JPH04219747A - Silver halide emulsion and silver halide photosensitive material containing the same - Google Patents

Abstract

PURPOSE:To provide a silver halide photosensitive material excellent in chemical-sensitization characteristic, spectral-sensitization characteristic and developing characteristic and therefore improved in sensitivity and image quality. CONSTITUTION:A silver halide photosensitive material using silver halide particles contained in at least one silver halide emulsion layer is formed into a multilayer structure consisting of more than three silver halide phases comprising an inner core, a middle core and an outermost core of different silver iodide contents, with the average silver iodide content of the inner core and the average silver iodide content of the outermost core both being not less than 6mol%, and the average silver iodide content of the silver halide phase of the middle core adjacent the outermost core being higher than the average silver iodide content of the outermost core by 1.0mol% or more.

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 material, and more particularly to a high-speed negative photographic material using an emulsion comprising silver halide grains having a novel structure.

0002

[Background of the Invention] Silver halide used in high-sensitivity silver halide photographic light-sensitive materials (hereinafter simply referred to as light-sensitive materials) is silver iodobromide, a composite of silver bromide, silver iodide, silver chloride, etc. Microcrystalline particles such as silver bromide. Conventionally, in order to achieve high sensitivity and high image quality, improvements or optimizations have been made to the structure of silver halide grains, the distribution of halogen composition, etc. from the viewpoint of improving or controlling light absorption efficiency, latent image formation efficiency, and developability. Efforts have been made to

Regarding light absorption efficiency, silver chloride, silver bromide,
It is known that the development activity increases in the order of silver iodide, but conversely, the development activity decreases in the above order. Furthermore, in the case of spectral sensitization using sensitizing dyes, it is common knowledge in the photographic field that most of the commonly used methine dyes have stronger adsorption in the order of silver chloride, silver bromide, and silver iodide.

Accordingly, based on these findings, photographic emulsions comprising silver halide grains having various structures suitable for practical use have been proposed.

[0005] As a technique for increasing light absorption without impairing development activity, various types of core/silver halide grains are used in which the silver iodide content in the silver halide grains is high in the interior (core part) and low in the outermost layer (shell part). Shell-type grain emulsions are disclosed in Japanese Patent Publication Nos. 43-13162, 57-154232, 59-177535,
It is disclosed in No. 60-138538, No. 60-143331, No. 61-88253, No. 61-112142, etc. Incidentally, the silver iodide content in the outermost layer of the silver halide grains described in the Examples of these patents is all 5 mol % or less.

However, these core/shell type particles
When a photosensitive material is stored under high humidity conditions, the sensitizing dye is easily desorbed, and the inherent desensitization caused by the sensitizing dye is large. Silver halide grains used in photosensitive materials were not necessarily satisfactory.

As a technique for improving the disadvantages of core/shell type grains, various types of core/shell type grain emulsions have been proposed in which the silver iodide content in the outermost layer of silver halide grains is higher than conventional ones. For example, JP-A-63-106745 discloses that silver halide grains have a silver iodobromide phase with a silver iodide molar fraction of 10 to 40 mol%, and this phase has a lower silver iodide content. Silver halide grains are disclosed in which the surface of the grains contains 5 mol % or more of silver iodide. In JP-A-1-183646, the outermost layer (shell part) has a high silver iodide content, and the innermost layer has a phase (core part) with a silver iodide content less than the outermost layer by 6 mol% or more. Silver halide grains in which the outermost layer and the inner phase are clearly separated are disclosed. Furthermore, silver halide grains having a similar structure are described in JP-A-1-284848. Further, JP-A No. 1-279237 discloses a layer structure having a layer structure separated by a plane substantially parallel to two opposing major planes, and in which the average iodine content of the outermost layer is higher than that of the entire silver halide grain. at least 1 mol% of the average iodine content of
Tabular silver halide grains having a high density of 100% or more have been disclosed. JP-A No. 2-12142 discloses a metal having an inner core made of silver chloroiodobromide, silver iodobromide, or silver bromide, and an outermost shell having a higher silver iodide content than the inner core, The outermost shell has a higher silver iodide content than the inner shell, the outermost shell has a silver iodide content of 6 mol% or more, and an intermediate layer is provided between the inner core and the outermost shell. Silver halide grains having at least one shell and an average aspect ratio of less than 8:1 are disclosed.

As an improvement technique that is somewhat different from the above-mentioned silver halide grains, Japanese Patent Laid-Open No. 1-273033 discloses a method in which the crystal surface of the silver halide grains has a coplanar index when viewed from the direction in which the projected area is maximum. and there are two or more parts having different halogen compositions, at least one of the parts has a silver iodide content of 5 to 45 mol%, and at least an intermediate shell is provided between the inner core and the outermost shell. One silver halide grain is mentioned.

Incidentally, the photosensitivity of silver halide grains subjected to spectral sensitization is not determined only by the efficiency of spectral sensitization, but also largely depends on the photosensitivity of the silver halide grains themselves. Therefore, in order to increase the latter efficiency, a chemical sensitization treatment (chemical sensitization) called chemical ripening in the art is generally performed. The silver halide grains disclosed in the above-mentioned patent group are recognized to have improved effects in terms of adsorption of spectral sensitizing dyes, spectral sensitization efficiency, etc.
The high silver iodide content of the outermost layer makes it difficult to perform chemical sensitization, which tends to reduce chemical sensitization efficiency, and also has the disadvantage of deteriorating development activity, making it difficult to achieve high sensitivity now and in the future. It has become clear that this is far from meeting the level of demand.

0010

OBJECTS OF THE INVENTION An object of the present invention is to provide a silver halide photographic material which has excellent chemical sensitization, spectral sensitization and developability, and therefore has improved sensitivity and image quality.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a result of extensive research, the present inventors have discovered that the above objects of the present invention can be achieved by a silver halide emulsion having the following structure and a silver halide photographic material containing the same.

That is, (1) the silver halide grain has a laminated structure consisting of three or more silver halide phases, an inner core, an intermediate shell, and an outermost shell, each having a different silver iodide content, and the inner core The average silver iodide content and the average silver iodide content of the outermost shell are both 6 mol% or more, and the average silver iodide content of the silver halide phase of the intermediate shell adjacent to the outermost shell is the highest. A silver halide emulsion comprising silver halide grains having an average silver iodide content higher than the average silver iodide content of the outer core by 1.0 mol% or more.

(2) The silver halide phase of at least some or all of the inner core, intermediate shell, and outermost shell of the silver halide grains described in (1) is formed in the presence of an aqueous protective colloid solution. A silver halide emulsion is a silver halide grain grown by supplying an emulsion consisting of fine-sized silver halide grains.

(3) At least one layer of (
A silver halide photographic material having an emulsion layer containing the silver halide emulsion described in item 1).

(4) At least one layer of (
2) A silver halide photographic material having an emulsion layer containing the silver halide emulsion described in item 2).

The characteristics of the silver halide emulsion according to the present invention are summarized below. (1) The average silver iodide content of the outermost shell is 6
The content is mol% or more, preferably 6 to 30 mol%, particularly preferably 6 to 15 mol%.

(2) The intermediate shell may have a laminated structure of a plurality of silver halide phases, but the average silver iodide content of the silver halide phase adjacent to the outermost shell of the intermediate shell is the highest. It is 1.0 mol% or more higher than the average silver iodide content of the outer shell. The preferred silver iodide content of the adjacent phase is 6 to 40 mol%, particularly preferably 7 to 35 mol%.

(3) The average silver iodide content of the inner core inside the intermediate shell is 6 mol % or more. Preferably 7-40
mol%, particularly preferred content is 10 to 40 mol%
It is.

(4) The silver iodide content of the entire grain is the volume ratio of the entire grain of the inner core, middle shell, and outermost shell, and the silver iodide content of the inner core, middle shell, and outermost shell. It can be adjusted by the rate. The preferred silver iodide content in the grains as a whole is 5 to 20 mol%, particularly preferably 7 to 17 mol%.

(5) The volume ratio of the outermost shell to the entire particle is preferably 50% or less.

(6) Even if the inner core, intermediate shell and outermost shell have a clearly distinguishable layered structure, the silver iodide content changes continuously and the interlayers are unclear. It may be .

Table 1 shows examples of preferred halogen composition structures of silver halide grains according to the present invention.

[0023]

[Table 1]

Analysis of the structure and halogen composition of the silver halide grains of the present invention having a structure in which three or more phases with different silver iodide contents are laminated is performed using XPS (X-ray Photo
This can be carried out using surface analysis (electron spectroscopy), analytical electron microscopy, X-ray diffraction, or the like.

The XPS surface analysis method is effective for analyzing the silver iodide content near the surface of silver halide grains, and in the silver halide grains of the present invention, it is effective for measuring the silver iodide content in the outermost shell. Particularly effective. Measurement by this XPS method is usually performed as follows.

Prior to measurement by the XPS method, the emulsion is pretreated as follows. First, a pronase solution is added to the emulsion and stirred at 40° C. for 1 hour to decompose gelatin. Next, the emulsion particles are sedimented by centrifugation, and after removing the supernatant, an aqueous pronase solution is added and gelatin decomposition is performed again under the above conditions. The sample is centrifuged again, the supernatant liquid is removed, and then distilled water is added to redisperse the emulsion particles in the distilled water, centrifuged, and the supernatant liquid is removed. After repeating this water washing operation three times, the emulsion particles are redispersed in ethanol. This is applied thinly onto a mirror-polished silicon wafer to use as a measurement sample.

For measurement by the XPS method, for example, an ESCA/SAM560 model manufactured by PHI is used as an apparatus, and the excitation X-ray is Mg-Kα ray, the X-ray source voltage is 15 KV, the X-ray source current is 40 mA, and the pass energy is 50 eV. Do it with conditions.

[0028] To determine the surface halide composition, Ag3d
, Br3d, I3d3/2 electrons are detected. The composition ratio is calculated by the relative sensitivity coefficient method using the integrated intensity of each peak. By using 5.10, 0.81, and 4.592 as Ag3d, Br3d, and I3d3/2 relative sensitivity coefficients, respectively, the composition ratio is given in atomic percent.

Analytical electron microscopy is effective for observing the laminated structure within silver halide grains and analyzing the silver iodide content of each phase.
(1990), pages 125 onwards, ultrathin sections of silver halide grains were observed using an electron microscope and EDS (Ene
rgy Dispersive Spectromet
er) There is a method to analyze it.

In this method, silver halide particles are dispersed in an electron microscope observation grid equipped with an energy dispersive X-ray analyzer, and the magnification is adjusted by cooling with liquid nitrogen so that one particle falls into the field of view of the CRT. Set and hold Ag for a certain period of time.
The intensities of Lα and ILα rays are integrated.

The silver iodide content can be calculated by preparing the intensity ratio of ILα/AgLα in advance and using a calibration curve.

The X-ray diffraction method is described by T. H. T by James
he theory of the photography
As stated on page 3 of phic Process, this is a method that applies the fact that there is a certain relationship between the lattice constant and the halogen composition.
By analyzing the diffraction profile of the ) plane or the (420) plane, the silver iodide content of each phase forming a layered structure within the grain and the volume ratio of each phase can be determined. For more detailed analysis, high-resolution measurements such as the Guinier X-ray diffraction method and the X-ray diffraction method using monochromatic synchrotron radiation can be used.

Various characteristic X-rays can be used as the X-ray source. Among them, Cukα that targets Cu
Lines are the most widely used.

Silver iodobromide has a rock salt structure, and the (420) diffraction line with the CuKα line has a relatively strong signal intensity observed at 71 to 74 degrees 2θ and a high angle, so the resolution is good and the crystal structure can be determined. It is ideal for investigating.

In measuring the X-ray diffraction of photographic emulsion,
It is necessary to remove gelatin, mix a standard sample such as silicon, and measure using the powder method.

Regarding the measurement method, see Basic Analytical Chemistry Course 2.
4 "X-ray analysis" (Kyoritsu Shuppan) etc. can be used as a reference.

[0037] Since it is not possible to distinguish between the presence of phases with different halogen compositions in the grains or the coexistence of silver halide grains with different halogen compositions with the X-ray diffraction method, EPMA (Electron Probe
The uniformity of the silver iodide content among silver halide grains must be evaluated using a MicroAnalyzer method or the like. Specific methods include those described by Ayato, Okuda et al. in the 47th Analytical Chemistry Conference Abstracts (1986).

In this EPMA method, a sample is prepared in which the emulsion grains are well dispersed so that they do not come into contact with each other, and then an electron beam is irradiated. Elemental analysis of extremely small parts can be performed by X-ray analysis using electron beam excitation. Therefore, by this method, the halogen composition of each grain can be determined by determining the characteristic X-ray intensities of silver and iodine emitted from each grain.

In the emulsion of the present invention, it is preferable that the silver iodide content among the grains is more uniform. When the average silver iodide content of individual silver halide grains is measured by the EPMA method, it is preferable that the relative standard deviation of the measured values is 20% or less. More preferably it is 15% or less, particularly preferably 12% or less.

The relative standard deviation here is, for example, the value obtained by dividing the standard deviation of the silver iodide content when measuring the silver iodide content of at least 100 emulsions by the average silver iodide content at that time. ×100.

The silver halide emulsion having a layered structure of the present invention can be prepared by selecting and combining various methods known in the art.

First, to prepare the inner core, methods such as acidic method, neutral method, ammonia method, etc., and methods for reacting soluble silver salt and soluble halogen salt include one-sided mixing method, simultaneous mixing method,
You can choose from a combination of them. As a method for supplying halogen and silver when the inner core is a mixed crystal, it is preferable to add silver halide grains having the same halogen composition as the inner core to be formed.

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a controlled double jet method can also be used. As another type of simultaneous mixing method, a triple jet method in which different soluble halogen salts are added independently (for example, soluble silver salt and soluble iodine salt) can also be used.

It is also possible to use the method disclosed in Japanese Patent Publication No. 48-36890, in which the addition rate is accelerated over time, or the method described in US Pat. No. 4,242,445, in which the addition concentration is increased over time. These two methods are effective for improving the monodispersity of particles.

[0045] The inner core is prepared using ammonia, rhodan salt,
It is possible to carry out the process in the presence of a silver halide solvent such as thioureas, thioethers, and amines, or it can also be carried out without a solvent.

The inner core is preferably monodisperse. Therefore, pBr during nucleation is preferably 1.70 or more, particularly preferably 2.00 to 4.00. Further, pBr during growth is preferably 1.20 or more, particularly preferably 1.40 to 3.50. Further, it is preferable to use a monodisperse seed emulsion for growth and formation.

[0047] Also, various gelatins or synthetic polymers can be used as a dispersion medium during internal nucleation.

[0048] The temperature during particle formation may be any temperature as long as the dispersion medium can be dissolved, but it is preferably 40 to 80°C.

[0049] Formation of the intermediate shell and the outermost shell can be performed successively after the completion of the internal nucleation. Alternatively, after forming the internal nucleus, it can be washed with water by a conventional flocculation method, gelatin is added thereto, and the mixture is used as a seed crystal. In this case, the size of the final particles can be easily controlled by adjusting the amount of seed crystals.

The final pH and pAg of the seed crystal are such that the pH is 7.0 or less and the pAg is 8.0 or less at 40° C. in order to avoid introducing electron traps such as Ag2 nuclei to the surface of the internal core as much as possible.
It is preferable to adjust the pH value to 0 or higher, particularly preferably a pH value of 6.0 or lower and a pAg of 8.6 or higher. Next, a method for forming the intermediate shell and the outermost shell will be described.

In order to make the silver iodide distribution uniform in the silver iodobromide layer having a high silver iodide content, the silver iodobromide layer is formed using ammonia, rhodan salt, thioureas, thioethers, amines, etc. It is preferable to use a silver halide solvent in which the solubility of silver halide is high. Therefore, when using Rodan salt, it is necessary to use pBr2.3 or more at 75°C, preferably pBr2.5 or more, and pBr2
．． 8 or more is particularly preferred. Further, even when ammonia, thiourea or thioether is used, it is preferable to form the middle shell and the outermost shell at a pBr of 2.3 or more.

[0052] The temperature during the formation of the intermediate shell and the outermost shell is preferably high in order to increase the solubility of silver halide. Preferably 40°C or higher, particularly preferably 60°C
That's all.

There are various methods for supplying iodine, bromine, chlorine and silver necessary for forming the intermediate shell and the outermost shell, similar to those shown in the internal nucleation method. Particularly preferred is the method of adding as

As a method for supplying halogen and silver when preparing a silver halide emulsion having a layered structure according to the present invention, a method for adding silver halide fine grains will be explained below.

The grain size of the fine-sized silver halide grains to be supplied is preferably 0.1 μm or less, more preferably 0.05 μm or less, still more preferably 0.03 μm or less. The particle size of the silver halide fine particles is, for example, an enlargement ratio of 3
It is determined by actually measuring the particle diameter in an electron micrograph of ~60,000 times, or the area when projected.

The fine grain emulsion may be prepared (a) prior to the formation of photosensitive silver halide grains, or (b) may be prepared and supplied in parallel.

In the case of (b), since the stagnation time from generation of nuclei of silver halide fine grains to addition is short, it is possible to suppress an increase in the size of fine grains due to Ostwald ripening between fine grains. In particular, a mode in which fine silver halide particles are prepared and continuously supplied is effective and preferable in shortening the above-mentioned stagnation time.

There are no particular restrictions on the silver halide composition and the number of types of silver halide fine grains to be supplied. (2) Two or more types of silver halide fine grains having different silver halide compositions may be used at a mixing ratio depending on the desired halide composition of the silver halide grains. , may be supplied simultaneously or separately.

[0059] Above (a) and (b), (1) and (2)
Any combination of these methods may be used, but when the fine particle supply method follows (a), it is preferable to combine (2) in terms of production efficiency. It is important to further reduce the particle size of the fine particles to be supplied in order to improve the solubility of the fine particles. By using a gelling-resistant dispersion medium as a protective colloid during the preparation of fine particles, it is possible to lower the preparation temperature of the fine particles, and the size of the fine particles can be further reduced.

[0060] Here, the "gelling-resistant dispersion medium" as used in the present invention is a dispersion medium that is difficult to gel (coagulate) compared to general photographic gelatin (average molecular weight of 70,000 or more). , and has protective colloidal properties for silver halide grains (
A) low molecular weight gelatin; (B) synthetic polymer compounds and natural polymer compounds other than gelatin. More specifically, (A) refers to those with an average molecular weight of 50,000 or less,
Preferably 500 to 30000, more preferably 100
Gelatin from 0 to 20,000.

[0061] The low molecular weight gelatin used in the present invention is
It can usually be produced as follows. Gelatin, which is generally used for photography and has an average molecular weight of about 100,000, is dissolved in water, and a gelatin-degrading enzyme is added to enzymatically decompose the gelatin molecules. This method is described in R. J. Cox: Photo
graphic Geratin II, Academy
c Press, London, 1976, 233~
The descriptions on pages 251 and 335 to 346 can be referred to. In this case, since the bond position that the enzyme decomposes is fixed, it is possible to obtain a low molecular weight with a relatively narrow molecular weight distribution, and the molecular weight can be adjusted by adjusting the enzymatic decomposition time (the longer the time, the lower the molecular weight) Therefore, it is preferable. others,
There are methods of hydrolyzing by heating in a low pH (1 to 3) or high pH (10 to 12) atmosphere, and methods of cutting crosslinks by ultrasonic irradiation. Note that, in addition to commonly used gelatin, modified gelatin or the like may be used for production. The molecular weight distribution and average molecular weight of gelatin can be determined by common methods such as gel filtration chromatography (GPC), coasolvation, and the like.

(B): Synthetic polymer compound a. Polyacrylamide Polymer Homopolymer of Acrylamide, U.S. Pat. No. 2,541,
Copolymer of polyacrylamide and imidized polyacrylamide shown in No. 474, West German Patent No. 1,202,
Copolymers of acrylamide and methacrylamide shown in No. 132, partially aminated acrylamide polymers shown in U.S. Pat. Substituted acrylamide polymers shown in British Patent No. 3,746,548 and British Patent No. 788,343.

b. Amino polymer U.S. Pat. No. 3,345,346, No. 3,706,504
No. 4,350,759, West German Patent No. 2,138,8
Aminopolymer shown in No. 72, British Patent No. 1,413
, 125, U.S. Pat. No. 3,425,836, and U.S. Pat. No. 3,511,8.
A polymer having an amino group and a carboxyl group as shown in No. 18, a polymer shown in US Pat. No. 3,832,185, etc.

c. Polymers having thioether groups U.S. Pat. No. 3,615,624, U.S. Pat. No. 3,860,428,
Polymers having a thioether group as shown in No. 3,706,564.

d. Polyvinyl alcohol Homopolymers of vinyl alcohol, organic acid monoesters of polyvinyl alcohol as shown in U.S. Pat. No. 3,000,741, maleic acid esters as shown in U.S. Pat. No. 3,236,653, U.S. Pat. No. 3,479,189 Copolymers of polyvinyl alcohol, polyhibinylpyrrolidone, etc. shown in

e. Acrylic Acid Polymer Acrylic Acid Homopolymer, U.S. Pat. No. 3,832,185
No. 3,852,073, an acrylic acid ester polymer having an amino group, U.S. Pat. No. 4,131,
471, cyanoalkyl acrylic esters shown in U.S. Pat. No. 4,120,727, and the like.

f. Polymers with Hydroxyquinoline U.S. Pat. Nos. 4,030,929 and 4,152,161
Polymers having hydroxyquinoline as shown in No.

g. Cellulose, starch British Patent No. 542,704, British Patent No. 551,659, U.S. Patent No. 2,127,573, British Patent No. 2,311,086,
Cellulose or starch derivatives shown in No. 2,322,085.

h. Acetal U.S. Patent Nos. 2,358,836 and 3,003,879
No. 2,828,204, British Patent No. 771,155
Polyvinyl acetals shown in No.

i. Polyvinylpyrrolidone A homopolymer of vinylpyrrolidone, a copolymer of acrolein and pyrrolidone shown in French Patent No. 2,031,396, etc.

j. polystine polystyrylamine polymers shown in US Pat. No. 4,315,071, halogenated styrene polymers shown in US Pat. No. 3,861,918, etc.

k. Ternary Polymer Special Publication No. 43-7561, German Patent No. 2,012,095
No. 2,012,970, ternary copolymers of acrylamide, acrylic acid, and vinylimidazole.

l. Other vinyl polymers having azaindene groups as shown in JP-A No. 59-8604, polyalkylene oxide derivatives as shown in U.S. Pat. No. 2,976,150, U.S. Pat.
022,623, U.S. Pat. No. 4,294,920, U.S. Pat. No. 4,089
, 688, U.S. Pat. No. 2,484,
No. 456, polyvinylpyridine, U.S. Pat.
Vinyl polymers having imidazole groups as shown in No. 520,857, vinyl polymers having triazole groups as shown in Japanese Patent Publication No. 60-658, Journal of the Photographic Society of Japan 29
Polyvinyl-2-methylimidazole and acrylamide-imidazole copolymer shown in Vol. 1, p. 18, dextran, water-soluble polyalkylene aminotriazoles shown in Zeitoschrift Bissenschaftliche Fotograf, Vol. 45, p. 43 (1950) .

In the present invention, when a gelling-resistant dispersion medium is used as a protective colloidal dispersion medium during the preparation of a fine grain emulsion for supply, after the crystal growth of silver halide grains is completed,
It is preferable to perform a water washing treatment using a coagulation method or the like to remove part or all of the gelling-resistant dispersion medium contained in the emulsion. One of the preferred embodiments of the present invention is to remove other dissolved substances, mainly salts, contained in the emulsion at the same time as removing the gelling-resistant dispersion medium.

The crystal habit of the silver halide grains of the present invention is not particularly limited.

The silver halide grains of the present invention are cubic, 8
The particles may be normal crystals such as a hedron, dodecahedron, dodecahedron, or icosahedron, twin crystals such as a tabular shape or other shapes, or irregularly shaped particles such as a potato shape. It may also be a mixture of these.

In the case of tabular twin crystals, it is preferable that the ratio of the projected area equivalent circular diameter of the grain to the grain thickness is 1 to 20, which accounts for 60% or more of the projected area, and more preferably 1.2 to 8. It is preferably less than .0, particularly preferably 1.5 or more and less than 5.0.

The silver halide emulsion of the present invention is preferably a monodisperse silver halide emulsion.

In the present invention, a monodisperse silver halide emulsion is defined as a monodisperse silver halide emulsion in which the weight of silver halide contained within a grain size range of ±20% around the average grain size dm is 70% of the total silver halide weight.
% or more, preferably 80% or more, more preferably 90% or more.

Here, the average particle diameter dm is defined as the particle diameter di when the product ni×di3 of the frequency ni of particles having the particle diameter di and di3 is maximum. (3 significant digits, minimum digit rounded to 4 to 5) The particle size referred to here is the diameter when the projected image of the particle is converted into a circular image with the same area.

The particle size can be obtained, for example, by magnifying the particles 10,000 to 50,000 times using an electron microscope, projecting the particles, and actually measuring the particle diameter or area at the time of projection on the print. (The number of grains to be measured is indiscriminately 1000 or more.) A particularly preferred highly monodispersed emulsion of the present invention is (particle size standard deviation/average grain size) x 100 = width of distribution (%
) is 20% or less, more preferably 15% or less.

[0082] The particle size measurement method here follows the measurement method described above, and the average particle size is the arithmetic mean.

Average grain size=Σdini/Σni The average grain size of the silver halide emulsion of the present invention is 0.1 μm to 1 μm.
It is preferably 0.0 μm, more preferably 0.0 μm.
2 μm to 5.0 μm, particularly preferably 0.3 μm to 3.0 μm.
It is 0 μm.

Monodisperse normal crystal emulsions are described, for example, in JP-A Nos. 59-177535, 60-138538, and 5
No. 9-52238, No. 60-143331, No. 60-
No. 35726, No. 60-258536 and No. 61-1
It can be manufactured by referring to the method disclosed in Japanese Patent No. 4636 and the like. A monodisperse twinned emulsion is
For example, it can be obtained by referring to the method for growing a spherical seed emulsion disclosed in JP-A-61-14636. Preparation of the emulsion of the present invention or other emulsions used in combination as necessary when constituting the light-sensitive material obtained using the emulsion of the present invention (hereinafter sometimes referred to as the light-sensitive material of the present invention) A substance other than gelatin that has adsorption properties to silver halide grains may be added at any time (including at the time of preparing the seed emulsion). Such adsorbing substances are useful, for example, compounds used in the art as sensitizing dyes, antifoggants or stabilizers, or heavy metal ions. Specific examples of the above-mentioned adsorptive substances are described in JP-A-62-7040.

Among the adsorbent substances, it is preferable to add at least one of an antifoggant and a stabilizer at the time of preparing the seed emulsion in order to reduce fog and improve stability over time of the emulsion. .

Among the antifoggants and stabilizers, heterocyclic mercapto compounds and/or azaindene compounds are particularly preferred. Specific examples of more preferred heterocyclic mercapto compounds and azaindene compounds are disclosed in JP-A No. 63-41848.
Details are given in the issue.

The amount of the heterocyclic mercapto compound and azaindene compound added is not limited, but is preferably 1 x 10-5 to 3 x 10-2 mol, more preferably 5 x 10-5 per mol of silver halide. ~3×10 −3 mol. This amount is appropriately selected depending on the manufacturing conditions of the silver halide grains, the average grain size of the silver halide grains, and the type of the above-mentioned compound.

[0088] The finished emulsion having predetermined grain conditions can be desalted by a known method after silver halide grain formation. As a method for desalting, the agglomerated gelatin agents described in JP-A-63-243936 and JP-A-1-185549 may be used, or the Nudel water washing method, which is performed by gelatinizing gelatin, may be used. good. Furthermore, a coagulation method using an inorganic salt consisting of a polyvalent anion, such as sodium sulfide, an anionic surfactant, or an anionic polymer (such as polystyrene sulfonic acid) may be used. Generally, the silver halide emulsion desalted as described above is redispersed in gelatin to prepare an emulsion.

In the light-sensitive material of the present invention, other silver halide grains may be used in combination with the silver halide grains of the present invention.

The silver halide grains used in combination may have any grain size distribution. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or a monodisperse emulsion with a narrow grain size distribution may be used.

The light-sensitive material of the present invention is formed by containing the silver halide grains of the present invention in at least one of the silver halide emulsion layers constituting it. Silver halide particles other than silver particles may be contained.

In this case, it is preferable that the emulsion containing the silver halide grains of the present invention accounts for 20% by weight or more, more preferably 40% by weight or more.

Further, when the light-sensitive material of the present invention has two or more silver halide emulsion layers, an emulsion layer consisting only of silver halide grains other than the silver halide grains of the present invention may be present.

In this case, the emulsion of the present invention preferably accounts for 10% by weight or more of the silver halide emulsion used in all the light-sensitive layers constituting the light-sensitive material, and more preferably accounts for 20% by weight or more. preferable.

[0095] The silver halide grains of the present invention were
Research Disclosure
Spectral sensitization can be carried out using the spectral sensitizers described in the volume and page shown below of ``Sure (hereinafter abbreviated as RD)'', or spectral sensitization can be carried out in combination with other sensitizers.

[0096]No. 17643 (P.23-24), N
o. 18716 (P.648-649), No. 308
119 (P.996, IV-A, B, C, D: H, I,
Section J) The effects obtained in the present invention become remarkable by spectrally sensitizing the silver halide grains of the present invention. In particular, when trimethine and/or monomethine cyanine dyes are used alone or in combination with other spectral sensitizers,
The effects of the present invention become more significant. Further, silver halide grains other than the silver halide grains of the present invention used in the light-sensitive material of the present invention, if necessary, can be optically sensitized to a desired wavelength range. In that case, there are no particular restrictions on the optical sensitization method, and for example, cyanine dyes such as zeromethine dyes, monomethine dyes, dimethine dyes, trimethine dyes, cyanine dyes such as merocyanine dyes, or optical sensitizers such as merocyanine dyes are used alone. Alternatively, they can be used together to optically sensitize. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself has no spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization. These technologies are described in US patents 2 and 6.
No. 88,545, No. 2,912,329, No. 3,39
No. 7,060, No. 3,615,635, No. 3,628
, No. 964, British Patent No. 1,195,302, No. 1, 2
No. 42,588, No. 1,293,862, West German patent (
OLS) No. 2,030,326, No. 2,121,780
No., Special Publication No. 43-14030, RD Volume 176, 1764
3 (issued December 1978), page 23, section IV, etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

In the present invention, various commonly used chemical sensitization treatments can be performed. Chalcogen sensitizers used in chemical sensitization include sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, but for use in photography, sulfur sensitizers,
Selenium sensitizers are preferred. As the sulfur sensitizer, known ones can be used. Examples include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. Patent No. 1,574,9
No. 44, No. 2,410,689, No. 2,278,94
No. 7, No. 2,728,668, No. 3,501,313
No. 3,656,955, West German Publication (OLS)
Sulfur sensitizers described in JP-A No. 1,422,869, JP-A No. 56-24937, JP-A No. 55-45016, etc. can also be used. The amount of sulfur sensitizer added may be sufficient to effectively increase the sensitivity of the emulsion. This appropriate amount is p
It varies over a considerable range under various conditions such as H, temperature, and silver halide grain size, but as a guide,
from about 10-7 moles to about 10-1 per mole of silver halide
A molar level is preferable.

Examples of selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids and esters, selenophosphates, diethylselenide, Selenides such as diethyldiselenide can be used, and specific examples thereof include U.S. Pat. Nos. 1,574,944 and 1,602,592;
It is described in No. 1,623,499.

The amount added varies over a wide range as with the sulfur sensitizer, but as a guide, it is preferably about 10@-7 mol to as low as 10@-1 mol per mol of silver halide.

In the present invention, the gold sensitizer may have a valence of +1 or +3, and various types of gold compounds can be used. Typical examples include chloroauric acids, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate,
Examples include tetracyanoauric acid, ammonium aurothiocyanate, pyridyltrichlorogold, and gold-dimethylrhodanine complex.

[0101] The amount of gold sensitizer added varies depending on various conditions, but as a guide, it is about 10-
A range of 7 mol to 10 −1 mol is preferred.

The gold sensitizer may be added at the same time as the sulfur or selenium sensitizer, during or after the sulfur or selenium sensitization step.

[0103] Sulfur sensitization or selenium sensitization in the present invention,
The pAg of the emulsion subjected to gold sensitization is 5.0 to 10.0, p
H is preferably in the range of 5.0 to 9.0.

[0104] The chemical sensitization method in the present invention can also be used in combination with a sensitization method using other noble metals, such as metal salts such as platinum, palladium, iridium, and rhodium, or complex salts thereof.

Furthermore, complexes of Rh, Pd, Ir, Pt and the like are effective as compounds that release gold ions from gold-gelatinate and promote adsorption of gold ions onto silver halide grains.

Specific compounds include (NH4)2[P
tCl4], (NH4)2[PdCl4], K3[Ir
Br6], (NH4)3[RhCl6]12H2O, etc., but particularly preferred is ammonium tetrachloropalladate(II) (NH4)2[PdCl4]
It is. The amount added is 10 to 10 in stoichiometric ratio (mole ratio) to the gold sensitizer.
A range of 100 times is preferred.

[0107] The addition time may be at the beginning of the chemical sensitization treatment, during its progress, or after the end of the chemical sensitization treatment, but preferably during the chemical sensitization treatment, and particularly preferably at the same time as the addition of the gold sensitizer. Or before or after that.

In the present invention, reduction sensitization can also be used in combination. There are no particular restrictions on the reducing agent, but
Known examples include stannous chloride, thiourea dioxide, hydrazine derivatives, and polyamines.

Reduction sensitization is carried out during the growth of silver halide grains, but it is preferably carried out after completion of chalcogen sensitization, gold sensitization and noble metal sensitization.

Furthermore, in the chemical sensitization treatment, a compound having a nitrogen-containing heterocycle, particularly preferably an azaindene ring, may be coexisting.

The amount of the nitrogen-containing heterocyclic compound added varies over a wide range depending on the emulsion grain size, composition, chemical sensitization conditions, etc., but it is preferable to add from a monomolecular layer to 10 molecules on the surface of the silver halide grains. It is preferable to add it in an amount sufficient to form a layer. The amount added can also be adjusted by controlling the adsorption equilibrium state by changing the pH and/or temperature during sensitization. Alternatively, two or more of the above compounds may be added to the emulsion so that the total amount falls within the above range.

The compound can be added to the emulsion by dissolving it in a suitable solvent (for example, water or aqueous alkaline solution) that does not have a harmful effect on the photographic emulsion, and then adding it as a solution. The timing of addition is preferably before or at the same time as adding a sulfur sensitizer or a selenium sensitizer for chemical sensitization. The gold sensitizer may be added during or at the end of sulfur or selenium sensitization.

Furthermore, these silver halide grains can be optically sensitized to a desired wavelength range using a sensitizing dye.

[0114] In carrying out the present invention, various additives can be used in the photosensitive material. For example, known photographic additives that can be used are exemplified in RD. The relevant entries are shown in the table below.

[Item] RD308119 page RD17643 RD1
8716 and item page
page color clouding prevention agent 1002
Section VII-I 25
650 Dye image stabilizer 1002
Section VII-J 25 increase white
Agent 998 V
24 UV absorber 1
003 VIIIC, XIIIC Sections 25-26 Light absorbing agent 1003 VIII
25-26 light scattering
Disturber 1003 VIII Filter dye 1003 VIII
25-26 binder
1003 IX
26 651 Static inhibitor 1006 XIII
27 650 Hardener 1004 X
26 65
1 Plasticizer 1006 X
II 27
650 lubricant
1006 XII 2
7 650 activator/coating aid
1005 XI
26-27 650 mat
Agent 1007 XVI development
Agent 1011 Item XXB (Contained in Photosensitive Material) Various couplers can be used in the present invention, and specific examples thereof are illustrated in the above RD. The relevant entries are shown in the table below.

[Item] [RD 3
08119 page] [RD 17643] Yellow coupler 1001 VII-
Section D VII Section C to G magenta coupler
1001 Section VII-D
VII C-G term cyan coupler
1001 VII-D Section VI
I C~G colored coupler
1002 VII-G term VII G term DIR coupler 10
01 VII-F section VII F section BAR
coupler 1002
VII-F Other useful residues
1001 VII-F Section Emitting Coupler Alkali Soluble Coupler 1001 VI
Section I-E The additive used in the present invention is RD308119
It can be added by the dispersion method described in XIV.

[0117] In the present invention, the above-mentioned RD17643
28 pages, RD18716647-8 and RD3081
The supports described in No. 19, XVII can be used.

The photosensitive material of the present invention includes the above-mentioned RD308.
Auxiliary layers such as filter layers and intermediate layers as described in Section 119VII-K can be provided.

The photosensitive material of the present invention is the above-mentioned RD30811.
Various layer configurations such as forward layer, reverse layer, and unit configuration described in Section 9VII-K can be adopted.

The present invention can be preferably applied to various color photosensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. can. Moreover, it can be used for various purposes such as black and white general use, X-ray use, infrared use, micro use, silver dye bleaching method, diffusion transfer method, and reversal use.

The photosensitive material of the present invention can be developed by commonly used known methods. For example, RD1
7643, pages 28-29, RD18716, page 615, and RD308119XIX.

[0122]

[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

Example-1 <Preparation of octahedral silver iodobromide emulsion EM-1> Average grain size 0
．． 33 μm monodispersed silver iodobromide grains (silver iodide content 2 mo
An octahedral silver iodobromide emulsion was prepared by the double-jet method using 1%) as a seed crystal.

[0124] Solution <G-1> was heated to a temperature of 75°C and a pAg of 7.
8. While keeping the pH at 7.0 and stirring well, 144.4 ml of a seed emulsion equivalent to 0.34 mol was added.

(Formation of internal nucleus) After that, <H-1> and <
S-1> was added at an accelerated flow rate (end flow rate 3.6 times the initial flow rate) over a period of 110 minutes while maintaining a flow ratio of 1:1.

(Formation of outermost shell) Next, pAg10.1
, while maintaining the pH at 6.0, <H-2> and <S-2> were heated at an accelerated flow rate of 1:1 (the flow rate at the end was 5.2 times the initial flow rate) for 60 minutes. and added. After the particle formation, the particles were washed with water by a conventional flocculation method, and the pH and pAg were adjusted to 5.8 and 8.06, respectively, at 40°C.

The obtained emulsion had an average grain size of 1.0 μm, a distribution width of 12.6%, and an average silver iodide content of 10.0 mol.
% of octahedral silver iodobromide grains. This emulsion is designated as EM-1.

<<Preparation of octahedral silver iodobromide emulsion EM-2>> An octahedral silver iodobromide emulsion was prepared in the same manner as emulsion EM-1. However, <H-3> and <S-3> were used instead of <H-2> and <S-2> as solutions to be supplied during the formation of the intermediate shell.

(Formation of outermost shell) Subsequently, <H-4> and <S-4> were supplied.

<<Preparation of octahedral silver iodobromide emulsion EM-3>> Emulsion 3 was prepared according to the method for preparing emulsion 3 described in Example 1 of JP-A-2-12142. Average particle size 0.99μ
m octahedral grains, average silver iodide content is 5.4 mol%
Met. <<Preparation of octahedral silver iodobromide emulsion EM-4>> The inner core and intermediate shell were prepared in the same manner as EM-1 and EM-2. However, the silver iodide content is 20 mol% and 10 mol%, respectively.
Potassium bromide, potassium iodide,
The amount of silver nitrate was adjusted.

Subsequently, while maintaining the pAg at 10.1 and the pH at 6.0, silver iodobromide fine particles (MC-3) were supplied in an amount equivalent to 1.77 mol to form an outermost shell.

The obtained emulsion had an average grain size of 1.0 μm, a distribution width of 12.8%, and an average silver iodide content of 9.5 mo
It was 1%.

<<Preparation of octahedral silver iodobromide emulsion EM-5>> Monodispersed silver iodobromide grains (silver iodide content 2 mol%) with an average grain size of 0.33 μm were used as seed crystals, and fine-sized halogen An octahedral silver iodobromide emulsion was prepared by supplying silver iodobromide grains.

[0134] Solution <G-1> was heated to a temperature of 75°C and a pAg of 7.
8. While keeping the pH at 7.0 and stirring well, 144.4 ml of a seed emulsion equivalent to 0.34 mol was added.

(Formation of internal core) Then, silver bromide fine particles (
MC-1) and silver iodide (MC-2) were added at an accelerated flow rate (the final flow rate was 3.6 times the initial flow rate) over a period of 27 minutes while maintaining a molar ratio of 70:30. . The fine particles consumed during this period were equivalent to the total of (MC-1) and (MC-2), 0.543 mol. (Formation of intermediate shell) Subsequently, pAg10.1, pH6.0
While maintaining the molar ratio of silver bromide fine grain emulsion (MC-1) and silver iodide fine grain emulsion (MC-2) at 89:11, the flow rate was accelerated (the flow rate at the end was 5.5% of the initial flow rate). 2
The mixture was added over a period of 65 minutes. The fine particles consumed during this period are 5.3 by adding up (MC-1) and (MC-2).
It was equivalent to 0 mol.

(Formation of outermost shell) Furthermore, under the same conditions as when forming the intermediate shell, silver bromide fine grains (MC-1) and silver iodide fine grain emulsion (MC-2) were mixed at a molar ratio of 92:8. While maintaining, 2.
An amount equivalent to 65 mol was supplied over 40 minutes to form the outermost shell.

[0137] After particle formation, washing with water was performed by a conventional flocculation method, and the pH and pAg were adjusted at 40°C.
were adjusted to 5.8 and 8.06, respectively.

The obtained emulsion had an average grain size of 0.99 μm,
Width of distribution is 10.9%, silver iodide content 9.6 mol%
It was a monodisperse emulsion containing octahedral silver iodobromide grains. This emulsion is designated as EM-5.

<<Preparation of octahedral silver iodobromide emulsion EM-6>> After forming an internal core in the same manner as EM-5, iodobromide with a silver iodide content of 3 mol% and 16 mol% is used as an intermediate shell. A silver phase was formed in a layered manner in this order on the inner core. For this purpose, MC-1 and MC-2 should be used in a molar ratio of 90:3, equivalent to 1.77 moles, and in a molar ratio of 84:16, equivalent to 4.42 moles.
Molar equivalents were used. Furthermore, in the same manner as EM-5, M
Keeping C-1 and MC-2 at a molar ratio of 90:9, 0.88
The amount equivalent to 3 moles was supplied to form the outermost shell.

The obtained emulsion had an average grain size of 1.0 μm, a distribution width of 12.2%, and a silver iodide content of 11.4 mol%.
It was a monodisperse emulsion containing octahedral silver bromide grains. This emulsion is designated as EM-6. <Preparation of octahedral silver iodobromide emulsion EM-7> After forming up to the intermediate shell in the same manner as EM-4, silver bromide fine grains (M
C-1) and silver iodide fine particles (MC-2) were supplied in a total amount equivalent to 1.77 mol while maintaining a molar ratio of 92:8 to form the outermost shell.

The obtained emulsion had an average grain size of 1.0 μm, a distribution width of 12.9%, and an average silver iodide content of 10.4 μm.
It was ol%.

<G-1> Ossein gelatin (average molecular weight 100,000)
100.0g Compound-I

25.0ml 28% ammonia aqueous solution
440.0ml 56% acetic acid aqueous solution

With 660.0ml water

5000.0ml Compound-I: 10% aqueous ethanol solution of polyisopropylene polyethyleneoxy disuccinate sodium salt <H-1> Ossein gelatin
82.4g
potassium bromide
192.4g potassium iodide
115.0g with water

1030.5ml <S-1> Silver nitrate
392.4
g with water
1030
．． 5ml <H-2> Ossein gelatin
302.1g
potassium bromide
713.4g potassium iodide
30.8g with water

3776.8ml <S-2> Silver nitrate
1050.
0g with water
377
6.8ml <H-3> Ossein gelatin
278.5g
potassium bromide
611.6g potassium iodide
26.4g with water

3482.4ml <S-3> Silver nitrate
900.0
g with water
3482
．． 4ml <H-4> Ossein gelatin
23.6g
potassium bromide
105.1g potassium iodide
14.7g with water

294.4ml <S-4> Silver nitrate
150.1
g with water
294
．． 4ml <Preparation of silver bromide fine grain emulsion MC-1> 9.6% by weight gelatin solution containing 0.05 mol of potassium bromide 50
00ml, 10.6 mol of silver nitrate and 1 potassium bromide
2500 ml of each aqueous solution containing 0.6 mol were added over 28 minutes at an accelerated flow rate (end flow rate 5 times the initial flow rate). The temperature during microparticle formation was kept at 35°C.

[0143] When the obtained silver bromide fine particles were confirmed with an electron micrograph at a magnification of 60,000 times, the average particle size was 0.032.
It was μm.

<<Preparation of silver iodide fine grain emulsion MC-2>>
5000 ml of a 9.6% by weight gelatin solution containing 0.05 mol of potassium iodide, 2500 ml each of an aqueous solution containing 10.6 mol of silver nitrate and 10.6 mol of potassium iodide.
was added over 28 minutes at an accelerated flow rate (end flow rate 5 times the initial flow rate). The temperature during particle formation is 35
It was kept at ℃.

[0145] When the obtained silver bromide fine particles were confirmed by an electron micrograph at a magnification of 60,000 times, the average particle size was 0.027.
It was μm.

<<Preparation of silver iodobromide fine grain emulsion MC-3>> 10.6 mol of silver nitrate was added to 5000 ml of a 9.6% by weight gelatin solution containing 0.05 mol of potassium bromide,
Potassium bromide 8.48 mol and potassium iodide 0.426 mol
2500 ml of each molar aqueous solution was added over 28 minutes at an accelerated flow rate (end flow rate 5 times the initial flow rate). The temperature during microparticle formation was kept at 35°C.

[0147] When the obtained silver bromide fine particles were confirmed with an electron micrograph at a magnification of 60,000 times, the average particle size was 0.030.
It was μm.

The above emulsions EM-1 to EM-7 are summarized in Table 2.

[0149]

[Table 2]

The values in the table are prescription silver iodide contents. When a silver iodobromide layer is formed in the presence of silver halide, the silver iodide ratio of the high iodide layer may decrease slightly due to conversion with the lower iodide layer. It does not deviate from this. Further, the total average silver iodide content is calculated by taking into account the seed emulsion.

<<Preparation of silver halide photographic material sample>>
Each of the emulsions EM-1 to EM-7 was optimally subjected to gold/sulfur sensitization and spectral sensitization, and these emulsions were used to form each layer with the composition shown below on a triacetyl cellulose film support. were sequentially formed from the support side to prepare a sample of a multilayer color photographic material.

[0152] In all the examples below, the amount added in the silver halide photographic material is expressed in grams per m2 unless otherwise specified. In addition, silver halide and colloidal silver are
Shown in terms of silver. The sensitizing dye is expressed in moles per mole of silver in the same layer.

The composition of multilayer color photographic material Sample-1 is as follows.

Sample-1 (comparison) 1st layer: antihalation layer (HC) black colloidal silver
0.2
UV absorber (UV-1)
0.23 High boiling point solvent (O
il-1)
0.18 Gelatin

1.4 Second layer: First intermediate layer (IL-1) Gelatin
1.3 Third layer: Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (EM-L)
1.0 Sensitizing dye (
SD-1)
1.8×10-5 Sensitizing dye (SD-2)
2.8×
10-4 Sensitizing dye (SD-3)
3.0×10-4
Cyan coupler (C-1)
0.70 Colored cyan coupler (CC-1)
0.066 DIR compound (D-1)
0.03
DIR compound (D-3)
0.01 High boiling point solvent (Oil-1)
0.64 Gelatin

1.2 Fourth layer: Medium red-sensitive emulsion layer (RM) Silver iodobromide emulsion (EM-M)
0.8 Sensitizing dye (
SD-1)
2.1×10-5 sensitizing dye (SD-2)
1.9×
10-4 Sensitizing dye (SD-3)
1.9×10-4
Cyan coupler (C-1)
0.28 Colored cyan coupler (CC-1)
0.027 DIR compound (D-1)
0.
01 High boiling point solvent (Oil-1)
0.26
gelatin
0.6 5th layer: High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (EM-1)
1.70 Sensitizing dye (SD-1)
1.9×10-5 Sensitizing dye (SD-2)
1.7
×10-4 Sensitizing dye (SD-3)
1.7×10-4
Cyan coupler (C-1)
0.05 Cyan coupler (C-2)
0.10 Colored cyan coupler (CC-1) 0.02
DIR compound (D-1)
0.025 High boiling point solvent (Oil-1)
0.17 Gelatin

1.2 6th layer: 2nd intermediate layer (
IL-2) Gelatin
0.8 7th layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (EM-L)
1.1 Sensitizing dye (
SD-4)
6.8×10-5 Sensitizing dye (SD-5)
6.2×
10-4 Magenta coupler (M-1)
0.54
Magenta coupler (M-2)
0.19 Colored magenta coupler (CM-1) 0
．． 06 DIR compound (D-2)
0.017
DIR compound (D-3)
0.01 High boiling point solvent (Oil-2)
0.81 Gelatin

1.8 8th layer: medium-sensitivity green-sensitive emulsion layer (GM) silver iodobromide emulsion (EM-M)
0.7 Sensitizing dye (
SD-6)
1.9×10-4 Sensitizing dye (SD-7)
1.2×
10-4 Sensitizing dye (SD-8)
1.5×10-5
Magenta coupler (M-1)
0.07 Magenta coupler (M-2)
0.03 Colored magenta coupler (CM-1) 0.04
DIR compound (D-2)
0.018 High boiling point solvent (Oil-2)
0.30 Gelatin

0.8 9th layer: High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (EM-1)
1.7 Sensitizing dye (SD-4)
2.1×10-5 sensitizing dye (S
D-6)
1.2×10-4 sensitizing dye (SD-7)
1.0×1
0-4 Sensitizing dye (SD-8)
3.4×10-6
Magenta coupler (M-1)
0.09 Magenta coupler (M-3)
0.04 Colored magenta coupler (CM
─1) 0.04 High boiling point solvent (Oil─2)
0.31 Gelatin

1.2 10th layer: Yellow filter layer (YC) Yellow colloidal silver

0.05 Color stain prevention agent (SC-1)
0.1 High boiling point solvent (Oil-2)
0.13 Gelatin

0.7 Formalin scavenger (HS-1) 0.0
9 Formalin scavenger (HS-2)
0.07 11th layer: Low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (EM-L)
0.5
Silver iodobromide emulsion (EM-M)
0.5 Sensitizing dye (SD
-9)
5.2×10-4 Sensitizing dye (SD-10)
1.9
×10-5 Yellow coupler (Y-1)
0.65
Yellow coupler (Y─2)
0.24 DIR compound
(D-1)
0.03 High boiling point solvent (Oi
l-2) 0
．． 18 Gelatin
1
．． 3 Formalin scavenger (HS-1)
0.08 12th layer: High-speed blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (EM-1
) 1.
0 Sensitizing dye (SD-9)
1.8×10-4
Sensitizing dye (SD-10)
7.9×10-5 Yellow coupler (Y-1)
0.15 Yellow coupler (Y-2
) 0.05
High boiling point solvent (Oil-2)
0.074
gelatin
1.3 Formalin scavenger (HS-1)
0.05 Formalin scavenger (HS
-2) 0.12 13th layer: 1st protective layer (Pro-1) Fine grain silver iodobromide emulsion (average grain size 0.08 μm
AgI 1 mol%) 0.4 Ultraviolet absorber (UV─
1) 0
．． 07 Ultraviolet absorber (UV-2)
0.10 High boiling point solvent (Oil-1)
0.07 High boiling point solvent
(Oil-3)
0.07 Formalin scavenger (H
S-1) 0.13
Formalin scavenger (HS-2)
0.37 Gelatin

1.3 14th layer: 2nd protective layer (Pro─
2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethyl methacrylate (average particle size 3 μm) 0.02
Sliding agent (WAX-1)
0.04 Gelatin
0.6 In addition to the above composition, coating aid Su-1, dispersion aid S
u-2, viscosity modifier, hardener H-1, H-2, stabilizer S
T-1, antifoggant AF-1, weight average molecular weight 10
,000 and 1,100,000 of AF-2 were added.

Emulsions EM-L and EM-M used in the above samples
is as shown below.

Each emulsion was optimally gold-sulfur sensitized.

(Emulsion composition) Emulsion name Average grain size
Average silver iodide crystal habit
(μm) Content (mol%) EM-L 0.
47 8.0
8-14 sided EM-M
0.82 8.0
octahedron

[0158]

[Chemical formula 1]

[0159]

[Case 2]

[0160]

[Chemical formula 3]

[0161]

[C4]

[0162]

[C5]

[0163]

[C6]

[0164]

[C7]

[0165]

[Chemical formula 8]

[0166]

[Chemical formula 9]

Next, in place of the silver iodobromide emulsion EM-1 in the fifth, ninth and twelfth layers in Sample-1, Table-2
Samples 2 to 7 were prepared using emulsions EM-2 to EM-7 as shown in FIG.

[0168] Each of the samples thus prepared was subjected to wedge exposure using white light, and then subjected to the following development treatment.

[0169] The composition of the treatment liquid used in each step is shown below.

<Color developer> 4-amino-3-methyl-N-ethyl-N-(β-
Hydroxyethyl) Aniline/sulfate

4.75g anhydrous sodium sulfite
4.2
5g Hydroxylamine 1/2 sulfate
2.0g anhydrous potassium carbonate
37.5g Sodium Bromide

1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide
1.0g Add water to make 1 liter (pH=10.1) <Bleach solution> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide
150.0g glacial acetic acid

Add 10.0 g of water to make 1 liter, and adjust the pH to 6.0 using aqueous ammonia.

<Fixer> Ammonium thiosulfate
175.0g Anhydrous sodium sulfite
8.5g Sodium metasulfite
Add 2.3 g water to make 1 liter, and adjust the pH to 6.0 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution)
1.5ml Konidax (manufactured by Konica Corporation)
Add 7.5 ml water to make 1 liter.

Immediately after the sample was prepared, relative fog and relative sensitivity were measured for each sample using red light (R), green light (G), and blue light (B). The measurement results are shown in Table-3.

[0174] Relative fog is a relative value of the minimum density (Dmin), and Dmin in each R, G, B measurement of sample-1.
The values are each expressed as 100.

[0175] Relative sensitivity is the relative value of the reciprocal of the exposure amount that gives a density of Dmin + 0.15, and
, B The sensitivity in each measurement is expressed as a value of 100.

[0176] Also, each sample was heated at a temperature of 50°C and a humidity of 80%RH.
After being stored for 5 days under high temperature and high humidity conditions, it was similarly exposed to a wedge of white light and developed.
, B relative sensitivity (the sensitivity of sample-1 immediately after preparation is set as 100) is also shown.

[0177]

[Table 3]

Example 2 Preparation of hexagonal tabular silver iodobromide emulsion EM-A Crystal growth was achieved by continuously supplying fine grains from a mixer for preparing fine grains installed near the reaction vessel. A hexagonal tabular silver iodobromide emulsion was prepared.

[0179] The solution <G-10> in the reaction vessel was heated to a temperature of 75
C, pAg 8.4, and pH 6.5, and a seed emulsion consisting of tabular silver iodobromide grains was added in an amount equivalent to 0.34 mol while stirring well.

(Formation of internal high iodine phase - core phase) <H-
A1>, <S-A1>, and <G-A1> were continuously added under pressure into the mixer at an accelerated flow rate by a triple jet method. The formed fine grain emulsion was continuously fed into the reaction vessel. During this time, the rotation speed of the stirring blades of the mixer was 400.
0r. p. m. At this time, the temperature was maintained at 15°C.

(Formation of external low iodine phase - shell phase) Subsequently, <H-A2>, <S-A2> and <G-A2> were similarly added to the mixing vessel. The formed fine grain emulsion was continuously fed into the reaction vessel. During this time, the rotation speed of the stirring blade of the mixer was 3500r. p. m. was held.

(Formation of surface phase) Furthermore, <H-A3> and <S
-A3> and <G-A3> were similarly added to the mixing vessel. The formed fine grain emulsion was continuously fed into the reaction vessel.

[0183] The particle size of the fine particles formed in the mixer was confirmed using an electron micrograph at a magnification of 60,000 times, and the average particle size was 0.014 μm.

After particle formation, low molecular weight gelatin was removed and desalted, gelatin (average molecular weight 100,000) was added and redispersed, and the pH and pAg were adjusted to 5.8 and 8.06, respectively, at 40°C. Adjusted to.

The obtained emulsion had an average grain size of 1.37 μm,
It was a monodisperse emulsion consisting of hexagonal tabular silver iodobromide grains with an aspect ratio of 4, a distribution width of 13.2%, and a silver iodide content of 9.3 mol%. This emulsion is designated as EM-A.

<<Hexagonal tabular silver iodobromide emulsion EM-B ~
Preparation of EM-D》Same as emulsion EM-A
Emulsions EM-B to EM-D were prepared. However, the compositions and amounts of the aqueous solutions of halide, silver nitrate, and gelatin added to the mixer are different from those of EM-A.

Emulsion thus obtained EM-A
~ An overview of EM-D is shown in Table-4.

[0188]

[Table 4]

The values in the table are prescription silver iodide contents. However, the total average silver iodide content is a value calculated taking into consideration the seed emulsion portion.

<G-10> Ossein gelatin (average molecular weight 100,000)
120.0g Compound-I

25.0ml 28% ammonia aqueous solution
440.0ml 56% acetic acid aqueous solution

With 660.0ml water

4000.0ml <H-A1> Potassium bromide
178.5g
potassium iodide
83.0g
with water
800.0ml
<S-A1> Silver nitrate
339.7
g with water
800
．． 0ml<G-A1> Low molecular weight gelatin (average molecular weight 10,000)
150.0g with water

1400.0ml <H-A2> Potassium bromide
678.4g
potassium iodide
49.8g
with water
2400.0ml<
S-A2> Silver nitrate
1019.2
g with water
2400
．． 0ml<G-A2> Low molecular weight gelatin
450.0g
with water
4200.0ml<
H-A3> Potassium bromide
56.6g
potassium iodide
2.4g
with water
196.0ml<
S-A3> Silver nitrate
83.2
g with water
196
．． 0ml<G-A3> Low molecular weight gelatin
36.8g
with water
343.0ml (Preparation of silver halide photographic material sample) EM-A to E
Gold/sulfur sensitization and spectral sensitization were optimally applied to each emulsion of M-D, and Sample-A to Sample-D were prepared in the same manner as in Example-1.

Each sample was subjected to exposure, development, and measurement of fog and sensitivity in the same manner as in Example-1. However, among the development processing, color development is 2 minutes 45 seconds and 3 minutes 15 seconds.
Two types of processing time were used: seconds. Color development for 2 minutes and 45 seconds is referred to as Process I, and color development for 3 minutes and 15 seconds is referred to as Process II. In both cases, the processing after color development was carried out in the same manner as in Example-1.

Table 5 shows the measurement results under green light.
Shown below.

[0193]

[Table 5]

[0194] Relative fog is expressed as a value based on the Dmin value of Sample-A in Process II being 100, and relative sensitivity is expressed as a value based on 100 as the sensitivity of Sample-A in Process II.

[0195] Also, results similar to those shown in Table 5 were obtained in measurements using red light and blue light.

As is clear from Tables 3 and 5, the silver halide emulsion according to the present invention and the photographic material using the emulsion have high sensitivity and low fog, and have excellent dye adsorption properties. It also has high spectral sensitization efficiency and excellent storage stability under high temperature and high humidity conditions.

[0197]

Effects of the Invention As described above, the silver halide emulsion of the present invention and the photographic light-sensitive material prepared using the same have increased sensitivity and reduced fog, as well as improved spectral sensitization efficiency and storage stability. Together we can fully achieve it.

Claims (4)

[Claims] Claim 1: A laminated structure consisting of three or more silver halide phases, an inner core, an intermediate shell, and an outermost shell, each having a different silver iodide content, the average silver iodide content of the inner core and the outermost shell having different silver iodide contents. The average silver iodide content of both shells is 6 mol% or more, and the average silver iodide content of the silver halide phase of the intermediate shell adjacent to the outermost shell is the average silver iodide content of the outermost core. 1. A silver halide emulsion comprising silver halide grains that are 1.0 mol % or more higher than that of silver halide. 2. At least some or all of the inner core, intermediate shell, and outermost shell of the silver halide grains according to claim 1 are made of fine particles formed in the presence of an aqueous protective colloid solution. 1. A silver halide emulsion, characterized in that the silver halide grains are grown and formed by supplying an emulsion consisting of silver halide grains of a certain size. 3. A silver halide photographic material comprising at least one emulsion layer containing the silver halide emulsion according to claim 1 on a support. 4. A silver halide photographic material comprising at least one emulsion layer containing the silver halide emulsion according to claim 2 on a support.