JP2003270750A - Silver halide emulsion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide emulsion which causes neither lowering of sensitivity nor lowering of contrast even in digital exposure such as laser scanning exposure and ensures high sensitivity and contrasty gradation. <P>SOLUTION: The silver halide emulsion comprises at least silver halide grains based on silver chloride and having a tetracosahedral outer shape. <P>COPYRIGHT: (C)2003,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 particularly to a silver halide emulsion capable of obtaining a highly sensitive and hard gradation even in digital exposure such as laser scanning exposure and ultra-rapid processing.

[0002]

2. Description of the Related Art 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 in order to improve productivity. Such a silver halide emulsion having a high silver chloride content is generally liable to cause low-sensitivity softening by high-intensity exposure such as laser scanning exposure, and also has a high fog density, and various techniques for improving these points. Is disclosed.

It is known to dope iridium to improve the high intensity failure of silver chloride emulsions. However, it is known that an iridium-doped silver chloride emulsion causes latent image sensitization in a short time after exposure. For example, Japanese Patent Publication No. 34103/1995 discloses a localized phase having a high silver bromide content. It has been disclosed that the problem of latent image sensitization can be solved by providing the above structure and doping it with iridium. The silver halide emulsion prepared by this method has high sensitivity and high contrast even when exposed to a relatively high illuminance of about 1/100 second, and does not cause a problem of latent image sensitization, but is required by a digital exposure method by laser scanning exposure. It has been clarified that it is difficult to obtain a hard gradation when trying to maintain high sensitivity up to an ultrahigh illuminance of 1 μsec. US Pat. No. 5,691,119
No. 1 discloses a method for preparing an emulsion having a localized phase having a high silver bromide content, which hardens a high-intensity gradation, but the effect is not sufficient and the performance is improved by repeating the preparation. It has the drawback of not being stable.

US Pat. Nos. 5,783,373 and 5,
Japanese Patent No. 783378 discloses a method of reducing high illuminance failure and hardening by using at least three kinds of dopants. However, the reason that a hard gradation can be obtained is that a dopant having a desensitizing and hardening effect is used, which is in principle incompatible with the high sensitivity.

US Pat. Nos. 5,726,005 and 5,
Japanese Patent No. 736310 discloses that an emulsion containing I having a maximum concentration on the subsurface of a high silver chloride emulsion can provide an emulsion having high sensitivity and high illumination intensity. As a result, the higher the illuminance exposure is, the higher the sensitivity can be obtained, but the gradation is extremely soft, and it is not suitable for digital exposure with a limited dynamic range of the light amount. Turned out to be unsuitable. US Pat. Nos. 5,728,516, 554
7827, 5605789 and JP-A-8-2
No. 34354 discloses a method for reducing the fog density of an emulsion containing I having a maximum density on the sub-surface of a high silver chloride emulsion, but all of them have sufficient effects for use as a printing material. Didn't.

JP-A-58-95736 and 58-10.
No. 8533, No. 60-222844, No. 60-22
No. 2845, No. 62-253143, No. 62-253.
No. 144, No. 62-253166, No. 62-2541.
No. 39, No. 63-46440, No. 63-46441
No. 63-89840, U.S. Pat. No. 4,820,624.
No. 48965962, 5399475 and 52
No. 84743 discloses that high sensitivity can be obtained by locally containing a phase having a high silver bromide content in various forms in an emulsion having a high silver chloride content. However,
According to the contents disclosed in these documents, the effect of softening the tone and improving the reciprocity law was not sufficient due to the formation of the high Br phase.

[0007]

DISCLOSURE OF THE INVENTION Problems to be solved by the present invention are halogens which do not cause lowering of sensitivity or softening even in digital exposure such as laser scanning exposure, and which provide high sensitivity and high gradation. It is to provide a silver halide emulsion.

[0008]

The above object has been achieved by the present invention described below. That is, the present invention is <1> a silver halide emulsion containing silver chloride as a main component and further containing at least silver halide grains having an outer shape of 24 faces. <2> The silver halide grains have an average Br content of 18
The silver halide emulsion according to <1>, which has a high silver bromide content of at least mol%.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. The silver halide emulsion of the present invention contains silver chloride as a main component, and further contains at least silver halide grains having an external shape of 24 sides. Usually, silver halide grains are {10
Although it tends to be cubic grains surrounded by the 0} plane, silver halide grains having a tetrahedral outer shape can be formed under the grain forming conditions described later. FIG. 1 is a perspective view showing the outline of a silver halide grain which is a tetrahedron. The tetrahedral silver halide grains do not have high growth activity in the corners, and when the high silver bromide-containing phase is formed, the high silver bromide-containing phase is less likely to be concentrated in the corners, and recrystallization is less likely to occur. Therefore, a uniform high silver bromide-containing phase can be formed in the shell portion of the grain. Further, it is preferable that the outer shape is also a tetrahedron even at a stage before the high silver bromide-containing phase growth.

The ratio of the silver halide grains having the outer shape of a tetrahedron to all the silver halide grains is preferably at least 30% or more, more preferably 50% or more, still more preferably the total projected area. It is 70% or more. The proportion of silver halide grains having a tetrahedral outer shape in the entire projected area can be determined by electron micrograph.

The silver halide grains of the present invention preferably have a high silver bromide-containing phase having an average Br content of 18 mol% or more. Here, the high-silver-bromide-containing phase means a portion having a higher content ratio than each grain, and means a portion having a high silver bromide concentration. The high silver bromide-containing phase may be present in the silver halide of the present invention in any state (layered, epitaxial, localized, etc.), but is preferably layered. The average thickness of the layer when the high silver bromide-containing phase is layered is 0.003 μm or more and 0.05 μm or more.
m or less is preferable, and 0.005 μm or more and 0.03 μm or less is more preferable. In the present invention, the average thickness means the amount of silver halide to be additionally grown from the prescribed value based on the cubic equivalent side length size L (μm) of the grain obtained from the electron micrograph after core formation, based on the total silver amount. When X%, it can be obtained from the following equation. Thickness T (μm) = L {1- (100 / 100-
X) ^-1/3 }

Further, in the present invention, the average Br content of the high silver bromide-containing phase means B added at the time of forming the high silver bromide-containing phase.
The ratio of r ion amount to silver ion is expressed in mol%. The average Br content is 10 mol% or more and 40
The amount is preferably mol% or less, more preferably 18 mol% or more and 40 mol% or less, and particularly preferably 15 mol% or more and 30 mol% or less. When the content is 10 mol% or more and 40 mol% or less, recrystallization is unlikely to occur and a high silver bromide-containing phase is easily obtained.
Also, reciprocity law and latent image improvement are sufficient.

The silver halide grain of the present invention contains silver chloride as a main component (85 mol% or more), but the preferable silver chloride content is 89 mol% or more, more preferably 93 mol%.
It is above, and 95 mol% or more and 98.5 mol% or less are particularly preferable. Further, the silver bromide content is 0.5 mol% or more and 6
The amount is preferably mol% or less, more preferably 1 mol% or more and 4 mol% or less. When the silver bromide content is 0.5 mol% or more, a silver bromide-containing phase having a content of 20 mol% or more can be formed without difficulty. On the other hand, when the silver bromide content is 6 mol% or less, the characteristics of silver chloride (such as fast processing time and low replenishment resistance) in developing and fixing are not lost,
Lattice irregularity due to the gap of the halogen composition with the core interface is small, and the low sensitivity and softening due to the internal sensitivity do not become apparent. The silver iodide content is preferably 0.05 mol% or more and 0.5 mol% or less. Particularly preferred is 0.05 mol% or more and 0.4 mol% or less.

A method for forming silver halide grains having an outer shape of 24 faces in the present invention will be described below. The tetrahedral silver halide grains are preferably formed at a low temperature of 40 ° C. or lower. The lower limit of temperature is not particularly limited, but is preferably 15 ° C or higher. The growth condition is 50% to 90% of the critical growth rate that causes re-nucleation.
Highly supersaturated growth of is preferably used. Here, the critical growth rate can be determined as 100% by increasing the supply rate of silver ions and halogen ions and adding the rate at which re-nucleation occurs. When the grain size is small and the ratio of the high silver bromide-containing phase to the whole grains is high, the critical growth rate changes with the growth of the high silver bromide-containing phase.
In such a case, the growth rate of the high silver bromide-containing phase can always be maintained at a constant rate with respect to the critical growth rate by using a means such as flow rate acceleration. In the present invention, flow rate accelerated growth is preferably used in order to achieve highly supersaturated growth of 50% to 90% of the critical growth rate. A preferable flow rate accelerated growth may be a linear function of time or a higher or higher order function. On the other hand, the protective colloid used for growth has a mass average molecular weight of 50,000 or more and 20,000.
Deionized gelatin of 0 or less is preferably used.

The preferable grain growth conditions for forming a high silver bromide-containing phase in the silver halide emulsion of the present invention are described below. The growth rate of the silver halide emulsion grains of the present invention at the time of forming the high silver bromide-containing phase is preferably 50% or more of the critical growth rate, and it is preferable to perform the high saturation growth. Particularly, it is preferable to set a growth rate of 70% or more and 95% or less with respect to the critical growth rate. If it is 70% or more with respect to the critical growth rate, the degree of supersaturation does not decrease, physical ripening and recrystallization accompanying it do not proceed, the inter-particle distribution of the Br ion content does not increase, and A uniform and stable high silver bromide-containing phase is obtained because recrystallization does not proceed. On the other hand, when the content is 95% or less with respect to the critical growth rate, re-nucleation is not manifested, stirring and mixing can be sufficiently performed, and a high silver bromide-containing phase can be uniformly obtained between grains and within grains. .

The growth temperature during the formation of the high silver bromide-containing phase is 38
C. or less is preferable. More preferably 10 ° C or higher and 35 ° C
The following are preferred. The growth temperature is preferably low, but in practice, it is preferably 5 ° C. or higher because the solvent is water and gelatin is used as the protective colloid.

The preferred embodiments of the host grains before forming the high silver bromide-containing phase are described below. Host particle is 0.05
It is preferable to contain silver iodide in an amount of mol% to 0.3 mol%. As a method of introducing silver iodide, 80% of host grains are used.
It is preferable to introduce iodo ions at the stage of growing the above, and as a method for introducing iodide ions, there is a method of adding Kippen or adding with other halogen ions (usually mainly chlorine ions). Since the solid solution limit of iodide ion is expected to be 10 mol% or less in silver chloride, the maximum concentration is near the surface of the host grain, whichever addition method is used. By increasing the concentration of iodine in the vicinity of the surface, the host becomes less soluble, recrystallization is suppressed, and the host particles are preferable for forming a high silver bromide-containing phase. However, it is preferable not to add iodide ions in the very initial stage of core formation. When iodide ions are added in the very early stage of core formation, the monodispersity of the particles may be reduced, or the iodide ion concentration near the surface may be reduced when the host particles are completed, and the effect of the present invention may be diminished. In addition, it is preferable that the shape of the host grain is not a grain having a rounded corner portion where recrystallization is likely to occur at the time of forming a high silver bromide-containing phase or the corner portion has a high {111} plane ratio.

As the silver halide emulsion of the present invention, an emulsion containing silver halide grains composed of silver iodobromochloride is preferably used. The silver chloride content in silver iodobromochloride silver halide grains is preferably 89 mol% to 99.7 mol%, and from the viewpoint of rapid processability, the silver chloride content is 93 mol% to 99. 5 mol% is preferable, and 95 mol% -98.5 mol% is more preferable. The silver bromide content is preferably 0.25 mol% to 10 mol%,
The content of silver bromide is 0.
It is more preferably from 5 mol% to 6 mol%, further preferably from 1 mol% to 4 mol%. The silver iodide content is preferably 0.05 mol% to 1 mol%, and is 0.05 to 1 mol% because it has high sensitivity and high contrast under high illuminance exposure.
It is preferably 0.6 mol%, and more preferably 0.1 to 0.4 mol%.

Preferred silver halide grains in the silver halide emulsion of the present invention may have a high silver bromide-containing phase in addition to the high silver bromide-containing phase described above. Here, the high silver iodide-containing phase means a portion having a higher content than each grain, and means a portion having a high silver iodide concentration. The halogen composition of the high silver bromide-containing phase or the high silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide- or silver iodide-containing phase may form a phase having a substantially constant concentration in a certain portion in the grain, or may be a maximum point having no spread.
The local silver bromide content of the silver bromide-containing phase is preferably 5 mol% or more, more preferably 10 to 80 mol%, and most preferably 15 to 50 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.2 mol% or more, more preferably 0.5 to 8 mol%, and further preferably 1 to 5 mol%. Most preferred. A plurality of such silver bromide or silver iodide-containing phases may be present in each grain, and the respective silver bromide or silver iodide contents may differ, but at least one is contained in each phase. It is preferable to have a phase.

The high silver bromide-containing phase or the high silver iodide-containing phase in the silver halide emulsion of the present invention can be layered so as to surround the grains. It is one preferable embodiment that the high silver bromide-containing phase or the high silver iodide-containing phase formed in a layer surrounding the grains has a uniform concentration distribution in the orbiting direction of the grains in each phase. However, in the high silver bromide-containing phase or the high silver iodide-containing phase that is layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the orbiting direction of the grain, and the concentration distribution May have. For example, when a layer having a high silver bromide-containing phase or a high silver iodide-containing phase is formed near the surface of the grain so as to surround the grain, the concentration of silver bromide or silver iodide at the corner or edge of the grain is different from that on the main surface. There are cases. Further, it may be a high silver bromide-containing phase or a high silver iodide-containing phase which is isolated at a specific portion of the grain, for example, a corner or an edge and does not surround the grain.

The high silver bromide-containing phase of the silver halide emulsion of the present invention may be formed as a layer so as to have a maximum silver bromide concentration inside the grain, or a maximum silver bromide concentration inside the grain. The portion having may be formed separately. Further, one grain may have a plurality of portions having a maximum silver bromide concentration. The high silver iodide-containing phase of the silver halide emulsion of the present invention is preferably formed in layers so that the grain surface has a maximum silver iodide concentration. Such a silver bromide-containing phase or a silver iodide-containing phase is composed of 3% or more and 30% or less of the grain volume in terms of increasing the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the amount of silver is 3% or more and 15% or less.

The silver bromide content or the silver iodide content necessary for exhibiting the effects of the present invention such as the enhancement of the sensitivity and the increase in the contrast is determined by the high silver bromide content phase or the high silver iodide content phase inside the grain. However, the silver chloride content may be reduced more than necessary and the rapid processability may be impaired. Therefore, it is preferable that the high silver bromide-containing phase and the high silver iodide-containing phase are adjacent to each other in order to concentrate these functions for controlling the photographic effect near the surface in the grain. From these points, the high silver bromide-containing phase is 50% of the grain volume measured from the inside.
To 100% of the grain volume, and the silver iodide-containing phase is preferably formed at any of 85% to 100% of the grain volume. Further, it is preferable that the high silver bromide-containing phase is formed at any of the positions of 70% to 95% of the grain volume, and the high silver iodide-containing phase is formed at any of the positions of 90% to 100% of the grain volume. preferable.

The introduction of the bromide or iodide ion to contain silver bromide or silver iodide in the silver halide emulsion of the present invention can be carried out by adding a solution of bromide salt or iodide salt alone or by adding a silver salt. A bromide salt or iodide salt solution may be added together with the addition of the solution and the high chloride salt solution. In the latter case, the bromide salt or iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of the bromide salt or iodide salt and the high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can be introduced by cleaving bromide ion or iodide ion from the organic molecule described in US Pat. No. 5,389,508. Fine silver bromide grains or fine silver iodide grains can also be used as another bromide or iodide ion source.

The addition of the bromide salt or iodide salt solution is
The particle formation may be concentrated in one period, or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in order to obtain an emulsion having high sensitivity and low fog. When the iodide ion is introduced inside the emulsion grains, the increase in sensitivity is small. Therefore, the addition of the iodide salt solution is preferably performed outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. The addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. When the addition of the iodide salt solution is completed slightly inside the grain surface, an emulsion having higher sensitivity and lower fog can be obtained. On the other hand, the bromide salt solution is preferably added to the outside of 50% of the grain volume, more preferably outside of 70%.

The distribution of the bromide or iodide ion concentration in the grain in the depth direction is determined by etching / TOF-SIMS.
(Time of Flight − Secondary Ion Mass Spectrometr
y) method, for example, TRIFT II type TO manufactured by Phi Evans
It can be measured using F-SIMS. The TOF-SIMS method is specifically described in "Surface Analysis Technology Selection Manual, Secondary Ion Mass Spectrometry" edited by The Surface Science Society of Japan, Maruzen Co., Ltd. (issued in 1999). Etching / TOF-SIMS
When the emulsion grains are analyzed by the method, it can be analyzed that even if the addition of the iodide salt solution is completed inside the grains, the iodide ions seep out toward the grain surface. In the emulsion of the present invention, it is preferable that the iodide ion has a maximum concentration on the surface of the grain and the iodide ion concentration decreases toward the inside, as determined by etching / TOF-SIMS analysis. It is preferable that the center of gravity of the distribution is inside, and that the concentration maximum is inside the particles.
The local concentration of silver bromide can also be measured by an X-ray diffraction method if the silver bromide content is high to some extent.

In the present specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to that of each particle. The emulsion of the present invention is required to have a very precise grain structure, and therefore it is preferable that the grain size distribution of the emulsion is monodisperse. The variation coefficient of the spherical equivalent diameter of all particles of the present invention is 20.
% Or less, more preferably 15% or less, and most preferably 10% or less.
The coefficient of variation of the sphere-equivalent diameter is expressed as a percentage of the standard deviation of the sphere-equivalent diameter of each particle with respect to the average of the sphere-equivalent diameters. 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 equivalent-sphere diameter of the silver halide grains contained in the silver halide emulsion of the present invention is preferably 0.6 μm or less, more preferably 0.5 μm or less, and 0.4 μm or less. Is most preferred. A particle having a sphere equivalent diameter of 0.6 μm corresponds to a cubic particle having a side length of about 0.48 μm, and a particle having a sphere equivalent diameter of 0.5 μm has a side length of about 0.4 μm.
m cubic particles, and a particle having a spherical equivalent diameter of 0.4 μm corresponds to a cubic particle having a side length of about 0.32 μm. The silver halide emulsion of the present invention may contain silver halide grains other than the silver halide grains contained in the silver halide emulsion defined in the present invention (that is, specific silver halide grains).
However, in the silver halide emulsion defined in the present invention, 50% or more of the total projected area of all the grains is preferably silver halide grains defined in the present invention, and more preferably 80% or more. , 90% or more is more preferable.

The sustained electron release time of the silver halide emulsion of the present invention is preferably between 10 ^-5 seconds 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. . When the electronic controlled release time is between 10 ^-5 seconds and 10 seconds, it is easy to obtain a high sensitivity and high contrast gradation in high-illuminance exposure, and latent image sensitization may occur during processing in a short time after exposure. It will not cause any problems. The electron sustained release time is more preferably 10 ⁻⁴ to 10 seconds, most preferably 10 ⁻³ to 1 second.

The sustained electron 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. If the exposure interval dependency of the second photoconductive signal intensity is taken by changing the exposure interval of two times, it becomes 2
It is possible to measure how the intensity of the photoconductive signal of the eye is decreasing. This represents the sustained release time of photoelectrons from the electron trap. The sustained release of electrons may continue to occur for a certain period of time after the exposure, but it is preferable that the sustained release is observed within 10 ⁻⁵ seconds to 10 seconds. 10 ^-4 seconds to 10
More preferably, sustained release is observed during 10 seconds, 10 ⁻³
More preferably, sustained release is observed between seconds and 1 second.

The specific silver halide grains in the silver halide emulsion of the present invention preferably contain iridium. As the iridium compound, a hexacoordinated complex having six ligands and iridium as a central metal is preferable because it can be uniformly incorporated into the silver halide crystal. As one preferable embodiment of iridium used in the present invention, a hexacoordinated complex having Ir as a central metal and having Cl, Br or I as a ligand is preferable, and Ir in which all six ligands are Cl, Br or I is A hexacoordination complex having a central metal is more preferable. In this case, Cl, Br or I may be mixed in the hexacoordinated complex. Cl, B
It is particularly preferable that the hexacoordination complex having Ir as a central metal and having r or I as a ligand is contained in the silver bromide-containing phase in order to obtain a hard gradation by exposure to high illuminance.

In the following, all 6 ligands are Cl, Br
Further, specific examples of the hexacoordinated complex of I having Ir as a central metal will be given, but the iridium in the present invention is not limited thereto. [IrCl ₆ ] ^2- [IrCl ₆ ] ^3- [IrBr ₆ ] ^2- [IrBr ₆ ] ^3- [IrI ₆ ] ^3-

As a different preferred embodiment of iridium used in the present invention, a hexacoordination complex having Ir as a central metal and having at least one ligand other than halogen or cyan is preferable, and H ₂ O, OH, O, OCN and thiazole are preferable. , A substituted thiazole, a thiadiazole, a substituted thiadiazole, a thiatriazole or a substituted hexathiatriazole as a ligand, preferably a 6-coordination complex having Ir as a central metal, and at least one H ₂ O, OH, O, OC
N, thiazole, substituted thiazole, thiadiazole, substituted thiadiazole, thiatriazole or substituted thiatriazole as a ligand and the rest of the ligands are C
A hexacoordination complex having Ir as a central metal and consisting of 1, Br or I 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.

Below, at least one H ₂ O, OH,
Specific examples of the hexacoordinated 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 the central metal are shown below, but the iridium in the present invention is not limited thereto. .

[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 object of the present invention is that all six ligands are C
One of a hexacoordination complex containing 1, 1, Br or I as a central metal with Ir or a six coordination complex with an Ir as a central metal having at least one ligand other than halogen or cyan is used alone. This is preferably achieved. However, in order to further enhance the effect of the present invention, a hexacoordination complex in which all six ligands are Cl, Br, or I with Ir as the central metal, and Ir having at least one ligand other than halogen or cyan are used.
It is preferable to use a 6-coordination complex having as a central metal together. Furthermore, at least one H ₂ O, OH, O, OC
Ir having N, thiazole or substituted thiazole as a ligand and the rest of the ligands consisting of Cl, Br or I
A hexacoordination complex having as a central metal is one of two ligands (H ₂ O, OH, O, OCN, thiazole or substituted thiazole and Cl, Br or I to 1).
It is preferable to use a complex composed of (seed).

The above-mentioned metal complexes are anions,
When a salt is formed with a cation, a counter cation which is easily dissolved in water is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, 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 These iridium complexes are added at 1 x 1 per mole of silver during grain formation.
It is preferable to add 1 × 10 ^-3 mol from 0 ^-10 mol, 1 ×
Most preferably, it is added from 10 ⁻⁸ mol to 1 × 10 ⁻⁵ mol.

In the present invention, the above iridium complex is
By adding directly to the reaction solution at the time of silver halide grain formation, or in an aqueous solution of a halide for forming silver halide grains, or in a solution other than that, and then adding to the grain formation reaction solution, the halogen It is preferably incorporated into silver halide grains. 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.

When these complexes are incorporated into silver halide grains, they may be made to exist uniformly inside the grains. JP-A-4-208936 and JP-A-2-12524
5, as disclosed in JP-A-3-188437, it is also preferable that the particles are present only in the particle surface layer,
It is also preferable that the complex is present only inside the particles and a layer not containing the complex is added to the surface of the particles. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical aging of fine particles in which a complex is incorporated to modify the surface phase of the particles. Is also preferable. Further, these methods may be used in combination, and plural kinds of complexes may be incorporated in one silver halide grain. There is no particular limitation on the halogen composition at the position where the above complex is contained, but all 6 ligands have Cl, Br, or I as the central metal 6
The coordination complex is preferably contained in the silver bromide concentration maximum part.

In the present invention, in addition to iridium, other metal ions can be doped inside and / or on the surface of the silver halide grain. The metal ion used is preferably a transition metal ion, of which iron, ruthenium, osmium, lead, cadmium, or zinc is preferable. 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 it is also preferable to use it by coordinating to any of the above-mentioned metal ions of iron, ruthenium, osmium, lead, cadmium, or zinc, and to use a plurality of types of ligands in one complex molecule. It is also preferable to use. 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 particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazan, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds having these compounds as a basic skeleton and substituents introduced therein are also preferable.

The combination of a metal ion and a ligand is preferably an iron ion or a ruthenium ion and a cyanide ion. In the present invention, it is preferable to use iridium and these compounds in combination. In these compounds, the cyanide ion preferably occupies a majority of the coordination numbers to the central metal iron or ruthenium, and the remaining coordination sites are thiocyan, ammonia, water, nitrosyl ion, dimethyl sulfoxide,
It is preferably populated with pyridine, 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. It is preferable to add 1 × 10 ^-8 mol to 1 × 10 ^-2 mol per mol of silver of the complex having a cyanide ion as a ligand, and 1 × 10 ^-6 mol to 5 × 10 5 mol per 1 mol of silver. It is most preferable to add ^-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. These complexes are used during the grain formation
It is preferable to add 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻⁶ mol per mol, and more preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁶ mol.

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.

For gold sensitization of the silver halide emulsion of the present invention, various inorganic gold compounds and 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 complex stability constant logβ _{2 of} gold 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 the general 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, a compound containing at least one unstable sulfur group capable of reacting with silver halide to form silver sulfide, a hydantoin compound, a thioether compound, a mesoionic compound, —SR. ', A heterocyclic compound, a phosphine compound, an amino acid derivative, a sugar derivative, and a thiocyano group, which may be the same 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 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-membered or 6-membered ring or a heterocycle containing the same, such as 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, the above-mentioned mesoionic compounds represented by L ¹ and L ² , —SR ′, and the heterocyclic compound are unstable sulfur groups capable of reacting with silver halide to produce silver sulfide. 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.

[0063]

[Chemical 1]

[0064]

[Chemical 2]

The compound represented by the general formula (I) can be prepared by a known method, for example, in Organic 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, JP-A-6-11788,
JP-A-6-501789, JP-A-4-267249
And JP-A-9-118685 and the like.

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.

[0067]

[Chemical 3]

[0068]

[Chemical 4]

[0069]

[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, a gold compound usually used (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. In addition, 5-described in EP 0447647
An arylamino-1,2,3,4-thiatriazole compound (wherein the aryl residue has at least one electron-withdrawing group) is also preferably used.

In the present invention, in order to improve the storage stability of the silver halide emulsion, the hydroxamic acid derivative described in JP-A-11-109576 and JP-A-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 may 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, it is in the range of 1.0 × 10 ⁻⁶ mol to 5.0 × 0 ⁻³ mol.

[Silver Halide Photosensitive Material] Next, the silver halide photographic material of the present invention will be described. The silver halide photographic light-sensitive material of the present invention may be black and white or color, but the silver halide emulsion of the present invention is preferably used in the silver halide color photographic light-sensitive material. The silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as "light-sensitive material") in which the silver halide emulsion of the present invention is preferably used is a silver halide emulsion layer containing a yellow dye-forming coupler on a support. And a silver halide emulsion layer containing a magenta dye-forming coupler and at least one silver halide emulsion layer containing a cyan dye-forming coupler. At least one layer is characterized by containing the silver halide emulsion of the present invention. 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 emulsion contained in each of the yellow color forming layer, the magenta color forming layer and the cyan color forming layer is sensitive to light in different wavelength regions (for example, light in blue region, green region and red region). It is preferable to have

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. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers and containing a white pigment such as titanium oxide in at least one of the water resistant resin layers (laminate layer) is preferable.

In the present invention, a more preferable reflective support is one having a polyolefin layer having fine pores on the paper base on which the 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 (rear surface) of the paper base from the photographic constituent layers from the viewpoint of increasing the rigidity of the reflection 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 reflection type support may be a transmission type support or the above-mentioned reflection 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, the 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 the 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 provided in 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.

In order to form the colored layer, a conventionally known method can be applied. 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. 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.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied in the present invention, and processing methods and processing additions applied for processing this light-sensitive 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.

Particularly, in the present invention, the above-mentioned reflection type support, silver halide emulsion, different metal ion species doped in silver halide grains, storage stabilizer of 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.

[0093]

[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 WO-98 / 33760 and the general formula (D) of JP-A-10-221825 may be added, which is preferable.

A pyrrolotriazole coupler is preferably used as a cyan dye-forming coupler (sometimes simply referred to as "cyan coupler") usable in the present invention, and it is represented by the general formula (I) in JP-A-5-313324. Or a coupler represented by (II) and JP-A-6-347960.
The couplers represented by the general formula (I) in JP-A No. 1993-154, and the exemplary 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. Cyan couplers other than those mentioned above include European Patent Nos. EP 0488248 and EP 0491197A.
1, a pyrroloazole-type cyan coupler,
2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716, US Pat.
Pyrazoloazole type cyan couplers having an electron-withdrawing group and a hydrogen bonding group at the 6-position described in JP-A-3,183 and JP-A-4,916,051, and particularly, JP-A-8-17
No. 1185, No. 8-311360, No. 8-3
The pyrazoloazole type cyan coupler having a carbamoyl group at the 6-position described in JP-A-39060 is also preferable.

Further, 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-eliminating 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.

Magenta dye-forming coupler used in the present invention (sometimes referred to simply 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 couplers used in the present invention are loadable latex polymers in the presence (or absence) of the high boiling organic solvents described in the table above (see, for example, US Pat. No. 4,20,20).
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, a compound having a triazine skeleton having a high molar extinction coefficient is preferably used as the ultraviolet absorber, and 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 an exposure step of irradiating light according to image information and a 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, cathode rays. 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 second harmonic emission light source (SHG) which is a combination of a solid-state laser using a semiconductor laser or 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.

The silver halide color photographic light-sensitive material containing the silver halide emulsion of the present invention has an emission wavelength of 420 nm to 46 nm.
Imagewise exposure is preferably carried out with coherent light of a 0 nm blue laser. Among the blue lasers, it is particularly preferable to use a blue semiconductor laser. As a laser light source, specifically, a blue semiconductor laser having a wavelength of 430 to 450 nm (presented by Nichia at the 48th Joint Lecture Meeting on Applied Physics, March 2001) and a semiconductor laser (oscillation wavelength of about 940 nm) in a waveguide shape Having an inverted domain structure of
About 470 nm blue laser and semiconductor laser (oscillation wavelength about 1060 nm) wavelength-converted and extracted by iNbO ₃ SHG crystal were wavelength-converted and extracted by LiNbO ₃ SHG crystal having a waveguide-like inversion domain structure. Green laser, wavelength about 685n
m red semiconductor laser (Hitachi type No. HL673
8 MG), a red semiconductor laser (Hitachi type No. HL6501MG) having a wavelength of about 650 nm, and the like are preferably used.

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 in combination 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 silver halide light-sensitive material containing the silver halide emulsion of the present invention is preferably applied as a light-sensitive material having rapid processing suitability. When rapid processing is carried out, the color development time is preferably 30 seconds or less, more preferably 25 seconds or less and 6 seconds or more, and still more preferably 20 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time is preferably 30 seconds or less, more preferably 25 seconds or less and 6 seconds or more, more preferably 20 seconds or less.
Seconds or less and 6 seconds or more. Also, the washing or stabilization time is
It is preferably 60 seconds or less, more preferably 40 seconds or less and 6 seconds or more.

The color developing time is the time from the photosensitive material entering the color developing solution to the bleach-fixing solution in the next processing step. For example, in the case of processing with an automatic developing machine, etc., the time during which the photosensitive material is immersed in the color developing solution (so-called in-liquid time), and the photosensitive material leaves the color developing solution to bleach-fix in the next processing step. The total of the time during which the film is transported in the air toward the bath (so-called air 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. Also, with washing or stabilization time,
It refers to the time (so-called in-liquid time) during which the light-sensitive material is in the liquid for washing process after entering the washing or stabilizing liquid.

The method of developing the light-sensitive material of the present invention after exposure may be 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.

Further, 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.

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

[0120]

The present invention will be described in detail below based on examples, but the present invention is not limited thereto.
In addition, "%" shows "mass%" in an Example. <Example 1> N was added to 1000 cc of an aqueous solution having a concentration of 5.8% in which deionized gelatin having a mass average molecular weight of 50,000 was dissolved.
The solution to which 3.7 g of aCl had been added was stirred while maintaining the temperature at 50 ° C., and silver nitrate and NaCl were added at 0.64 mol each over 17 minutes to form silver chloride grain nuclei. After that, 0.96 mol of silver nitrate and NaCl were added at a constant flow rate for 60 minutes to grow grains. The core particles thus obtained were cubic particles having an average side length of 0.27 μm, and the side length variation coefficient was 15%.

Further, K corresponding to 4 mol% relative to the total silver amount
Na containing Br and yellow blood salt equivalent to 2 × 10 ^-5 mol
A fixed amount of a silver nitrate solution equimolar to the Cl solution was added. At this time, the final amount of added silver nitrate was 2.0 mol. The growth rate at this time is 3 with respect to the critical growth rate obtained separately.
It was grown at a growth rate of 0%. Thus, the average silver bromide content is 4 mol% (that is, the average silver chloride content is 96 mol%).
And the content of bromine in the high silver bromide-containing phase is 20 mol%
To obtain silver chlorobromide fine particles. The particles were cubic particles having an average particle size of 0.30 μm and a coefficient of variation of 12%.

After that, a desalting water washing step is carried out, and p
It was adjusted to H5.0 and pAg 7.5 and redispersed. This redispersion liquid was kept at 50 ° C., 8 × 10 −4 mol of sodium benzenethiosulfonate was added, and 1 × 10 ⁻⁴ mol of a solid dispersion of sensitizing dye A and 1- (5-methylureidophenyl) were added. After adding 2 × 10 ⁻⁴ mol of -5-mercaptotetrazole, 52.7 × 10 ⁻⁵ mol% of (S-2) was added.
And sulfur sensitizer-A were added at 2 × 10 ⁻⁶ mol%. After the temperature was raised to 60 ° C., it was aged for 100 minutes. Thereafter, 1.77 × 10 ⁻³ mol of 1-phenyl-5-mercaptotetrazole was added to stop the aging, and 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to 2.7 × 1.
After adding 0 ^-3 mol and continuing stirring for 15 minutes, the temperature was lowered to 40 ° C or lower. The emulsion thus prepared was used as Emulsion A-1.
And

[0123]

[Chemical 6]

Among the adjusting conditions of Emulsion A-1, the core growing condition and the shell growing condition were changed as shown in Table 2 to obtain Emulsion A.
-2-A-6 was produced. The total Br addition amount was kept constant and the particle size was kept constant. The growth rate is shown as a ratio to the critical growth rate.

[0125]

[Table 2]

Corona discharge treatment was applied to the surface of a support having both sides of paper coated with polyethylene resin, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. The photographic constituent layers of No. 1 were sequentially coated to prepare a sample of a silver halide color photographic light-sensitive material having the following layer constitution. The coating liquid for each photographic constituent layer was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY-1) 57 g, color image stabilizer (Cpd-1) 7 g, color image stabilizer (Cpd-2) 4 g,
7 g of color image stabilizer (Cpd-3), color image stabilizer (Cpd-
8) 2 g was dissolved in a solvent (Solv-1) 21 g and ethyl acetate 80 ml, and this liquid was emulsified in 220 g of a 23.5 mass% gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate by a high-speed stirring emulsifier (dissolver). After dispersion, 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.

The coating liquid for the second layer was prepared in the same manner as the coating liquid for the first layer. The gelatin hardener for each layer is 1-
Oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used. Further, Ab-1, Ab-2, Ab-3, and Ab- are provided in each layer.
4, the total amount is 15.0 mg / m ² , 60.0 mg
/ M ² , 5.0 mg / m ² and 10.0 mg / m ² were added.

[0129]

[Chemical 7]

[0130]

[Chemical 8]

[0131]

[Chemical 9]

[0132]

[Chemical 10]

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). Silver halide emulsion,
Indicates the coating amount in terms of silver. Support polyethylene resin laminated paper [white pigment (TiO ₂ ; polyethylene resin on the first layer side;
Content 16% by mass, ZnO; content 4% by mass) and fluorescent whitening agent (4,4′-bis (5-methylbenzoxazolyl) stilbene. Content 0.03% by mass), bluish dye ( Including ultramarine) First layer (blue-sensitive emulsion layer) Emulsion 0.26 Gelatin 1.25 Yellow coupler (ExY-1) 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

[0134]   Second 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

[0135]

[Chemical 11]

[Sensitometry] The sample thus obtained was designated as Sample 101. In sample 101,
The emulsion of the emulsion layer was changed to the emulsion shown in Table 3, and the emulsion 102
To 106 were produced.

The following experiments were conducted to examine the photographic characteristics of these samples. A high-illuminance exposure sensitometer (HIE type manufactured by Yamashita Denso Co., Ltd.) and a standard illuminance sensitometer (tungsten light source) were used for each coated sample for 10 seconds / 1 /
Sensitometry with 10 seconds and 10 ⁻⁴ seconds exposure was performed with gradation exposure. A blue filter was used as the filter.

After exposure, color development processing A shown below was carried out. [Color development processing A] A sample of the above light-sensitive material was processed into a roll having a width of 127 mm, and after imagewise exposure using a mini lab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., the color development tank capacity was changed in the following processing steps. Continuous processing (running test) was performed until the replenishment was doubled. 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 Bleaching and fixing 38.0 ° C 45 seconds 35 ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds − Rinse (3) ** 38.0 ° C. for 20 seconds − Rinse (4) ** 38.0 ° C. for 30 seconds 121 ml * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Rinse screening method 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 4,5-dihydroxybenzene-1,3- Sodium disulfonate 0.5g 0.5g Potassium chloride 10.0g- Potassium bromide 0.040g 0.010g Triazinylaminostilbene fluorescent 2.5g 5.0g Whitening agent (Hakkor FWA-SF / Showa Kagaku) 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-ami No-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

[0140] [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

[0141] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5μS / cm or less)                             1000 ml 1000 ml pH 6.5 6.5

The yellow color density of each sample after treatment was measured to obtain a characteristic curve of illuminance for each sample. The sensitivity (S) is
Sample 1 is expressed by the antilogarithm of the reciprocal of the exposure amount that gives a color density 0.7 higher than the minimum color density, and the light amount is corrected at each illuminance.
It was expressed as a relative value with the 1/10 sensitivity of 01 being 100. The larger the value, the higher the sensitivity and the more preferable. The gradation was obtained from the slope of the straight line connecting the points of density 1.0 and density 2.0 at the time of 1/10 second exposure. The larger the value, the harder it is and the more preferable. The results are shown in Table 3.

[0143]

[Table 3]

As is clear from the results shown in Table 3, the samples using the silver halide emulsion of the present invention were found to be excellent in high sensitivity and high gradation at all illuminances.

<Example 2> Emulsions B-1 to B- were prepared by changing the Br content of the high silver bromide-containing phase as shown in Table 4 with respect to the conditions for forming the high silver bromide-containing phase under the adjusting conditions of Emulsion A-3.
5 was produced.

[0146]

[Table 4]

In the same manner as in Example 1, emulsions B-1 to B-5 were used to prepare coated samples for sensitometry, and sensitometric evaluation was carried out. The results are shown in Table 5.
Shown in.

[0148]

[Table 5]

As is apparent from Table 5, the light-sensitive material using the silver halide emulsion of the present invention showed excellent photographic performance.

Example 3 The surface of a support obtained by coating both sides of paper with a polyethylene resin was subjected to corona treatment, and then 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 Emulsion G-1) Lime-treated gelatin 3
% Aqueous solution (1000 ml) was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were stirred vigorously at 45 ° C.
And mixed at the same time. From the time when the addition of silver nitrate was 80% to the time when it was 90%, the K ₄ [Ru (CN) ₆ ] aqueous solution had a Ru amount of 3 × per mol of the finished silver halide.
An amount of 10 ⁻⁵ mol was added. 83% addition of silver nitrate
From the time point of 1 to 88%, an aqueous solution of K ₂ [IrCl ₆ ] was added in an amount such that the Ir amount was 5 × 10 ⁻⁸ mol per mol of the finished silver halide. Addition of silver nitrate is 9
From the time point of 2% to the time point of 95%, K ₂ [Ir (5
-Methylthiazole) Cl ₅ ] aqueous solution was added, and the amount of Ir was 5 × 10 ⁻⁷ per mol of the finished silver halide.
Molar amounts were added. Furthermore, the addition of silver nitrate is 95%
From the time point of 98% to the time point of K ₂ [Ir (H ₂ O)
Cl ₅ ] aqueous solution was added in an amount such that the Ir amount was 5 × 10 ⁻⁷ mol per mol of the finished silver halide. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grains were silver halide emulsions in which cubic silver chloride grains having a sphere-equivalent diameter of 0.35 μm and a coefficient of variation of 10% occupied about 100% of the total projected area. This emulsion was dissolved at 40 ° C. and sodium thiosulfonate was added at 2 × 1 per mol of silver halide.
0 ^-5 mol was added and aged for optimal at 60 ° C. using a sodium thiosulfate pentahydrate and a gold sensitizer as a sulfur sensitizer (S-2). After the temperature was lowered to 40 ° C., the sensitizing dye D was 6 × 10 ⁻⁴ mol and the 1-phenyl-5-mercaptotetrazole was 1 mol of silver halide per mol of silver halide.
2 × 10 ^-4 mol per mol, 1- (5-methylureidophenyl) -5-mercaptotetrazole is 8 × 10 ^-4 mol per mol of silver halide, and potassium bromide is 7 × 10 mol per mol of silver halide. ^-3 mol was added. The emulsion thus obtained was designated as Emulsion G-1.

[0152]

[Chemical 12]

(Preparation of Emulsion R-1) Lime-treated gelatin 3
% Aqueous solution (1000 ml) was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were stirred vigorously at 45 ° C.
And mixed at the same time. From the time of addition of silver nitrate of 80% to the time of 100%, potassium bromide was added with vigorous mixing in an amount of 4 mol% per mol of the finished silver halide. From the time when the addition of silver nitrate was 80% to the time when it was 90%, the K ₄ [Ru (CN) ₆ ] aqueous solution had a Ru amount of 3 × per mol of the finished silver halide.
An amount of 10 ⁻⁵ mol was added. 83% addition of silver nitrate
From the time point of 1 to 88%, an aqueous solution of K ₂ [IrCl ₆ ] was added in an amount such that the Ir amount was 5 × 10 ⁻⁸ mol per mol of the finished silver halide. Addition of silver nitrate is 9
At the end of 0%, an aqueous potassium iodide solution was added with vigorous mixing so that the amount of I was 0.1 mol% per mol of the finished silver halide. 92 addition of silver nitrate
% To 95%, K ₂ [Ir (5-
An aqueous solution of methylthiazole) Cl ₅ ] was added in an amount of 5 × 10 ⁻⁷ mol of Ir per mol of the finished silver halide. Further, from the time when the addition of silver nitrate was 95% to the time when 98% was added, K ₂ [Ir (H ₂ O) C
1 ₅ ] aqueous solution was added in such an amount that the Ir amount became 5 × 10 ⁻⁷ mol per mol of the finished silver halide. After desalting at 40 ° C., add 168 g of lime-processed gelatin,
The pH was adjusted to 5.5 and pCl1.8. The obtained grains were cubic silver iodobromochloride grains having a spherical equivalent diameter of 0.35 μm and a coefficient of variation of 10%, which accounted for almost 100% of the total projected area of the silver halide emulsion. This emulsion was dissolved at 40 ° C. and sodium thiosulfonate was added at 2 × 1 per mol of silver halide.
0 ^-5 mol was added and aged for optimal at 60 ° C. using a sodium thiosulfate pentahydrate and a gold sensitizer as a sulfur sensitizer (S-2). After cooling to 40 ° C., the sensitizing dye H was added to the silver halide at 2 × 10 ⁻⁴ mol and the 1-phenyl-5-mercaptotetrazole was added to the silver halide at 1 mol.
2 × 10 ⁻⁴ mol per mol, 1- (5-methylureidophenyl) -5-mercaptotetrazole 8 × 10 ⁻⁴ mol per mol silver halide, Compound I 1 × 10 ⁻ mol per mol silver halide. ³ mol and potassium bromide were added at 7 × 10 ⁻³ mol per mol of silver halide. The emulsion thus obtained was designated as Emulsion R-1.

[0154]

[Chemical 13]

Preparation of coating solution for first layer Yellow coupler (ExY-1) 57 g, color image stabilizer (Cpd-1) 7 g, color image stabilizer (Cpd-2) 4 g,
7 g of color image stabilizer (Cpd-3), color image stabilizer (Cpd-
8) 2 g was dissolved in a solvent (Solv-1) 21 g and ethyl acetate 80 ml, and this liquid was emulsified in 220 g of a 23.5 mass% gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate by a high-speed stirring emulsifier (dissolver). After dispersion, 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.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 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. Further, Ab-1, Ab-2, Ab-3, and Ab-4 were added to each layer in a total amount of 15.0 mg / m ² , 60.
0 mg / m ² , 5.0 mg / m ² and 10.0 mg / m ²
Was added.

Further, 1-phenyl-5-mercaptotetrazole was added to the green-sensitive emulsion layer and the red-sensitive emulsion layer.
1.0 × 10 ⁻³ mol and 5.9 × 10 ⁻⁴ mol were added per mol of silver halide, respectively. Further, 1-phenyl-5-mercaptotetrazole was also added to the second layer, the fourth layer, and the sixth layer at 0.2 mg / m ² and 0.2 mg, respectively.
/ M ² and 0.6 mg / m ² . Copolymer latex of methacrylic acid and butyl acrylate in the red-sensitive emulsion layer (mass ratio 1: 1, average molecular weight 200,000)
˜400000) was added at 0.05 g / m ² . Also,
Catechol-3,5-disulfonate disodium was added to the second layer, the fourth layer, and the sixth layer at 6 mg / m ² and 6 m, respectively.
g / m ² and 18 mg / m ² were added. Also,
To prevent irradiation, the following dyes (the amount in parentheses represents the coating amount) were added.

[0158]

[Chemical 14]

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). Silver halide emulsion,
Indicates the coating amount in terms of silver. Support polyethylene resin laminated paper [white pigment (TiO ₂ ; polyethylene resin on the first layer side;
Content 16% by mass, ZnO; content 4% by mass) and fluorescent whitening agent (4,4′-bis (5-methylbenzoxazolyl) stilbene. Content 0.03% by mass), bluish dye ( Ultramarine)] First layer (blue-sensitive emulsion layer) Emulsion A-1 0.26 Gelatin 1.25 Yellow coupler (ExY-1) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilization Agent (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21

[0160]   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

[0161]   Third layer (green sensitive emulsion layer)     Emulsion G-1 0.15     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

[0162]   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

[0163]   Fifth layer (red sensitive emulsion layer)     Emulsion R-1 0.13     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

[0164]   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

The sample obtained as described above was used as sample 3
It was set to 01. A sample was prepared in the same manner as Sample 301 except that the emulsion of the blue-sensitive emulsion layer was replaced with the silver halide emulsion of the present invention prepared in Examples 1 and 2.

The following experiments were conducted to examine the photographic characteristics of these samples. A ^10-6 second high intensity gradation exposure for gray color sensitometry was applied to each coated sample using a high intensity exposure photometer (HIE type manufactured by Yamashita Denso Co., Ltd.). After the exposure, the same color development processing A as in Examples 1 and 2 was performed.

The yellow color density of each sample after the treatment was measured to obtain a characteristic curve of 10 ⁻⁶ second high illuminance exposure. Sensitivity (S)
Is represented by the reciprocal of the reciprocal of the exposure amount that gives a color density of 0.7 higher than the minimum color density, and is expressed as a relative value with the sensitivity of Sample 301 as 100. The larger the value, the higher the sensitivity and the more preferable.
The gradation (γ) was obtained from the slope of the straight line connecting the points of density 1.0 and density 2.0. The larger the value, the harder it is and the more preferable. It was confirmed that the sample of the present invention was excellent in that the yellow color-forming layer had high sensitivity and showed a high gradation.

Example 4 A sample 401 was prepared by thinning the layers of the sample 301 of Example 3 by changing each layer as follows. First layer (blue-sensitive emulsion layer) Emulsion A-10 0.14 Gelatin 0.75 Yellow coupler (ExY-1) 0.34 Color image stabilizer (Cpd-1) 0.04 Color image stabilizer (Cpd-2) ) 0.02 color image stabilizer (Cpd-3) 0.04 color image stabilizer (Cpd-8) 0.01 solvent (Solv-1) 0.13

[0169]   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

[0170]   Third layer (green sensitive emulsion layer)     Emulsion G-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

[0171]   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

[0172]   Fifth layer (red sensitive emulsion layer)     Emulsion R-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

[0173]   Sixth layer (UV absorption layer)     Gelatin 0.32     Ultraviolet absorber (UV-C) 0.42     Solvent (Solv-7) 0.08

[0174]   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

The sample thus obtained was used as sample 4
It was set to 01. Further, the emulsion of the blue-sensitive layer was replaced with the emulsion of the present invention prepared in Examples 1 and 2 to prepare multi-layer coating materials.

The following experiments were conducted to examine the photographic characteristics of these samples by laser scanning exposure. As a laser light source, a blue semiconductor laser having a wavelength of about 440 nm (presented by Nichia at the 48th Joint Lecture Meeting on Applied Physics, March 2001), a semiconductor laser (oscillation wavelength of about 1060)
nm) having a waveguide-like inversion domain structure
Approximately 53 wavelength converted by O ₃ SHG crystal
A 0 nm green laser and a red semiconductor laser with a wavelength of about 650 nm (Hitachi type No. HL6501MG) were used. The laser light of each of the three colors moves in the direction perpendicular to the scanning direction by the polygon mirror, and
Sequential scanning exposure was made possible. 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 d
pi), and the average exposure time per pixel is 1.7.
× 10 ⁻⁷ seconds. By this exposure method, gradation exposure for gray color sensitometry was applied.

With respect to each exposed sample, color development processing was carried out according to the following development processing, and an ultra-rapid processing was carried out.

[Processing] A sample of the above light-sensitive material was 127 mm
Processed into a roll of width, using an experimental processor modified from Fuji Photo Film Co., Ltd. minilab printer processor PP350 so that the processing time and processing temperature can be changed. After exposure, continuous processing (running test) was performed 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.

Processing Step 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 seconds − Rinse 3 ** 40.0 ° C 8 seconds-rinse 4 38.0 ° C 8 seconds 121mL dry 80.0 ° C 15 seconds (Note) * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. Attach to (3) and rinse (3)
The rinse liquid is taken out from the pump and sent to a reverse osmosis module (RC50D) by a pump. The permeated water sent in the same tank is supplied to the rinse, and the concentrated liquid is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day. The rinse was a 4-tank countercurrent system from (1) to (4).

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher] Water 800mL 600mL 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- 4,5-dihydroxybenzene- Sodium 1,3-disulfonate 0.50 g 0.50 g Disodium-N, N-bis (sulfonate Ethyl) hydroxylamine 8.5 g 14.5 g 4-amino-3-methyl-N-ethyl-N- (Β-methanesulfonamidoethyl) aniline ・ 3/2 Sulfate ・ Monohydrate 10.0g 22.0g Potassium carbonate 26.3g 26.3g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with sulfuric acid and KOH) 10.35 12.6

[0181] [Bleaching fixer] [Tank solution] [Replenisher] Water 800mL 800mL Ammonium thiosulfate (750 g / mL)                                   107 mL 214 mL Succinic acid 29.5g 59.0g Ethylene diamine tetraammonium 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 the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with nitric acid and aqueous ammonia) 6.00 6.00

[0182] [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

The yellow color density of each processed sample was measured and a characteristic curve of laser exposure was obtained. It was found that the sample using the emulsion of the present invention showed excellent performances in terms of sensitivity and gradation. It was

The structural formulas of the compounds used in this example are shown below.

[0185]

[Chemical 15]

[0186]

[Chemical 16]

[0187]

[Chemical 17]

[0188]

[Chemical 18]

[0189]

[Chemical 19]

[0190]

[Chemical 20]

[0191]

[Chemical 21]

[0192]

[Chemical formula 22]

[0193]

[Chemical formula 23]

[0194]

INDUSTRIAL APPLICABILITY The present invention can provide a silver halide emulsion which does not cause sensitivity lowering or softening even in digital exposure such as laser scanning exposure and which can obtain high sensitivity and high gradation.

[Brief description of drawings]

FIG. 1 is a perspective view showing an outline of a tetrahedral silver halide grain.

Claims (2)

[Claims] 1. A silver halide emulsion containing silver chloride as a main component and further containing at least silver halide grains having an outer shape of 24 faces. 2. The silver halide emulsion according to claim 1, wherein the silver halide grains have a high silver bromide-containing phase having an average Br content of 18 mol% or more.