621 gazette, German Patent No. 1
9739797A, European Patent 711804A
The compounds described in JP-A No. 8-501291 and the like can be used.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As preferable gelatin, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably 5 ppm or less,
More preferably, it is 3 ppm or less. The amount of calcium contained in the light-sensitive 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, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, a bactericidal / mold-proofing agent as described in JP-A-63-271247 is used. It is preferable to add it. Further, the film pH of the light-sensitive material is preferably 4.0 to 7.0, and more preferably 4.0 to 6.5.

In the present invention, a surfactant can be added to the light-sensitive material from the viewpoints of improving the coating stability of the light-sensitive material, preventing the generation of static electricity, adjusting the charge amount, and the like. Examples of the surfactant include anionic surfactants, cationic surfactants, betaine surfactants and nonionic surfactants, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. Particularly, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but preferably in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , and preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. It is 1} g / m ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ² .

The light-sensitive material of the present invention can form an image by the exposure step of being irradiated with light according to image information and the developing step of developing the light-irradiated light-sensitive material. The light-sensitive material of the present invention is used in a cathode ray (CR) in addition to being used in a printing system using an ordinary negative printer.
It is also suitable for the scanning exposure method using T). A cathode ray tube exposure apparatus is simpler and more compact than an apparatus using a laser, and is low in cost. Moreover, the optical axis and color can be easily adjusted. For the cathode ray tube used for image exposure, various light-emitting bodies that emit light in the spectral region are used as necessary. For example, any one of a red light emitting body, a green light emitting body, and a blue light emitting body, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a fluorescent substance that emits light in a yellow, orange, violet, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.

When the light-sensitive material has a plurality of light-sensitive layers having different spectral sensitivity distributions, and the cathode tube also has a phosphor that emits light in a plurality of spectral regions, a plurality of colors are exposed at once, that is, the cathode ray. Image signals of a plurality of colors may be input to the tube to cause the tube surface to emit light. A method of sequentially inputting image signals for each color to sequentially emit light of each color and exposing through a film that cuts colors other than that color (field sequential exposure)
In general, field sequential exposure is preferable for high image quality because a high resolution cathode ray tube can be used.

The light-sensitive material of the present invention comprises a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a second harmonic light emitting source (SHG) which is a combination of a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal.
A digital scanning exposure method using monochromatic high-density light such as is preferably used. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) combining a semiconductor laser or a solid-state laser with a nonlinear optical crystal. In particular, it is preferable to use a semiconductor laser in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set depending on the wavelength of the scanning exposure light source used.
A solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal can halve the oscillation wavelength of the laser, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be provided in the normal three wavelength regions of blue, green and red. When the exposure time in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ⁻⁴ seconds or less, more preferably 10 ⁻⁶ seconds or less.

The silver halide color photographic light-sensitive material of the present invention can be preferably used by combining it with the exposure and development system described in the following known materials. Examples of the developing system include an automatic printing and developing system described in JP-A-10-333253, and JP-A-2000.
No. 10206, a photosensitive material conveying device, a recording system including the image reading device described in JP-A-11-215312, color images described in JP-A-11-88619 and JP-A-10-202950. Exposure system consisting of recording method, JP-A-10-210206
A digital photo print system including a remote diagnosis method described in Japanese Patent Publication No. 10-159187, and a photo print system including an image recording apparatus described in Japanese Patent Application No. 10-159187 are listed.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table.

When the light-sensitive material of the present invention is exposed to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. In the present invention, European patent EP 0789270A
As described in No. 1 specification and EP 0789480 A1 specification, a yellow microdot pattern may be pre-exposed and copy regulation may be applied in advance before image information is added.

The processing of the light-sensitive material of the present invention is described in JP-A-2-
207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column, line 17 to page 18, lower right column, line 20. The treatment materials and treatment methods of are preferably applicable. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

The present invention is preferably applied to a light-sensitive material having suitability for rapid processing. In the case of rapid processing, the color development time is preferably 60 seconds or less, more preferably 50 seconds.
Seconds or less 6 seconds or more, more preferably 30 seconds or less 6 seconds or more. Similarly, the bleach-fixing time is preferably 60 seconds or less,
More preferably 50 seconds or less and 6 seconds or more, more preferably 3
0 seconds or less and 6 seconds or more. The washing or stabilizing time is preferably 150 seconds or less, more preferably 130 seconds or less and 6 seconds or more. The color developing time means the time from the time when the light-sensitive material enters the color developing solution to the time when it enters the bleach-fixing solution in the next processing step. For example, in the case of processing with an automatic processor, etc., the time during which the light-sensitive material is immersed in the color developing solution (so-called in-liquid time) and the light-sensitive material leaves the color developing solution, and bleaching in the next processing step occurs. The total of the time during which it is transported in the air toward the fixing bath (so-called aerial time) is called the color development time. Similarly, the bleach-fixing time refers to the time from when the light-sensitive material enters the bleach-fixing solution until it enters the next washing or stabilizing bath. The washing or stabilizing time is the time during which the light-sensitive material is in the washing or stabilizing liquid and is in the liquid for the drying step (so-called in-liquid time).
Say.

The method of developing after development the light-sensitive material of the present invention is a conventional method of developing with a developer containing an alkali agent and a developing agent, or an alkaline solution containing a developing agent in the light-sensitive material and containing no developing agent. In addition to a wet method such as a method of developing with an activator solution such as, a heat development method without using a processing solution can be used. In particular, the activator method is a preferable method because the processing solution does not contain a developing agent, so that the processing solution can be easily managed and handled, and that the load at the time of processing the waste solution is small and the environment can be preserved. In the activator method, the developing agent or its precursor incorporated in the light-sensitive material is, for example, JP-A-8-2343.
88, 9-152686, 9-152.
693, 9-21118, 9-16
The hydrazine type compounds described in Japanese Patent No. 0193 are preferable.

A developing method in which the amount of silver coated on the light-sensitive material is reduced and an image amplification process (intensification process) using hydrogen peroxide is also preferably used. In particular, it is preferable to use this method as an activator method. Specifically, JP-A-8
Image forming methods using an activator solution containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152695 are preferably used. In the activator method, after the treatment with an activator solution, desilvering is usually carried out.However, in the image amplification processing method using a light-sensitive material having a low silver content, desilvering processing is omitted and washing or stabilization processing is simple. Can be done in any way. Further, in the method of reading image information from a light-sensitive material with a scanner or the like, even when a light-sensitive material having a high silver content such as a light-sensitive material for photographing is used,
A processing mode that does not require desilvering processing can be adopted.

As the activator solution, the desilvering solution (bleaching / fixing solution), the washing and stabilizing solution used in the present invention, known materials and methods can be used. Preferably, Research Disclosure Item 3654
4 (September 1994) pp. 536 to 541, JP-A-8-234388 can be used.

[0129]

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

[Example 1] (Preparation of emulsion A-1: <{111} silver chloride tabular grain Cu
b = 0.452 μm [AgCl _98.6 Br ₁ I _0.4 ]: Comparative example>) H ₂ O: 1.2 liter, sodium chloride 1.0 g and inert gelatin 2.5 g were added to the reaction vessel,
In a container kept at 30 ° C, while stirring, an aqueous solution of silver nitrate (B-1 solution: 0.24 g / ml of silver nitrate) and an aqueous solution of sodium chloride (N-1 solution: 0.083 g / m of sodium chloride).
1 and 0.01 g / ml of inert gelatin) were added with vigorous stirring at 75 ml / min for 1 minute. One minute after the completion of the addition, 20 ml of an aqueous solution (K-1) containing 0.9 mmol of the crystal habit controlling agent 1 was added. 10% after 1 minute
340 ml of phthalated gelatin aqueous solution (HG-1) and 2.0 g of sodium chloride were added. In the next 25 minutes, the temperature of the reaction vessel was raised to 55 ° C. and the mixture was aged at 55 ° C. for 30 minutes.
As a growth process, the B-2 solution (silver nitrate 0.4 g / ml) was 516 ml and the N-2 solution (sodium chloride 0.17 g / m).
l) 445 ml was added over 27 minutes at an accelerated flow rate. During this period, an aqueous solution containing 2.1 mmol of the crystal habit controlling agent 1 at an accelerated flow rate (proportional to the amount of silver nitrate added (K-
2) 280 ml was added simultaneously. Furthermore, solution B-3 (silver nitrate 0.4 g / ml) and solution P-6 (potassium iodide 0.0
077 g / ml) from a flow rate of 10.0 ml / min to 15 ml
142 ml was added while increasing linearly to 1 / min, and at the same time, N-3 solution (sodium chloride 0.14 g / ml) was simultaneously added so that the silver potential decreased linearly from 100 mV to 85 mV. After that, B-4 solution (silver nitrate 0.08 g
/ Ml) and P-8 liquid (potassium bromide 0.056 g / m
1) was added at 35.5 ml / min for 1 minute. Also, N-
A K ₄ [Ru (CN) ₆ ] aqueous solution was added to the 3rd solution in an amount such that the Ru amount was 3 × 10 ⁻⁵ mol per mol of the finished silver halide. Further, an aqueous solution of K ₂ [IrCl ₆ ] was added to the N-2 solution in such an amount that the Ir amount was 3 × 10 ⁻⁸ mol per mol of the finished silver halide.

[0131]

[Chemical 6]

Thereafter, the precipitate was washed with water at 30 ° C. for desalting. Further, 130 g of inactive gelatin was added to adjust the pH to 6.
0, pAg 7.2.

A part of the emulsion thus obtained was sampled, and an electron micrograph image (TEM image) of a grain replica was observed. According to this, 98.2% or more of the projected area of all silver halide grains are tabular grains having a main plane of {111} planes and an average aspect ratio of 2 or more, and the average grain size is 0.
The particles were 97 μm, the average particle thickness was 0.123 μm, the average aspect ratio was 7.2, and the cubic side length was 0.450 μm. The coefficient of variation of the equivalent spherical diameter of this emulsion was 17%.

This emulsion was dissolved at 40 ° C. and sodium thiosulfonate was added at 5 × 10 ^-5 per mol of silver halide.
A molar amount was added, and sodium thiosulfate pentahydrate was used as a sulfur sensitizer and (S-2) was used as a gold sensitizer, and aging was performed at 60 ° C. so as to be optimum. Further, the sensitizing dye A is 2 × 10 ⁻⁴ mol per mol of silver halide, the sensitizing dye B is 5 × 10 ⁻⁴ mol per mol of silver halide, and 1-phenyl-5.
-Mercaptotetrazole 2 × 10 ^-4 mol per mol of silver halide, 1- (5-methylureidophenyl)
-5-Mercaptotetrazole was added in an amount of 8 x 10 ^-4 mol per mol of silver halide, and potassium bromide was added in an amount of 2 x 10 ^-3 mol per mol of silver halide. The emulsion thus obtained was designated as Emulsion A-1.

[0135]

[Chemical 7]

(Preparation of Emulsion A-2: Comparative Example) Emulsion A-1
Respect, the N-2 _{solution, K 2 [IrCl 6] K} 2 [IrBr 6] per mol of silver halide Ir amounts of the finished aqueous solution instead of the aqueous solution 3 × 10 ^- added in an amount of ⁸ mol Emulsion A-2 was prepared.

(Preparation of Emulsion A-3: Present Invention) Emulsion A-1
On the other hand, in the N-2 solution, an aqueous solution of K ₂ [IrCl ₅ (H ₂ O)] was used instead of the aqueous solution of K ₂ [IrCl ₆ ] in which the Ir amount was 1 × 10 ⁻⁶ mol per mol of the finished silver halide. To prepare an emulsion A-3.

(Preparation of Emulsion A-4: Present Invention) Emulsion A-1
Respect, the N-2 _solution, K 2 [IrCl _6] Instead K ₂ [Ir aqueous solution (5-methylthiazole)
Cl ₅ ] aqueous solution added in an amount such that the Ir amount becomes 1 × 10 ⁻⁶ mol per mol of the finished silver halide Emulsion A-
4 was prepared.

(Preparation of Emulsion A-5: Present Invention) Emulsion A-1
On the other hand, the K ₂ [IrCl ₆ ] aqueous solution was not added to the N-2 solution, and the K ₂ [IrCl ₅ (H ₂ O)] aqueous solution was added to the P-8 solution, and the amount of Ir was 1 mol per mol of the finished silver halide. Is 1 × 1
Emulsion A-5 was prepared by adding an amount of 0 ^-6 mol.

(Preparation of Emulsion A-6: Present Invention) Emulsion A-3
On the other hand, a K ₂ [IrCl ₆ ] aqueous solution was further added to the P-8 solution so that the Ir amount was 2 × 1 per mol of the finished silver halide.
Emulsion A-6 was prepared by adding an amount of ^0-8 mol.

(Preparation of Emulsion A-7: <{100} silver chloride tabular grains Cub = 0.503 μm>: Comparative Example) H ₂ O: 1.7 liters, inert gelatin (methionine content: approx. 35.5 g of 40 μmol / g deionized alkali-treated bone gelatin), 1.4 g of sodium chloride, and 6.4 ml of 1N nitric acid solution were added (pH was 4.5), and the temperature was kept constant at 29 ° C. Next, an aqueous solution of silver nitrate (Liquid A-1: 0.2 g of silver nitrate)
/ Ml) and an aqueous solution of sodium chloride (M-1 solution: sodium chloride 0.069 g / ml) were added with vigorous stirring at 68.2 ml / min for 45 seconds. 2 minutes later P
-2 solution (potassium bromide: KBr 0.021 g / ml) was added at 186 ml / min for 14 seconds. After 3 minutes, A-
Solution 2 (silver nitrate 0.4 g / ml) and solution M-3 (sodium chloride: 0.15 g / ml) were simultaneously mixed and added at 34 ml / min for 135 seconds. As the ripening process, 1 minute later, an aqueous gelatin solution G-1 [H ₂ O: 120 ml, gelatin 20
g, NaOH: 1 N liquid 7 ml, NaCl: 1.7 g] was added, the temperature was raised to 75 ° C. in 15 minutes, and the mixture was aged for 10 minutes. Next, as a growth process, solution A-3 (silver nitrate 0.4 g /
466 ml while linearly increasing the flow rate from 5.0 ml / min to 9.5 ml / min, and at that time, add M-4 solution (sodium chloride: 0.15 g / ml) to a silver potential of 12
It was added at the same time while keeping it at 0 mV. Further, A-4 solution (silver nitrate 0.4 g / ml) and P-6 solution (potassium iodide 0.0077 g / ml) were added at a flow rate of 5.0 ml / min to 7.
142 ml was added while linearly increasing to 4 ml / min, and at the same time, M-5 solution (sodium chloride: 0.14 g / m
l) was added simultaneously so that the silver potential increased linearly from 120 mV to 140 mV. In addition, K in M-5 solution
₄ [Ru (CN) ₆ ] aqueous solution was added in an amount such that the Ru amount was 3 × 10 ^-5 mol per mol of the finished silver halide. Further, an aqueous solution of K ₂ [IrCl ₆ ] was added to the M-4 solution so that the amount of Ir was 3 × 10 3 per mol of the finished silver halide.
^-8 mol was added.

After that, desalting was performed by washing with sedimented water at 40 ° C. 130 g of inert gelatin was added and the emulsion was redispersed to pH 6.0 and pAg 7.0.

A part of the emulsion thus obtained was sampled, and an electron micrograph image (TEM image) of a grain replica was observed. According to it, 94.1% of the projected area of all silver halide grains are tabular grains having a {100} plane as a main plane, and the average grain size is 0.94 μm and the average grain thickness is 0.180.
μm, average aspect ratio 5.1, average adjacent side ratio 1.1
5 particles were obtained. The coefficient of variation of the equivalent spherical diameter of this emulsion was 18%.

This emulsion was melted at 40 ° C. and
3 × 10 sodium salt per mol of silver halide^-Five
Molar added, sodium thiosulfate 5 water as sulfur sensitizer
Optimum at 60 ° C using Japanese products and gold sensitizer (S-2)
So matured. Further, sensitizing dye A was added to silver halide 1
1.5 x 10 per mole^-FourMolar, sensitizing dye B is halogen
4 x 10 per mol of silver halide^-FourMole, 1-phenyl-5
Mercaptotetrazole per mol of silver halide
1.5 x 10^-FourMolar, 1- (5-methylureidopheni
Ru) -5-mercaptotetrazole to silver halide
6 × 10 per le ^-FourMol, potassium bromide to silver halide
1.5 × 10 per mole^-3Mol added. in this way
The emulsion thus obtained was designated as Emulsion A-7.

(Preparation of Emulsion A-8: Present Invention) Emulsion A-7
On the other hand, in the M-4 solution, an aqueous solution of K ₂ [IrCl ₅ (H ₂ O)] was used instead of the aqueous solution of K ₂ [IrCl ₆ ] in which the Ir amount was 1 × 10 ⁻⁶ mol per mol of the finished silver halide. To prepare Emulsion A-8.

(Preparation of Emulsion A-9: Present Invention) Emulsion A-7
Respect, the M-4 _{solution, K 2 [IrCl 6] K} 2 in place of the aqueous solution [Ir (5-methylthiazole)
Cl ₅ ] aqueous solution added in an amount such that the Ir amount becomes 1 × 10 ⁻⁶ mol per mol of the finished silver halide Emulsion A-
9 was prepared.

The grain shapes and dopant species of Emulsions A-1 to A-9 are listed in Table 2 below.

[0148]

[Table 2]

(Preparation of Sample) After the corona discharge treatment was applied to the surface of a support having both sides of paper coated with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Layers to a seventh photographic constituent layer were sequentially coated to prepare a sample of a silver halide color photographic light-sensitive material having the following layer structure. The coating liquid for each photographic constituent layer was prepared as follows.

-Preparation of First Layer Coating Solution-Yellow coupler (ExY) 54 g, color image stabilizer (Cp
d-1) 7 g, color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-3) 7 g, color image stabilizer (Cpd-8) 2
21 g of solvent (Solv-1) and 80 m of ethyl acetate
22 g of a 23.5% by weight gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate.
Emulsified and dispersed in 0 g by a high-speed stirring emulsifying machine (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, the emulsified dispersion A and the emulsion A-1 were mixed and dissolved to prepare a coating solution for the first layer having the composition described below. The emulsion coating amount indicates a coating amount equivalent to silver.

-Preparation of Second Layer to Seventh Layer Coating Liquids-The coating liquids for the second to seventh layers were prepared in the same manner as the first layer coating liquid. 1-Oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used as a gelatin hardening agent for each layer. Also,
Ab-1, Ab-2, Ab-3, and Ab-4 were added to each layer in a total amount of 15.0 mg / m ² and 60.0 mg / m ² , respectively.
m ² , 5.0 mg / m ² and 10.0 mg / m ² were added.

[0152]

[Chemical 8]

[0153]

[Chemical 9]

The silver chlorobromide emulsions of the green and red sensitive emulsion layers include
The following spectral sensitizing dyes were used respectively. Green sensitive emulsion layer

[0155]

[Chemical 10]

(The sensitizing dye D was added per mol of silver halide:
3.0 x 10 for large emulsions ^-FourMole, small size
3.6 × 10 for emulsions^-FourMolar and sensitizing dye E
Per mole of silver halide for large size emulsions
4.0 x 10^-Five7.0 × for moles, small size emulsions
10^-Five1 mole of sensitizing dye F to 1 mole of silver halide
2.0 × 10 for large emulsions^-FourMole, small
2.8 × 10 for Izu emulsion^-FourMol added. )

Red-sensitive emulsion layer

[0158]

[Chemical 11]

(Sensitizing dyes G and H were used in an amount of 8.0 × 1 per mol of silver halide for a large-sized emulsion.
0 ^-5 mol, and 10.7 × 10 ^-5 mol was 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. )

[0160]

[Chemical 12]

For the green-sensitive emulsion layer and the red-sensitive emulsion layer,
In contrast, 1- (3-methylureidophenyl) -5-mel
Captotetrazole was added to 1 mol of silver halide
1.0 × 10^-3Molar and 5.9 x 10^-FourMole added
It was In addition, the second layer, the fourth layer, the sixth layer and the seventh layer
Each 0.2 mg / m ², 0.2 mg / m², 0.
6 mg / m², 0.1 mg / m²Was added.
In addition, for blue-sensitive emulsion layers and green-sensitive emulsion layers, 4-hi
Droxy-6-methyl-1,3,3a, 7-tetrazai
1 x 1 for each mole of silver halide.
0^-FourMole, 2 × 10^-FourMol added. Also, red-sensitive emulsion
Copolymer latex of methacrylic acid and butyl acrylate
Cousin (mass ratio 1: 1, average molecular weight 200,000-400)
000) is 0.05 g / m²Was added. Also the second layer,
Catechol-3,5-disulfone on the 4th and 6th layers
6 mg / m 2 of disodium acid², 6 mg / m²,
18 mg / m²Was added. Also, Iraje
The following dyes are used to prevent
Represents) is added.

[0162]

[Chemical 13]

-Layer Structure- The structure of each layer is shown below. Numbers are coating amount (g / m ² )
Represents The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene resin laminated paper [White pigment (TiO ₂ ; content 16% by mass; ZnO; content 4% by mass) and fluorescent whitening agent (4,4′-bis (5 -Methylbenzoxazolyl) stilbene, content 0.03% by mass, including bluing dye (ultraviolet)] First layer (blue-sensitive emulsion layer) Emulsion A-1 0.24 Gelatin 1.25 Yellow coupler ( ExY) 0.54 Color 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

[0164]   Second layer (color mixing prevention layer)     Gelatin 0.99     Color mixing 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

[0165]   Third layer (green sensitive emulsion layer)   Silver chlorobromide emulsion B (gold sulfur sensitized cube, large with an average grain size of 0.45 μm 1: 3 mixture of size emulsion and small size emulsion of 0.35 μm (silver molar ratio). particle Coefficients of variation of size distribution are 0.10 and 0.08, respectively. Silver iodide for each size emulsion 0.15 mol% is contained in the vicinity of the grain surface, and silver bromide 0.4 mol% is localized on the grain surface. Included)                                                           0.14     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) 0.03     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

[0166]   Fourth layer (color mixing prevention layer)     Gelatin 0.71     Color mixing 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

[0167]   Fifth layer (red sensitive emulsion layer)   Silver chlorobromide emulsion C (gold sulfur sensitized cube, large with an average grain size of 0.40 μm) 5: 5 mixture of size emulsion and 0.30 μm small size emulsion (silver molar ratio). particle Coefficients of variation of size distribution are 0.09 and 0.11. Each size emulsion has each size Both emulsions contain 0.1 mol% of silver iodide near the surface of grains and 0.8 mol% of silver bromide. Localized inclusion on the particle surface)                                                           0.12     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

[0168]   Sixth layer (UV absorption layer)     Gelatin 0.46     UV absorber (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     (Modification degree 17%) 0.04     Liquid paraffin 0.02     Surfactant (Cpd-13) 0.01

[0169]

[Chemical 14]

[0170]

[Chemical 15]

[0171]

[Chemical 16]

[0172]

[Chemical 17]

[0173]

[Chemical 18]

[0174]

[Chemical 19]

[0175]

[Chemical 20]

[0176]

[Chemical 21]

[0177]

[Chemical formula 22]

[0178]

[Chemical formula 23]

The sample obtained as described above was used as sample A
-1 was set. Sample A-1 was prepared in the same manner as the sample in which the emulsion of the blue-sensitive emulsion layer (BL) was changed from A-2 to A-9.
Samples A-2 to A-9 were used, respectively.

(Evaluation) The following experiments were conducted to examine the photographic characteristics of these samples. A gray scale exposure for sensitometry was applied to each coated sample using a high-illuminance exposure sensitometer (HIE type manufactured by Yamashita Denso Co., Ltd.).
The exposure temperature was 15 ° C. and 35 ° C., respectively, and high illuminance was 10 ⁻⁶ seconds. After the exposure, 30 seconds later, color development processing A shown below was performed.

The processing steps are shown below. [Processing A] The above light-sensitive material sample was processed into a roll having a width of 127 mm, imagewise exposed using a mini-lab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., and then doubled to the capacity of the color developing tank in the following processing step. Until then, continuous treatment (running test) was performed. The treatment using this running liquid was designated as treatment A. Treatment process Temperature Time Replenishment amount * Color development 38.5 ° C. 45 seconds 45 ml Bleach 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 ° C. for 20 seconds − Rinse (4) ** 38.0 ° C. for 30 seconds 121 ml * Replenishment amount per 1 m ^{2 of the} light-sensitive material ** Rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. The rinsing liquid is taken out from the rinsing device (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the same 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 performed from the tank countercurrent system from (1) to (4).)

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher] 800 ml water 800 ml Dimethylpolysiloxane-based surfactant 0.1g 0.1g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8g 8.8g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0g 10.0g Sodium 4,5-dihydroxybenzene-1,3-disulfonate                                     0.5g 0.5g Potassium chloride 10.0g- Potassium bromide 0.040g 0.010g Triazinyl amino stilbene-based optical brightener (HAKCOL FWA-SF / Showa Kaika (Made by Gakusha)                                     2.5g 5.0g Sodium sulfite 0.1g 0.1g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine                                     8.5g 11.1g 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 1000 ml 1000 ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid)                                   10.15 12.50

[0183] [Bleach fixer] [Tank solution] [Replenisher] Water 700 ml 600 ml Ethylenediaminetetraacetate Iron (III) ammonium                                   47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g m-carboxybenzenesulfinic acid                                       8.3g 16.5g Nitric acid (67%) 16.5g 33.0g Imidazole 14.6g 29.2g 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 Add water 1000 ml 1000 ml pH (adjusted with 25 ° C / acetic acid and ammonia)                                     6.0 6.0

[0184] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5μS / cm or less)                             1000 ml 1000 ml pH (25 ° C) 6.5 6.5

The yellow color density of each sample after the treatment was measured, and a characteristic curve of 10 ⁻⁶ second exposure and high illuminance exposure was obtained. The sensitivity was defined as the logarithm of the reciprocal of the exposure amount that gives a color density of 0.7 higher than the minimum color density, and the difference in sensitivity between exposure at 15 ° C and exposure at 35 ° C was expressed.

[0186]

[Table 3]

As is clear from the results shown in Table 3, the samples A-3 to A-6, A-8 and A-9 of the present invention have exposure temperature dependence when processed in a short time after exposure to high illuminance. It was found to be small. Further, among the samples A-3 to A-6, the sample A-6 in which the iridium complex was used together was the most improved. Further, A of tabular grains having the {111} plane as the main plane
-3 to A-5 were better than A-8 and A-9 of the tabular grains having the {100} plane as the main plane.

[Example 2] The sample of Example 1 was prepared by changing the layer structure as follows to prepare a thin sample.

[0189] (Preparation of sample)   First layer (blue sensitive emulsion layer)     Emulsion A-1 0.24     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     Color image stabilizer (Cpd-8) 0.02     Solvent (Solv-1) 0.21

[0190]   Second layer (color mixing prevention layer)     Gelatin 0.60     Color mixing 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

[0191]   Third layer (green sensitive emulsion layer)     Silver chlorobromide emulsion B (same as sample A-1) 0.14     Gelatin 0.73     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 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

[0192]   Fourth layer (color mixing prevention layer)     Gelatin 0.48     Color mixing prevention layer (Cpd-4) 0.07     Color image stabilizer (Cpd-5) 0.006     Color image stabilizer (Cpd-7) 0.006     Ultraviolet absorber (UV-C) 0.04     Solvent (Solv-5) 0.09

[0193]   Fifth layer (red sensitive emulsion layer)     Silver chlorobromide emulsion C (same emulsion as sample A-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) 0.04     Ultraviolet absorber (UV-7) 0.02     Solvent (Solv-5) 0.09

[0194]   Sixth layer (UV absorption layer)     Gelatin 0.32     Ultraviolet absorber (UV-C) 0.42     Solvent (Solv-7) 0.08

[0195]   Seventh layer (protective layer)     Gelatin 0.70     Acrylic modified copolymer of polyvinyl alcohol     (Modification degree 17%) 0.04     Liquid paraffin 0.01     Surfactant (Cpd-13) 0.01     Polydimethylsiloxane 0.01     Silicon dioxide 0.003

Emulsion A- as described above as the emulsion of the blue-sensitive emulsion layer.
The sample using 1 was designated as sample G-1. Samples G-1 to B-9 were prepared in the same manner by changing the emulsions in the blue-sensitive emulsion layer from A-2 to A-9, respectively.

(Evaluation) The following experiments were conducted to examine the photographic characteristics of these samples. A gray scale exposure for sensitometry was applied to each coated sample using a high-illuminance exposure sensitometer (HIE type manufactured by Yamashita Denso Co., Ltd.).
The exposure temperature was 15 ° C. and 35 ° C., respectively, and high illuminance was 10 ⁻⁶ seconds. After the exposure, 30 seconds later, color development processing A shown below was carried out to carry out an ultra-rapid processing.

The processing steps are shown below. [Processing B] The above-described photosensitive material sample was processed into a roll having a width of 127 mm, and a photosensitive material was used by using an experimental processor in which a minilab printer processor PP350 manufactured by Fuji Photo Film Co., Ltd. was modified so that the processing time and the processing temperature could be changed. The sample was imagewise exposed from a negative film having an average density, and continuously processed (running test) until the capacity of the color developing replenisher used in the following processing steps became 0.5 times the capacity of the color developing tank.

Treatment Process Temperature Time Replenishment Amount * Color development 45.0 ° C. 15 seconds 45 ml Bleach 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 sec-Rinse (4) ** 38.0 C 8 sec 121 ml Dry 80 C 15 sec (Note) * Replenishment amount per 1 m ^{2 of} photosensitive material ** The phosphorus screening system RC50D manufactured by Fuji Photo Film Co., Ltd. is installed in the rinse (3), and the rinse solution is taken out from the rinse (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the same 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 performed from the tank countercurrent system from (1) to (4).)

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher] Water 800 ml 600 ml Optical brightener (FL-1) 5.0 g 8.5 g Triisopropanolamine 8.8g 8.8g Sodium p-toluenesulfonate 20.0 g 20.0 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium sulfite 0.10g 0.50g Potassium chloride 10.0g- Sodium 4,5-dihydroxybenzene-1,3-disulfonate                                     0.50g 0.50g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine                                     8.5g 14.5g 4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl ) Aniline, 3/2 sulfate, monohydrate                                   10.0 g 22.0 g Potassium carbonate 26.3g 26.3g Add water to make 1000 ml 1000 ml pH (25 ° C / adjusted with sulfuric acid and KOH) 10.35 12.6

[0201] [Bleach fixer] [Tank solution] [Replenisher] 800 ml water 800 ml Ammonium thiosulfate (750 g / l)                               107 ml 214 ml Succinic acid 29.5g 59.0g Ethylenediaminetetraammonium iron (III) acetate                                   47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g Nitric acid (67%) 17.5g 35.0g Imidazole 14.6g 29.2g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Add water to make 1000 ml 1000 ml pH (25 ℃ / adjusted with nitric acid and ammonia water)                                     6.00 6.00

[0202] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5 μS / cm or less)                             1000 ml 1000 ml pH (25 ° C) 6.5 6.5

[0203]

[Chemical formula 24]

The yellow color density of each sample after the treatment was measured to obtain a characteristic curve of 10 ⁻⁶ second exposure and high illuminance exposure. The sensitivity was defined as the logarithm of the reciprocal of the exposure amount that gives a color density of 0.7 higher than the minimum color density, and the difference in sensitivity between exposure at 15 ° C and exposure at 35 ° C was expressed.

[0205]

[Table 4]

As is clear from the results shown in Table 4, the samples G-3 to G-6, G-8 and G-9 of the present invention were processed in a short time after exposure to high illuminance even during rapid processing. It was confirmed that the exposure temperature dependency was small.

Example 3 Using the sample of Example 2, an image was formed by laser scanning exposure. As a laser light source, a semiconductor laser GaAlAs (oscillation wavelength:
YAG solid-state laser (oscillation wavelength: 946 nm) using 808.5 nm as an excitation light source was wavelength-converted by a SHG crystal of LiNbO ₃ having an inversion domain structure and extracted at 473 nm, and a semiconductor laser GaAlAs (oscillation wavelength: 808.7 nm). 532 nm obtained by wavelength conversion of a YVO ₄ solid-state laser (oscillation wavelength: 1064 nm) using an SHG as an excitation light source by an SHG crystal of LiNbO ₃ having an inversion domain structure, and AlGaInP (oscillation wavelength:
About 680 nm: Type No. manufactured by Matsushita Electric Industrial Co., Ltd. LN9R20)
And were used. The laser light of each of the three colors was moved in a direction perpendicular to the scanning direction by a polygon mirror so that the sample could be sequentially scanned and exposed. Fluctuations in the amount of light due to the temperature of the semiconductor laser are suppressed by using a Peltier device to keep the temperature constant. The effective beam diameter is 80 μm and the scanning pitch is 42.3 μm (600
The average exposure time per pixel is 1.
It was 7 × 10 ⁻⁷ seconds.

When the color development processing B was carried out while changing the exposure temperature, it was confirmed that the samples of the present invention had a small exposure temperature dependency, as in the case of the high illuminance exposure in Example 2. It was also found to be suitable for image formation using scanning exposure.

From these examples, by using the silver halide emulsion of the present invention, a highly sensitive and hard gradation can be obtained even in digital exposure such as laser scanning exposure, and it is stable to the exposure environment, It can be seen that a silver halide photographic light-sensitive material suitable for rapid processing can be obtained.

[0210]

As described above, according to the present invention, it is possible to obtain a silver halide light-sensitive material having a digital exposure suitability such as a laser scanning exposure and a rapid processing suitability, a high sensitivity and an excellent exposure temperature dependency. It is possible to provide a silver halide emulsion and a silver halide light-sensitive material (especially silver halide photographic light-sensitive material) using the same.

Claims (3)

[Claims] 1. In a silver halide emulsion containing silver halide grains having a silver chloride content of 90 mol% or more, 80% or more of the projected area of the silver halide grains has an average aspect ratio of 2 or more and an average thickness of 0.3 μm. Tabular grains of less than
And the variation coefficient of the spherical equivalent diameter of all particles is 20% or less,
A silver halide emulsion comprising a hexacoordinated iridium complex having Ir as a central metal and having at least one non-halogen or non-cyan ligand. 2. In a silver halide emulsion containing silver halide grains having a silver chloride content of 90 mol% or more, 80% or more of the projected area of the silver halide grains has an average aspect ratio of 2 or more and an average thickness of 0.3 μm. Tabular grains of less than
And the variation coefficient of the spherical equivalent diameter of all particles is 20% or less,
At least one of six-coordinate iridium complexes having Ir as a central metal and having at least one non-halogen or non-cyan as a ligand, and six chlorines as ligands 6
A silver halide emulsion containing at least one kind of coordination iridium complex. 3. A silver halide light-sensitive material comprising the silver halide emulsion according to claim 1 or 2.