JPH05346632A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To provide a photographic emulsion which gives silver halide photographic sensitive material having high sensitivity and excellent graininess by incorporating a metal complex having fulminate ligands. CONSTITUTION:A six-ligand metal complex expressed by formula [M(CNO)m L6-m]<n> having at least one fulminate ligand is incorporated into the silver halide emulsion. In formula, M is a metal atom or ion, (m) is the number of fulminate ligands, L is a ligand except for fulminate ligand, (n) is the valence of the metal complex. The number of fulminate ligands is preferably >=4, and more preferably, 6, which means that the all ligands are fulminate ligands. M is preferably Fe, Co, Ru, Rh, Re, Os, Ir, or Au, and the silver halide is preferably silver bromide or silver iodide. The add amt. of this metal complex is preferably between >=10<-8>mol and <=10<-1>mol per one mol of silver halide particle.

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 specifically to a silver halide photographic light-sensitive material having improved sensitivity and graininess and excellent adaptability to environment. It relates to a silver halide photographic emulsion used for the material.

[0002]

2. Description of the Related Art The spread of photography equipment such as cameras has been increasing in recent years.
Opportunities for taking photographs using silver halide photographic light-sensitive materials are also increasing. Along with this, demands for higher sensitivity and higher image quality of silver halide photographic light-sensitive materials are also increasing.

[0003] One of the dominant factors for high sensitivity and high image quality of silver halide photographic light-sensitive materials is silver halide grains, and silver halide grains aiming at higher sensitivity and higher image quality Particle development has traditionally been pursued in the industry.

However, as is generally done, as the grain size of silver halide grains is made smaller in order to improve image quality, the sensitivity tends to decrease, and both high sensitivity and high image quality are satisfied. There was a limit.

A technique for improving the sensitivity / size ratio per silver halide grain is being researched in order to further improve the sensitivity and the image quality. One of them is tabular silver halide grain. The technology used is JP-A-58-111935
No. 58, No. 58-111936, No. 58-111937, No. 58
-ll3927 and 59-99433. Comparing these tabular silver halide grains with so-called normal crystal silver halide grains such as octahedron and hexahedron,
When the volume of silver halide grains is the same, tabular silver halide grains have a larger surface area, and therefore, more sensitizing dye can be adsorbed on the surface of silver halide grains, and higher sensitivity can be achieved. There is.

Further, JP-A-63-92942 discloses a technique of providing a core having a high silver iodide content inside a tabular silver halide grain, and JP-A-63-151618 discloses a hexagonal tabular halide. The technique of using silver grains, JP-A-63-163451 discloses a technique of using tabular silver halide grains having a ratio of grain thickness to the longest distance between twin planes of 5 or more. , 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 photoelectrons and holes in the silver halide grains are doped by doping the silver halide grains with metal ions. Techniques for improving movement and modifying its photographic properties are known.

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

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic emulsion which provides a silver halide photographic light-sensitive material having high sensitivity and excellent graininess.

[0010]

It has been found that the objects of the present invention are achieved by a silver halide photographic emulsion of substructure. That is, (1) A silver halide emulsion containing a metal complex having at least one fluminate ligand. (2) The silver halide emulsion according to the above (1), wherein the metal complex is a hexacoordinated complex. (3) The silver halide emulsion as described in (1) or (2) above, wherein the silver halide is silver bromide or silver iodobromide.

The present invention will be described in more detail below.

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

[0013]

[Chemical 1] Refers to a metal atom or ion coordinated with a C atom.

The hexacoordinate metal complex having at least one fluminate ligand is represented by the following formula [2].

[0015]

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

As the number of fluminate ligands,
It is preferably 4 or more, and particularly preferably 6, that is, all the ligands are fluminate ligands.

As M, any compound capable of forming a complex of the formula [2] may be used, but Fe, Co, Ru, Rh, Re and O may be used.
s, Ir, and Au are preferable.

Specific examples of the complex compound having a fluminate ligand satisfying the requirements of the present invention are shown below, but the complex compound is not necessarily limited thereto.

[0019]

[Chemical 3] The silver halide grain contained in the silver halide emulsion of the present invention may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal form such as a cube, octahedron or tetradecahedron,
It may have an irregular crystal shape such as a sphere or a plate. In these grains, any ratio of {100} plane to {111} plane can be used. Further, those having a composite form of these crystal forms may be used, and grains of various crystal forms may be mixed, but preferably twinned silver halide grains having two opposing parallel twin planes are used. Be done.

A twin is a silver halide crystal having one or more twin planes in one grain, and the morphology of twins is classified by Klein and Moiser in the article Photographiesche Correspondents. (Photographishe Korresponden
z] Volume 99, page 99, volume 100, page 57.

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

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

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

As the monodisperse silver halide emulsion, the weight of silver halide contained in the grain size range of ± 20% around the average grain size r is 60% or more of the total weight of silver halide grains. A certain amount is preferable, more preferably 70% or more, 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 becomes maximum (three significant digits, minimum). Digits are rounded to 4).

The term "particle size" as used herein means the diameter of a projected image of a silver halide grain converted into a circular image having the same area.

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

Particularly preferred highly monodisperse emulsions of the present invention are

[0030]

[Equation 1] When the breadth of distribution is defined by, it is 20% or less, more preferably 15% or less.

The average particle size and standard deviation are obtained from the particle size ri defined above.

In the present invention, when silver iodobromide is used as the silver halide, the content of the silver iodide is 0.1 mol% or more as an average silver iodide content of the entire silver halide grains.
It is preferably 5 mol% or less, more preferably 5 mol% or more and 12 mol% or less, and particularly preferably 6 mol%.
It is above 10 mol.

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

The core / shell type particles are particles composed of a core that serves as a core and a shell that coats the core, and the shell is formed of one or more layers. It is preferable that the core and the shell have different silver iodide contents, and it is particularly preferable that the core and the shell are formed with the highest silver iodide content.

The silver iodide content of the above core is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 25 mol% or more. The silver iodide content of the outermost shell of the shells, that is, the shell which usually forms the outermost surface layer is preferably 5 mol% or less, more preferably 0 to 2 mol%. The ratio of the core is preferably 2 to 60% of the volume of the whole particle, more preferably 5 to 50%.

The silver halide grains contained in the silver halide photographic emulsion of the present invention are prepared by preliminarily containing an aqueous solution containing a protective colloid and seed grains in a reaction vessel and, if necessary, silver ions, halogen ions or silver halide fine grains. Is supplied to grow seed crystals. 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,
It may be 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 tetradecahedron, or an irregular crystal such as a sphere or a plate. It may have a shape. In these particles,
Any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.
It is preferable to use the monodisperse spherical seed particles described in Japanese Patent No. 178.

As the means for forming the 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,
The double jet method, the triple jet method and the like can be used in any combination. Further, a method of controlling pAg and pH in the liquid phase in which silver halide is produced according to 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 the acidic method, the neutral method and the ammonia method.

In the production of the silver halide photographic emulsion of the present invention, the halide ion and the silver ion may be mixed at the same time, or while either one is present, the other may be mixed. Alternatively, halide ions and silver ions may be grown successively or simultaneously while controlling the pH and pΛg in the mixing vessel while considering the critical growth rate of silver halide crystals. The conversion method may be used at any step of silver halide formation to change the silver halide composition of the grains. 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 or thiourea can be present.

The silver halide grains contained in the silver halide photographic emulsion of the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salt is formed in the process of forming and / or growing the grain. Contained), rhodium salt (including complex salt) and iron salt (including complex salt), and at least one metal ion is added to the inside of the particle and / or
Alternatively, these metal elements can be contained on the grain surface, and reduction sensitizing nuclei can be imparted to the inside of the grain and / or the grain surface by placing in a suitable reducing atmosphere.

In the silver halide photographic emulsion of the present invention, unnecessary soluble salts may be removed after the completion of the growth of silver halide grains, or may remain contained. When removing the salts, Research Disclosure (Re
search disclosure (hereinafter abbreviated as RD)) 17643, Item 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 generally used in the art in which an additive is added to the silver halide photographic emulsion can be applied. For example, these compounds can be dissolved in a suitable organic solvent represented by alcohols or water in advance and added. Furthermore, a dispersion method described as a method for dispersing a spectral sensitizing dye in the specification of Japanese Patent Application No. 4-714 can be used. That is, it is possible to add the metal complex of the present invention in an amount exceeding the solubility and mechanically disperse it into solid fine particles of 1 μm or less in an aqueous system in which an organic solvent and / or a surfactant does not substantially exist.

In the present invention, the metal complex may be added at any time during the production process of the silver halide photographic emulsion, but it is preferably before the growth of silver halide grains is completed.

In the silver halide photographic emulsion of the present invention,
To add a metal complex to the silver halide photographic emulsion, a solution containing the metal complex can be added directly to the silver halide photographic emulsion, and when it is added during the growth of silver halide grains, a halide can be added. 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 grains. Further, the addition of the solution containing the metal complex may be carried out instantaneously,
Alternatively, it may be added continuously using an arbitrary function.

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

Conditions other than those mentioned above in the production of the silver halide photographic emulsion according to the present invention are described in JP-A-61-6643.
No. 61, No. 14-14630, No. 61-112142, No. 62-157.
No. 024, No. 62-18556, No. 63-92942, No. 63-1
The optimum conditions can be selected with reference to known methods such as 51618, 63-l63451, 63-220238, and 63-311244.

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

When a color photographic light-sensitive material is constituted by using the silver halide photographic emulsion of the present invention, the silver halide emulsion which has been physically ripened, chemically ripened and spectrally sensitized is used. Additives used in such processes are Research Disclosure No.17643, No.l8716 and N.
o.308119 (hereinafter referred to as RDl7643, RDl8716 and RD3081
(Abbreviated as 19)). Table 1 shows the locations.

[0051]

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

[0052]

[Table 2] Further, various couplers can be used in the case of forming a color photographic light-sensitive material using the silver halide photographic emulsion of the present invention. Specific examples thereof are RDl7643 and RD308119 below.
It is described in. Table 3 shows the related description.

[0053]

[Table 3] Additives used when constructing 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 is used.
The supports described on page RD18716 pages 647-8 and RD308119 page 1009, section XVII can be used.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can be provided with auxiliary layers such as a filter layer and an intermediate layer described in the above-mentioned RD308119 VII-K.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention has various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above-mentioned RD308119 VII-K. You can

The silver halide photographic emulsion of the present invention is a color negative film for general use or movies, a color reversal film for slides or televisions, color paper,
It can be preferably applied to various color photographic light-sensitive materials represented by color positive films and color reversal papers.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is described above in RD1764328-29, RD187616.
It can be developed by the usual method described on page 15 and RD308119 XIX.

[0059]

The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. 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 in Japanese Patent Application No. 2-408178. .. (Solution J) Ocein gelatin 80 g Potassium bromide 47.4 g Polyisopropylene-polyethyleneoxy-disuccinate sodium salt-10% methanol solution 2.0 ml Water 8.0 liters (Solution K) Silver nitrate l.2 kg Water 1.6 liters ( Solution L) Ocein gelatin 32.2 g Potassium bromide 840 g Water 1.6 liters (solution M) Ammonia water 470 ml Solution K and solution L were added to the solution J that was vigorously stirred at 40 ° C for 11 minutes by the double jet method. Nucleation was performed. During this period, pBr was kept at 1.60.

Then, over 12 minutes, the temperature is lowered to 30 ° C.,
It was aged for another 18 minutes. Furthermore, the solution M was added over 1 minute, followed by aging for 5 minutes. K during aging
The Br concentration was 0.07 mol / liter and the ammonia concentration was 0.63 mol / liter.

After completion of aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. When the seed emulsion grains were observed with an electron microscope, they 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) Ocein gelatin 208.2 g Distilled water 4.0 liter Polyisopropylene-polyethyleneoxy-disuccinic acid ester sodium salt-10% methanol solution 1.5 ml 28 wt% ammonia solution 528.0 ml 56 wt% acetic acid solution 795.0 ml Distilled water Make 5390.0 ml. (Solution B) 3.5N ammoniacal silver nitrate aqueous solution (however, the pH was 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 The following is a method for preparing 0.844 mol of a fine grain emulsion composed of silver iodide grains (average grain size: 0.05 μm).

6.0% by weight containing 0.06 mol of potassium iodide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added to 5000 ml of the gelatin solution of (2) over 10 minutes. PH during particle formation
Was controlled to 2.0 with nitric acid and the temperature was controlled to 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. (Solution E) Fine grain emulsion comprising silver iodobromide grains (average grain size 0.04 μm) containing 1 mol% of silver iodide, prepared in the same manner as the silver iodide fine grain emulsion described in Solution D.
2.20 mol However, the temperature during fine particle formation was controlled at 30 ° C. (Solution F) 1.75N potassium bromide aqueous solution Necessary amount (Solution G) 56% by weight acetic acid aqueous solution Necessary amount (Solution H) Seed emulsion (Em-1) 0.341 mol To 70 ° C in the reaction vessel (Solution A) After (Solution H) was added, (Solution B), (Solution C) and (Solution D) were added by the simultaneous mixing method over 163 minutes, followed by (Solution E) over 12 minutes. And added at a constant rate independently.

Here, the addition rates of (Solution B) and (Solution C) were changed in a function-like manner with respect to time so as to be commensurate with 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 cause polydispersion due to 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 the silver iodide content (mol%) shown in Table 4 is formed, a multiple structure is formed. A core / shell type silver halide emulsion having the above 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 pAg and pH were measured by a conventional method using a silver sulfide electrode and a glass electrode.

After grain growth, desalting treatment was carried out by a conventional method, and then gelatin was added and redispersed, and the pH was adjusted to 5.8 at 40 ° C.
0 and pAg were adjusted to 8.06.

When the silver halide grains contained in the obtained silver halide emulsion were observed with a scanning electron microscope, it 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 the preparation of Emulsion Em-2, except that Solution H was added and then Solution M-1 described below was added.
3 was prepared. (Solution Ml) K ₄ [Fe (CN) ₆ ] .3H ₂ O 0.5 wt% Solution 75.1cc Preparation of Silver Halide Emulsion (Em-4) In the preparation of Emulsion Em-2, after adding Solution H An emulsion Φm-4 of the present invention was prepared in the same manner except that the following solution M-2 was added. (Solution M-2) K ₄ [Fe (CNO) ₆ ] 0.5 wt% Solution 82.6cc Preparation of Silver Halide Emulsion (Em-5) In the preparation of Emulsion Em-2, Solution C was adjusted to have Fe ion concentration of 9 Emulsion Em-5 was prepared in the same manner except that the solution (Solution C-2) to which the solution M-1 was added so as to have a concentration of × 10 ^-4 N was used instead of the solution C. Preparation of Silver Halide Emulsion (Em-6) Emulsion Em-6 of the present invention in the same manner except that Solution M-2 was used instead of Solution M-1 in the preparation of Emulsion Em-5.
Was prepared.

Sensitizing dyes SD-A and SD-B shown below were added to each of the silver halide emulsions Em-2 to Em-6 at a temperature of 55 ° C. in an amount of 1.4 × 10 ^-4 mol and 1.4 mol per mol of silver, respectively.
After spectral sensitization by simultaneously adding and adsorbing ^{x10 -4} mol and then optimally chemical sensitizing with sodium thiosulfate and chloroauric acid, emulsions Em-2S, Em-3S,
Em-4S, Em-5S, and Em-6S were created.

Next, magenta couplers M-A, M-B,
After adding M-C, 2-hydroxy-
Samples 1 to 4 were prepared by uniformly adding an appropriate amount of 4,6-dichlorotriazine sodium, coating each emulsion on an undercoated triacetate cellulose support so that the coating silver amount was 2.0 g / m ² , and drying. Got 5.

[0072]

[Chemical 4] Each of these samples was subjected to wedge exposure (1/100 second exposure) by a normal method using green light, and color development was performed according to the following color processing steps, and photographic performances were comparatively evaluated. The results are shown in Table 5.
Shown in.

The sensitivities in Table 5 are shown as relative sensitivities when the sensitivity of Sample 1 (comparative) is 100. The relative sensitivity is the relative value of the reciprocal of the received light amount that gives the fog density +0.1.

Treatment process Treatment temperature 38 ° C. Treatment time Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry each The composition of the processing liquid used in the processing step is as follows. <Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 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 1000 ml, and adjust to pH 10.6 with sodium hydroxide. <Bleach> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0g Add water to make 1000 ml, and adjust to pH 6.0 with ammonia water. To do. <Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1000 ml, and the pH is adjusted to 6.0 with acetic acid. <Stabilizer> Formalin (37% aqueous solution) 1.5 ml Conidax (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 light-sensitive materials 101 to 105 were prepared. Em
-2S to Em-6S are used for the high-sensitivity green sensitive layer and are designated as emulsion A in the following formulation.

Unless otherwise specified, the addition amount is the number of grams per 1 m ² . Also, silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes are shown in the number of moles per mole of silver. First layer; antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (Oil-1) 0.16 Gelatin 1.23 Second layer: Intermediate layer Compound (SC-1) 0.15 High boiling point solvent (Oil-) 2) 0.17 Gelatin 1.27 Third 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 Sensitizing 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 point solvent (Oil) -1) 0.53 Gelatin 1.30 4th layer; Medium-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm) (silver iodide content 8.0 m %) 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 grain 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 point solvent (Oil-1) 0.14 Gelatin 0.91 6th layer; Intermediate layer Compound (SC-1) 0.09 High boiling point 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) (iodination) 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 point 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 point solvent (Oil-2) 0.50 Gelatin 1.00 9th 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 point solvent (Oil-1) 0.27 High boiling point 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 point 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 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 point solvent (Oil-2) 0.046 Gelatin 0.80 Fifteenth 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 point solvent (Oil-1) 0.07 High boiling point 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 Lubricant (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1, dispersion aid Su-2, viscosity modifier, hardener H -1, H-2, stabilizer ST-1, antifoggant AF-1, weight average molecular weight: 1
Two AF-2 of 0,000 and 1,100,000 and a preservative DI-
1 was added. The amount of DI-1 added was 9.4 mg / m ² .

The structures of the compounds used in the above samples are shown below.

[0078]

[Chemical 5]

[0079]

[Chemical 6]

[0080]

[Chemical 7]

[0081]

[Chemical 8]

[0082]

[Chemical 9]

[0083]

[Chemical 10]

[0084]

[Chemical 11]

[0085]

[Chemical formula 12]

Sensitometry exposure (exposure time 1/100 sec) was given to these samples with white light, and the samples were processed in the following processing steps to evaluate the sensitivity. Processing step (38 ℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry Used in each processing step The composition of the treatment liquid is as follows. <Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 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 Water is added to make 1 liter, and the pH is adjusted to 10.0. <Bleach> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0g Add water to make 1 liter and adjust the pH to 6.0 with ammonia water. To do. <Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid. <Stabilizer> Formalin (37% aqueous solution) 1.5 ml Conidax (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 relative value of the reciprocal of the received light amount that gives the fog density +0.1, and is shown as a value with the green sensitivity of the sample 101 being 100.

[0089]

[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 light-sensitive material.

[0090]

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

Claims (3)

[Claims] 1. A silver halide emulsion containing a metal complex having at least one fluminate ligand. 2. The silver halide emulsion according to claim 1, wherein the metal complex is a hexacoordinated complex. 3. The silver halide emulsion according to claim 1, wherein the silver halide is silver bromide or silver iodobromide.