JP3260164B2 - Silver halide photographic emulsion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion used for a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved sensitivity and graininess and excellent environmental adaptability. The present invention relates to a silver halide photographic emulsion used for a material.

[0002]

2. Description of the Related Art In recent years, the use of photographing devices such as cameras has become increasingly popular.
Opportunities for photography using silver halide photographic light-sensitive materials are also increasing. Accordingly, demands for higher sensitivity and higher image quality of silver halide photographic light-sensitive materials have been increasing.

One of the dominant factors in increasing the sensitivity and image quality of silver halide photographic light-sensitive materials is silver halide grains. Silver halide grains aiming at higher sensitivity and higher image quality. Particle development has traditionally been pursued in the art.

However, as is generally practiced, the sensitivity tends to decrease as the grain size of silver halide grains is reduced in order to improve image quality, and both high sensitivity and high image quality are satisfied. Had limitations.

Techniques for improving the sensitivity / size ratio per silver halide grain have been studied in order to achieve higher sensitivity and higher image quality. One of such techniques is tabular silver halide grains. The technology used is JP-A-58-111935
No. 58-111936, No. 58-111937, No. 58
-ll3927 and 59-99433. When these tabular silver halide grains are compared with so-called normal crystal silver halide grains such as octahedral and hexahedral,
When the silver halide grains have the same volume, tabular silver halide grains have a larger surface area, so that more sensitizing dyes can be adsorbed on the surface of the silver halide grains, resulting in higher sensitivity. There is.

JP-A-63-92942 discloses a technique of providing a core having a high silver iodide content inside tabular silver halide grains, and JP-A-63-151618 discloses a hexagonal tabular halide. The technique using silver grains is disclosed in JP-A-63-163451, and the technique using tabular silver halide grains in which the ratio of the grain thickness to the longest distance between twin planes is 5 or more is mentioned. The effect on graininess is shown.

As described above, in addition to the technique for improving the sensitivity by improving the grain structure and shape, the doping of metal ions into the silver halide grains allows the generation of photoelectrons and holes in the silver halide grains. Techniques are known for improving motion and modifying its photographic properties.

As a technique for achieving high sensitivity by doping metal ions, Japanese Patent Application Laid-Open No. 2-20853 discloses rhenium,
A doping technique for ruthenium and osmium cyano complexes is disclosed, but no mention is made of the ligand of the present invention. Japanese Patent Application Laid-Open No. 1-121844 discloses a technique in which divalent Fe ions are doped into the minimum portion of the band gap in silver halide grains. However, even in the examples of the patent, only the iron cyano complex is described, and there is no specific description of the iron compound containing the ligand of the present invention in the specification.

[0009]

An object of the present invention is to provide a silver halide photographic emulsion which provides a silver halide photographic light-sensitive material having high sensitivity and excellent graininess.

[0010]

SUMMARY OF THE INVENTION It has been found that the objects of the present invention are achieved by a silver halide photographic emulsion of the substructure. (1) A silver halide emulsion containing a metal complex having at least one luminate ligand. (2) The silver halide emulsion according to the above (1), wherein the metal complex is a six-coordinate complex. (3) The silver halide emulsion according to the above (1) or (2), wherein the silver halide is silver bromide or silver iodobromide.

Hereinafter, the present invention will be described in more detail.

The luminate ligand referred to in the present invention is represented by the following formula [1]:

[0013]

Embedded image It refers to one coordinated with a metal atom or ion and a C atom.

The six-coordinate metal complex having at least one luminate ligand is described by the following formula [2].

[0015]

Embedded image Here, M represents a metal atom or an ion. m is the number of ligands of the luminate ligand. L represents a ligand other than the luminate ligand, n is the valence of the entire metal complex represented by the formula [2], and n = -1, -2, -3, -4
Is preferred.

The number of ligands of the luminate ligand is as follows:
It is preferably 4 or more, and particularly preferably 6, that is, all the ligands are luminate ligands.

M may be any as long as it forms a complex of the formula [2], but may be Fe, Co, Ru, Rh, Re, O
s, Ir and Au are preferred.

Hereinafter, specific examples of the complex compound having a luminate ligand satisfying the requirements of the present invention will be shown, but the present invention is not necessarily limited thereto.

[0019]

Embedded image The silver halide grains contained in the silver halide emulsion of the present invention may be grains whose latent image is mainly formed on the surface or grains whose latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal form such as cubic, octahedral or tetradecahedral,
It may have an irregular crystal form such as a sphere or a plate. In these particles, the ratio between the {100} plane and the {111} plane can be arbitrarily used. Further, those having a complex form of these crystal forms may be used, and grains of various crystal forms may be mixed, but twin silver halide grains having two opposed parallel twin planes are preferably used. Can be

A twin is a silver halide crystal having one or more twin planes in one grain, and a classification of the twin is based on a report by Klein and Moiser in Photographic Corspondents. (Photographe Korresponden
z] It is described in detail in Volumes 99, 99 and 100, 57.

In the present invention, when tabular silver halide grains are used, the average value of the ratio of the diameter to the thickness of the tabular grains (also referred to as the aspect ratio) is preferably less than 5, more preferably 1.1 or more. Less than 4.5, particularly preferably
1.2 or more and less than 4. This average value is obtained by averaging the ratio of the diameter to the thickness of all tabular grains.

The diameter of a silver halide grain is represented by a circle-equivalent diameter of the projected area of the silver halide grain (diameter of a circle having the same projected area as the silver halide grain).
It is preferably 5.0 μm, more preferably 0.2 to 4.0 μm, particularly preferably 0.3 to 3.0 μm.

The silver halide photographic emulsion according to the present invention may be any emulsion such as a polydisperse emulsion having a wide grain size distribution or a monodisperse emulsion having a narrow grain size distribution, but is preferably a monodisperse emulsion.

Here, as the monodispersed silver halide emulsion, the weight of silver halide contained within a grain size range of ± 20% around the average grain size r is 60% or more of the total weight of silver halide grains. Some are preferred, more preferably 70% or more, and still more preferably 80% or more.

Here, the average particle size r is defined as the particle size ri when the product ni × ri ³ of the frequency ni and ri ³ of the particles having the particle size ri is maximum (three significant figures, minimum Digits are rounded off to the nearest 5).

Here, the particle size is a diameter when a projected image of silver halide grains is converted into a circular image having the same area.

The particle diameter can be obtained, for example, by photographing the particle with an electron microscope at a magnification of 10,000 to 70,000 and measuring the particle diameter or the area at the time of projection on the print (measurement particle). The number shall be indiscriminately 1,000 or more.)

Particularly preferred highly monodispersed emulsions of the present invention are:

[0030]

(Equation 1) Is defined as 20% or less, and more preferably 15% or less.

Here, the average particle diameter and the standard deviation are determined from the particle diameter ri defined above.

In the present invention, when silver iodobromide is used as the silver halide, the silver iodide content is 0.1 mol% or more as an average silver iodide content in the whole silver halide grains.
It is preferably at most 5 mol%, more preferably at least 5 mol% and at most 12 mol%, particularly preferably at least 6 mol%.
Not less than 10 mol.

The silver halide grains contained in the silver halide photographic emulsion of the present invention are preferably so-called core / shell grains in which silver iodide is concentrated.

The core / shell type particles are particles composed of a core serving as a nucleus and a shell covering the core, and the shell is formed by one or more layers. The silver iodide content of the core and the shell are preferably different from each other, and it is particularly preferable that the core and the shell are formed with the maximum silver iodide content.

The core has a silver iodide content of preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 25 mol% or more. The silver iodide content of the outermost shell in the shell, that is, the shell that normally forms the outermost surface layer is preferably 5 mol% or less, more preferably 0 to 2 mol%. The proportion occupied by the core is desirably 2 to 60%, preferably 5 to 50%, of the total volume of the particles.

The silver halide grains contained in the silver halide photographic emulsion of the present invention are prepared by preliminarily providing an aqueous solution containing a protective colloid and seed grains in a reaction vessel, and if necessary, silver ions, halide ions or silver halide fine grains. Is supplied to cause seed particles to grow. here,
Seed particles can be prepared by a single jet method or a controlled double jet method well known in the art. The halogen composition of the seed particles is arbitrary,
Any of silver bromide, silver iodide and silver iodobromide,
Silver bromide and silver iodobromide are preferred.

When seed particles are used in the present invention, the seed particles may have a regular crystal form such as a cube, an octahedron, or a tetrahedron, or an irregular crystal such as a sphere or a plate. It may have a shape. In these particles,
Any ratio can be used for the {100} plane and the {111} plane. Further, those having a composite form of these crystal forms may be used, and particles of various crystal forms may be mixed.
It is preferable to use the monodisperse spherical seed particles described in JP-A-178-178.

As a means for forming a silver halide photographic emulsion according to the present invention, various methods well known in the art can be used. That is, the single jet method,
Any combination of the double jet method, the triple jet method, and the like can be used. Further, a method of controlling pAg and pH in a liquid phase in which silver halide is formed in accordance with the growth rate of silver halide can also be used.

The silver halide photographic emulsion of the present invention can be produced by any of an acidic method, a neutral method, and an ammonia method.

In the production of the silver halide photographic emulsion of the present invention, halide ions and silver ions may be mixed at the same time, or one of them may be mixed in the presence of the other. Further, the growth may be carried out by adding halide ions and silver ions successively or simultaneously while controlling the pH and pΛg in the mixing vessel in consideration of the critical growth rate of silver halide crystals. The silver halide composition of the grains may be changed by using a conversion method in any step of silver halide formation. Further, halide ions and silver ions may be supplied as fine silver halide particles into the mixing vessel.

In the production of the silver halide photographic emulsion of the present invention, a known silver halide solvent such as ammonia, thioether, thiourea and the like can be used.

The silver halide grains contained in the silver halide photographic emulsion of the present invention may be used in the step of forming and / or growing the grains during the formation of cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (complex salts). ), A rhodium salt (including a complex salt) and an iron salt (including a complex salt), and adding a metal ion to the inside of the particle.
Alternatively, these metal elements can be contained on the surface of the grains, and a reduction sensitizing nucleus can be provided inside the grains and / or on the surface of the grains by placing the metal element in an appropriate reducing atmosphere.

In the silver halide photographic emulsion of the present invention, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or may be kept contained. When removing the salts, use Research Disclosure (Re
search Disclosure (hereinafter abbreviated as RD) can be performed based on the method described in 17643, paragraph II.

In the silver halide photographic emulsion of the present invention,
In order to incorporate the metal complex of the present invention into the silver halide photographic emulsion, a method in which an additive is generally added to the silver halide photographic emulsion in the art can be applied. For example, these compounds can be dissolved in a suitable organic solvent represented by alcohols or water in advance and added. Further, a dispersion method described in Japanese Patent Application No. 4-714 as a method of dispersing a spectral sensitizing dye can be used. That is, the metal complex of the present invention can be added in an amount exceeding the solubility and mechanically dispersed into solid fine particles of 1 μm or less in an aqueous system substantially free of an organic solvent and / or a surfactant, and then added.

In the present invention, the timing of adding the metal complex may be any time during the production process of the silver halide photographic emulsion, but is preferably before the completion of the growth of the silver halide grains.

In the silver halide photographic emulsion of the present invention,
When the metal complex is contained in the silver halide photographic emulsion, a solution containing the metal complex can be directly added to the silver halide photographic emulsion. When the metal complex is added during the growth of silver halide grains, a halide is used. The metal complex may be added in advance to an aqueous solution containing ions, an aqueous solution containing silver ions, or a solution containing fine silver halide particles. Further, the addition of the solution containing the metal complex may be performed instantaneously,
Or you may add continuously using an arbitrary function.

The addition amount of the metal complex in the present invention is preferably from 10 ^-8 mol to 10 ^-1 mol, more preferably from 10 ^-7 mol to 10 ^-2 mol, most preferably from 1 mol to 10 mol per mol of silver halide grains. Is from 10 ^-6 mol to 10 ^-3 mol.

In the production of the silver halide photographic emulsion according to the present invention, conditions other than those described above are described in JP-A-61-6643.
No. 61-14630, No. 61-112142, No. 62-157
No. 024, No. 62-18556, No. 63-92942, No. 63-1
Optimal conditions can be selected with reference to known methods such as those disclosed in JP-A-51618, JP-A-63-163451, JP-A-63-220238, and JP-A-63-311244.

The silver halide photographic emulsion of the present invention can be preferably used for a silver halide color photographic light-sensitive material.

In constructing a color photographic light-sensitive material using the silver halide photographic emulsion of the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. Additives used in such a process are Research Disclosure Nos. 17643, No. l8716 and N
o.308119 (hereinafter RD17643, RD18716 and RD3081 respectively)
19). Table 1 shows the locations described.

[0051]

[Table 1] Known photographic additives that can be used in forming a color photographic light-sensitive material using the silver halide photographic emulsion of the present invention are also described in the above-mentioned Research Disclosure.
Table 2 shows the relevant descriptions.

[0052]

[Table 2] In constructing a color photographic light-sensitive material using the silver halide photographic emulsion of the present invention, various couplers can be used, and specific examples thereof are RD17643 and RD308119 described below.
It is described in. Table 3 shows the relevant descriptions.

[0053]

[Table 3] Additives used when constituting a color photographic light-sensitive material using the silver halide photographic emulsion of the present invention are RD308119 1007
It can be added by the dispersion method described in page XIV.

When a color photographic light-sensitive material is constructed using the silver halide photographic emulsion of the present invention, the above-mentioned RD17643 28
The supports described in pages RD18716 pages 647-8 and RD308119 page 1009 section XVII can be used.

A color photographic light-sensitive material using the silver halide photographic emulsion of the present invention may be provided with an auxiliary layer such as a filter layer or an intermediate layer described in the aforementioned RD308119 VII-K.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention may have various layer constitutions such as a forward layer, a reverse layer and a unit constitution described in the aforementioned RD308119 VII-K. Can be.

The silver halide photographic emulsion of the present invention can be used as a general or movie color negative film, a slide or television color reversal film, a color paper,
It can be preferably applied to various color photographic light-sensitive materials represented by a color positive film and a color reversal paper.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is described in RD1764328-29, RD187716 above.
Development can be carried out by a usual method described on page 15 and RD308119 XIX.

[0059]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. Example 1 Preparation of spherical seed emulsion (Em-1) A monodisperse spherical seed emulsion (Em-1) was prepared by the following method with reference to the description of Japanese Patent Application No. 2-408178. . (Solution J) Ossein gelatin 80 g Potassium bromide 47.4 g Polyisopropylene-polyethyleneoxy-disuccinate sodium salt -10% methanol solution 2.0 mL 8.0 L with water (Solution K) Silver nitrate 1.2 kg 1.6 L with water ( Solution L) Ossein gelatin 32.2 g Potassium bromide 840 g 1.6 L with water (Solution M) Ammonia water 470 mL To Solution J vigorously stirred at 40 ° C., Solution K and Solution L were added in 11 minutes by a double jet method. Nucleation was performed. During this time, pBr was kept at 1.60.

Over the next 12 minutes, the temperature is lowered to 30 ° C.
Aging was performed for another 18 minutes. Further, the solution M was added for 1 minute, followed by aging for 5 minutes. K at aging
The Br concentration was 0.07 mol / l and the ammonia concentration was 0.63 mol / l.

After completion of ripening, the pH was adjusted to 6.0, and desalting was performed according to a conventional method. Observation of the seed emulsion grains with an electron microscope revealed that the grains were spherical seed emulsions containing spherical silver halide grains having an average diameter of 0.318 μm and having two twin planes parallel to each other. Preparation of Silver Halide Emulsion (Em-2) (Em-2) was prepared using the following eight kinds of solutions. (Solution A) Ossein gelatin 208.2 g Distilled water 4.0 L Polyisopropylene-polyethyleneoxy-disuccinate sodium salt -10% methanol solution 1.5 mL 28% by weight aqueous ammonia 528.0 mL 56% by weight acetic acid aqueous solution 795.0 mL With distilled water Make up to 5390.0 ml. (Solution B) 3.5N ammoniacal silver nitrate aqueous solution (pH adjusted to 9.0 with ammonium nitrate) (Solution C) 3.5N potassium bromide aqueous solution containing 4.0% by weight gelatin (Solution D) 3% by weight gelatin and 0.844 mol of a fine grain emulsion composed of silver iodide grains (average grain size: 0.05 μm) is described below.

6.0% by weight containing 0.06 mol of potassium iodide
2,000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide was added to 5000 ml of the gelatin solution over 10 minutes. PH during microparticle formation
Was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. (Solution E) Fine grain emulsion comprising silver iodobromide grains containing 1 mol% of silver iodide (average grain size 0.04 μm), prepared in the same manner as the silver iodide fine grain emulsion described in Solution D
2.20 mol However, the temperature during the formation of the fine particles was controlled at 30 ° C. (Solution F) 1.75N aqueous solution of potassium bromide required amount (Solution G) 56% by weight aqueous solution of acetic acid required amount (Solution H) Seed emulsion (Em-1) 0.341 mol Maintained at 70 ° C. in the reaction vessel (Solution A) After adding (Solution H), (Solution B), (Solution C) and (Solution D) are added by the simultaneous mixing method over a period of 163 minutes, followed by (Solution E) over 12 minutes. At a constant rate.

Here, the rate of addition of (Solution B) and (Solution C) was changed in a function-wise manner with time so as to match the critical growth rate, and the generation of small particles other than the growing seed crystal and Ostwald It was added at an appropriate addition rate so as not to be polydispersed by aging. By setting the ratio of the addition rate of (Solution D) to the addition rate of (Solution B) so that a silver halide phase having a silver iodide content (mol%) shown in Table 4 is formed, a multiple structure is obtained. A core / shell type silver halide emulsion was prepared.

During the growth of silver halide grains, pAg and pH were controlled as shown in Table 4 by appropriately using (solution F) and (solution G).

The measurement of pAg and pH was carried out using a silver sulfide electrode and a glass electrode according to a conventional method.

After the grain growth, a desalting treatment was carried out by a conventional method, and then gelatin was added and redispersed.
0, pAg was adjusted to 8.06.

When the silver halide grains contained in the obtained silver halide emulsion were observed with a scanning electron microscope, the emulsion was found to be an octahedral twin monodisperse emulsion having an average diameter of 1.0 μm and a distribution width of 10.3%. confirmed.

[0068]

[Table 4]

Preparation of silver halide emulsion (Em-3) Emulsion Em- was prepared in the same manner as in preparation of emulsion Em-2 except that solution H was added and then solution M-1 described below was added.
3 was prepared. (Solution M-1) Preparation of 0.5 wt% solution of K ₄ [Fe (CN) ₆ ] · 3H ₂ O 75.1 cc Preparation of silver halide emulsion (Em-4) In the preparation of emulsion Em-2, after adding solution H An emulsion # m-4 of the present invention was prepared in the same manner except that the following solution M-2 was added. (Solution M-2) Preparation of 82.6 cc Silver Halide Emulsion (Em-5) K ₄ [Fe (CNO) ₆ ] 0.5% by weight Solution Emulsion Em-5 was prepared in the same manner except that a solution (solution C-2) to which solution M-1 was added so as to be × 10 ^-4 N was used instead of solution C. Preparation of silver halide emulsion (Em-6) Emulsion Em-6 of the present invention was prepared in the same manner as in the preparation of emulsion Em-5 except that solution M-2 was used instead of solution M-1.
Was prepared.

Sensitizing dyes SD-A and SD-B shown below were added to silver halide emulsions Em-2 to Em-6 at a temperature of 55 ° C. at 1.4 × 10 ^-4 mol and 1.4 ^-4 mol, respectively, per mol of silver.
After spectral sensitization by simultaneous addition and adsorption of × 10 ^-4 mol, sodium thiosulfate and chloroauric acid were optimally subjected to chemical sensitization to obtain emulsions Em-2S, Em-3S,
Em-4S, Em-5S and Em-6S were prepared.

Next, magenta couplers MA, MB,
After adding MC, 2-hydroxy-
An appropriate amount of 4,6-dichlorotriazine sodium was uniformly added, and each emulsion was coated on a triacetate cellulose support which had been coated so that the coated silver amount was 2.0 g / m ² , dried, and dried. 5 was obtained.

[0072]

Embedded image Each of these samples was subjected to wedge exposure (exposure to 1/100 second) using green light in a usual manner, color-developed according to the following color processing steps, and photographic performance was comparatively evaluated. Table 5 shows the results
Shown in

The sensitivities in Table 5 were expressed as relative sensitivities with the sensitivity of Sample 1 (comparative) taken as 100. Note that the relative sensitivity is a relative value of the reciprocal of the amount of received light that gives fog density + 0.1.

Processing step Processing temperature 38 ° C Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fix 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry each The composition of the processing solution used in the processing step is as follows. <Color developing solution> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to 1000 ml, and adjust to pH 10.6 with sodium hydroxide. <Bleaching solution> Ammonium salt of iron (III) ethylenediaminetetraacetate 100.0 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Add water to make 1000 ml, and adjust to pH 6.0 using aqueous ammonia. I do. <Fixing solution> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1000 ml, and adjust to pH 6.0 with acetic acid. <Stabilizing solution> Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1000 ml.

[0075]

[Table 5] As is clear from Table 5, the samples using the emulsion of the present invention have high sensitivity. Example 2 Using the emulsions Em-2S to Em-6S prepared in Example 1, multilayer color photosensitive materials 101 to 105 were prepared. Em
-2S to Em-6S are used in the high-sensitivity green-sensitive layer and are described as Emulsion A in the following formulation.

The amount of addition indicates grams per 1 m ² unless otherwise specified. Silver halide and colloidal silver were expressed in terms of silver, and sensitizing dyes were expressed in moles per mole of silver. First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling solvent (Oil-1) 0.16 Gelatin 1.23 Second layer: Intermediate layer Compound (SC-1) 0.15 High boiling solvent (Oil-) 2) 0.17 gelatin 1.27 3rd layer; low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm) (silver iodide content 8.0 mol%) 0.50 silver iodobromide emulsion (average grain size 0.27 μm) ( (Silver iodide content: 2.0 mol%) 0.21 sensitizing dye (SD-1) 2.8 × 10 ^-4 sensitizing dye (SD-2) 1.9 × 10 ^-4 sensitizing dye (SD-3) 1.9 × 10 ^-5 sensitization Dye-sensitive dye (SD-4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High boiling solvent (Oil) -1) 0.53 gelatin 1.30 4th layer; middle-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm) (silver iodide content 8.0 mol %) 0.62 Silver iodobromide emulsion (average grain size 0.38 .mu.m) (silver iodide content 8.0 mol%) 0.27 Sensitizing dye (SD-1) 2.3 × 10 -4 Sensitizing dye (SD-2) 1.2 × 10 ^-4 sensitizing dye (SD-3) 1.6 × 10 ^-5 sensitizing dye (SD-4) 1.2 × 10 ^-4 cyan coupler (C-1) 0.15 cyan coupler (C-2) 0.18 colored cyan coupler (CC- 1) 0.030 DIR compound (D-1) 0.013 High boiling point solvent (Oil-1) 0.30 Gelatin 0.93 Fifth layer; High sensitivity red-sensitive layer Silver iodobromide emulsion (average particle size 1.0 μm) (Silver iodide content 8.0 Mol%) 1.27 Sensitizing dye (SD-1) 1.3 × 10 ^-4 Sensitizing dye (SD-2) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Cyan coupler (C-2) 0.12 Colored cyan coupler (CC-1) 0.013 High boiling solvent (Oil-1) 0.14 Gelatin 0.91 6th layer; Intermediate layer Compound (SC-1) 0.09 High boiling solvent (Oil-2) 0.1 1 Gelatin 0.80 7th layer; low-sensitivity green-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm) (silver iodide content 8.0 mol%) 0.61 Silver iodobromide emulsion (average grain size 0.27 μm) (iodide (Silver content 2.0 mol%) 0.20 Sensitizing dye (SD-4) 7.4 × 10 ^-5 Sensitizing dye (SD-5) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.41 Colored magenta coupler (CM-1) 0.12 High boiling solvent (Oil-2) 0.75 Gelatin 1.95 Eighth layer; Medium-sensitive green-sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm) (Silver iodide content 8.0 mol% 0.87 Sensitizing dye (SD-6) 2.4 × 10 ^-4 Sensitizing dye (SD-7) 2.4 × 10 ^-4 Magenta coupler (M-1) 0.058 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-) 1) 0.070 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling solvent (Oil-2) 0.50 1.00 ninth layer; high-sensitivity green-sensitive layer silver iodobromide emulsion (emulsion A) 1.27 sensitizing dye (SD-6) 1.4 × 10 ^-4 sensitizing dye (SD-7) 1.4 × 10 ^-4 magenta coupler ( M-2) 0.084 Magenta coupler (M-3) 0.064 Colored magenta coupler (CM-1) 0.012 High boiling solvent (Oil-1) 0.27 High boiling solvent (Oil-2) 0.012 Gelatin 1.00 10th layer; Yellow filter layer Yellow Colloidal silver 0.08 Color stain inhibitor (SC-2) 0.15 Formalin scavenger (HS-1) 0.20 High boiling solvent (Oil-2) 0.19 Gelatin 1.10 11th layer; Intermediate layer Formalin scavenger (HS-1) 0.20 Gelatin 0.60 12th Layer: low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size: 0.38 μm) (silver iodide content: 8.0 mol%) 0.22 Silver iodobromide emulsion (average grain size: 0.27 μm) (silver iodide content: 2.0 mol) %) 0.03 Sensitizing dye (SD-8) 4.9 ^10-4 Yellow coupler (Y-1) 0.75 DIR compound (D-1) 0.010 High boiling solvent (Oil-2) 0.30 Gelatin 1.20 13th layer: middle sensitivity blue-sensitive layer Silver iodobromide emulsion (average particle size 0.59μm ) (Silver iodide content 8.0 mol%) 0.30 sensitizing dye (SD-8) 1.6 × 10 ^-4 sensitizing dye (SD-9) 7.2 × 10 ^-5 yellow coupler (Y-1) 0.10 DIR compound (D -1) 0.010 High boiling point solvent (Oil-2) 0.046 Gelatin 0.47 14th layer; high-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size: 1.0 μm) (silver iodide content: 8.0 mol%) 0.85 sensitizing dye (SD-8) 7.3 × 10 ^-5 sensitizing dye (SD-9) 2.8 × 10 ^-5 yellow coupler (Y-1) 0.11 high boiling solvent (Oil-2) 0.046 gelatin 0.80 15th layer; first protective layer Silver iodobromide (average grain size: 0.08 µm) (silver iodide content: 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 UV absorber (UV-2) 0.10 High boiling solvent (Oil-1) 0.07 High boiling solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31 16th layer; 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethyl Methacrylate (average particle size: 3 μm) 0.04 Slip agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1, dispersing aid Su-2, viscosity modifier, hardener H -1, H-2, stabilizer ST-1, antifoggant AF-1, weight average molecular weight: 1
0,000 and 1,100,000 two AF-2 and preservative DI-
1 was added. The amount of DI-1 added was 9.4 mg / m ² .

The structure of the compound used in the above sample is shown below.

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These samples were exposed to white light for sensitometry (exposure time: 1/100 second) and processed in the following processing steps to evaluate the sensitivity. Processing step (38 ° C) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fix 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry Used in each processing step The composition of the processing solution is as follows. <Color developing solution> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter, and adjust the pH to 10.0. <Bleaching solution> Ethylene (III) ammonium salt of ethylenediaminetetraacetic acid 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Add water to make 1 liter, and adjust the pH to 6.0 using aqueous ammonia. I do. <Fixing solution> Ammonium thiosulfate 175.0 g Sodium sulfite anhydrous 8.5 g Sodium metasulfite 2.3 g Add water to make 1 liter, and adjust the pH to 6.0 using acetic acid. <Stabilizing solution> Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1 liter.

Table 6 shows the sensitivity evaluation results of Samples 101 to 105.

The relative sensitivity is the reciprocal of the amount of received light that gives fog density +0.1, and is shown as a value with the green sensitivity of the sample 101 being 100.

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[Table 6] From Table 6, it is clear that the sample using the emulsion of the present invention has high sensitivity even in a multilayer photosensitive material.

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The silver halide photographic emulsion of the present invention can provide a silver halide photographic light-sensitive material having high sensitivity and excellent graininess.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-5-113617 (JP, A) JP-A-5-165164 (JP, A) JP-A-5-204071 (JP, A) JP-A-4- 125629 (JP, A) JP-A-4-305644 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 1/08-1/09

Claims (3)

(57) [Claims] 1. A silver halide emulsion containing a metal complex having at least one luminate ligand. 2. The silver halide emulsion according to claim 1, wherein the metal complex is a six-coordinate complex. 3. The silver halide emulsion according to claim 1, wherein the silver halide is silver bromide or silver iodobromide.