JPH11184028A - Silver halide photographic emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic emulsion and the silver halide photographic sensitive material for both realizing enhancement of sensitivity and reduction of fog impossible to be attained by the conventional techniques by creating and allotting suitable sites for chemical intesification and color intesification on the surface of the silver halide grains. SOLUTION: This photographic emulsion comprises a dispersion medium and the silver halide grains containing silver chloride in the uppermost layer and the silver halide proportion in this layer satisfys A1/A2<1.0, where A1 is an average silver iodide content of the silver halide grains in the upper-most layer and A2 is an average silver iodide content of the silver halide grains.

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, and more particularly, to a silver halide photographic emulsion having excellent sensitivity and granularity, and a silver halide photographic material using the same.

[0002]

2. Description of the Related Art Photographic equipment such as cameras has become increasingly popular in recent years, and opportunities for taking photographs using silver halide photographic materials have been increasing. Demands for higher sensitivity and higher image quality are increasing.

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

However, the sensitivity tends to decrease as the size of silver halide grains is reduced to improve image quality, as is generally practiced. To achieve both high sensitivity and high image quality. Had limitations.

Techniques for improving the sensitivity / grain size ratio per silver halide grain have been studied in order to achieve higher sensitivity and higher image quality. As one of them, a technique using tabular silver halide grains is disclosed in JP-A-58-11.
No. 1935, No. 58-111936, No. 58-111
No. 937, No. 58-113927, No. 59-9943
No. 3 and the like. When these tabular silver halide grains are compared with so-called normal silver halide grains such as octahedral, tetrahedral, or hexahedral grains, when the silver halide grains have the same volume, the surface area increases, and thus Many sensitizing dyes can be adsorbed on the silver particle surface, and there is an advantage that the sensitivity can be further increased.

JP-A-6-230491, JP-A-6-235
988, 6-258745, 6-289516
And the like have also studied using tabular silver halide grains having a higher aspect ratio than before.

Further, Japanese Patent Application Laid-Open No. 63-92942 discloses a technique for providing a core having a high silver iodide content inside tabular silver halide grains, and Japanese Patent Application Laid-Open No. 63-163541 discloses a technique for forming a core between twin planes. A technique using tabular silver halide grains having a ratio of grain thickness to long distance of 5 or more is disclosed, and shows effects on sensitivity and graininess, respectively.

Further, Japanese Patent Application Laid-Open No. 63-106746 discloses that
Tabular silver halide grains having a substantially layered structure in a direction parallel to two opposite main planes are disclosed in
No. 279237 has a layered structure separated by a plane substantially parallel to two opposite main planes, and the average silver iodide content of the outermost layer is the average silver iodide of the whole silver halide grains. It describes a technique using tabular silver halide grains at least 1 mol% higher than the content.

Japanese Patent Application Laid-Open No. 3-121445 discloses a silver halide grain composed of an interface layer having parallel twin planes and regions having different iodine contents from each other.
No. 305343 discloses a tabular silver halide grain having a development start point near the vertex.
Silver halide grains having a (0) plane and a (111) plane are disclosed.

[0010] In addition, JP-A-1-183644 describes that
A technique using tabular silver halide grains, characterized in that the silver iodide distribution of silver halide containing silver iodide is completely uniform is disclosed.

Further, there is disclosed a technique for controlling carriers by metal doping, that is, a technique for improving photographic characteristics by mainly including a polyvalent metal oxide in silver halide grains.

JP-A-3-196135 and JP-A-3-189
No. 641 and the like disclose a silver halide emulsion produced in the presence of an oxidizing agent for silver, and the effect on sensitivity and fog when a silver halide photographic material using the same is used.

Further, for example, Japanese Patent Application Laid-Open No. 63-220238
In Japanese Patent Application Laid-Open No. Hei 3-175440, a technique using a silver halide emulsion containing tabular silver halide grains in which the positions of dislocation lines are defined is disclosed in JP-A-3-175440. A technique using a silver halide emulsion containing silver halide grains is disclosed in Japanese Patent Publication No. 3-186.
No. 95 discusses a technique using silver halide grains having a clear core / shell structure, and Japanese Patent Publication No. 3-31245 discusses a technique relating to silver halide grains having a core / shell three-layer structure. It has been studied as a sensitivity enhancement technique.

JP-A-6-11781 and 6-1178
No. 2, No. 6-27564, No. 6-250309, No. 6-250310, No. 6-250311, No. 6-2
Nos. 50313, 6-242527, etc., realize high sensitivity and improved fog / pressure resistance by using an iodide ion releasing compound in forming silver halide grains.

However, these conventional techniques have limitations in achieving both high sensitivity and high image quality, and are insufficient to satisfy recent demands on photosensitive materials. Was rare.

In order to perform more effective chemical sensitization and color sensitization on silver halide grains for improving the photographic performance, more precise photosensitive nucleus sites and halogens on the surface of the silver halide grains than ever before. There is a need to develop technologies that allow for composition control, and previous studies in the industry have not adequately responded to this need.

[0017]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic emulsion and a silver halide photographic light-sensitive material while maintaining the uniformity between silver halide grains and the halogen in the vicinity of the outermost surface of the silver halide grains. More precise control and formation of silver halide composition by removing unnecessary salts during silver halide phase formation in the silver halide phase, eliminating non-uniformity when adding additives, and limiting the growth direction of the silver halide phase. By making it possible to create optimal sites for each of chemical sensitization and color sensitization on the surface of silver halide grains, it is possible to improve sensitivity and fog level that could not be achieved by conventional technology. An object of the present invention is to provide a silver halide photographic emulsion realized and a silver halide photographic material using the silver halide photographic emulsion.

[0018]

The above objects of the present invention have been attained by the following constitutions.

(1) In a silver halide photographic emulsion containing a dispersion medium and silver halide grains, the silver halide grains contain silver chloride in the outermost layer, and silver iodide in the outermost layer of the silver halide grains. When the average of the content is A1, and the average of the silver iodide content of the silver halide grains is A2, A1 / A2 <
A silver halide photographic emulsion, characterized by being 1.0.

(2) In a silver halide photographic emulsion containing a dispersion medium and silver halide grains, the silver halide grains contain silver chloride in the outermost layer, and silver iodide in the outermost layer of the silver halide grains. The content is B1 and the silver iodide content of the subsurface layer is B
2. A silver halide photographic emulsion characterized in that when B2 / B2 <1.0, 50% or more (number) of silver halide grains satisfying B1 / B2 <1.0.

(3) In a silver halide photographic emulsion containing a dispersion medium and silver halide grains, the silver halide grains contain silver chloride in the outermost layer, and silver iodide in the outermost layer of the silver halide grains. A silver halide photographic emulsion characterized in that tabular silver halide grains satisfying I1> I2 are 50% or more (number) when the content is I1 in the main plane portion and I2 in the side surface portion.

(4) In a silver halide photographic emulsion containing a dispersion medium and silver halide grains, the silver halide grains contain silver chloride in the outermost layer, and the silver bromide content ratio of the silver halide grains is controlled by A silver halide photographic emulsion wherein tabular silver halide grains satisfying C1 / C2 <1.0, where C1 is at the fringe portion and C2 is near the apex, is 50% or more (number).

(5) A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion according to any one of the above items 1 to 4 in at least one silver halide emulsion layer on a support. .

Hereinafter, the present invention will be described specifically.
In the present invention, the dispersion medium is a substance that can form a protective colloid, and it is preferable to use gelatin for the protective colloid.

In the present invention, when gelatin is used as the dispersion medium, lime-treated gelatin, acid-treated gelatin, ion-exchanged gelatin and the like can be used. Gelatin having an adenine content of 0.2 ppm or less described in U.S. Pat. For details on the gelatin production method, see Arthur Weiss, "The Macromolecular Chemistry of
Gelatin "(Academic Press, 1964)
And so on.

Examples of substances that can form protective colloids other than gelatin include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethylcellulose, carboxymethylcellulose, and cellulose sulfate. Cellulose derivatives such as sodium alginate, starch derivatives, etc., polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-n-vinylpyrrolidone, polyacrylic acid, polyacrylamide, polymethacrylic acid, polyvinylimidazole, polyvinylpyrazole, etc. Examples include various types of synthetic or semi-synthetic hydrophilic high-molecular substances such as mono- or copolymers.

In the present invention, the outermost layer of the silver halide grains means a silver halide phase including the surface of the silver halide grains and extending from the surface of the silver halide grains to a depth of 50 °.

The present invention is characterized in that the outermost layer of the silver halide grains contains silver chloride.

The inclusion of silver chloride in the outermost layer of the silver halide grains makes the silver halide composition of the silver halide grains X
By using the line diffraction technique, it can be confirmed from the silver chloride content ratio before and after the formation of the outermost layer.

For the X-ray diffraction technique, reference can be made to Basic Analytical Chemistry Lecture 24 “X-ray analysis” (Kyoritsu Shuppan).

The silver halide composition of the outermost layer is silver chloride,
Any of silver iodochloride, silver iodochlorobromide, silver chlorobromide and the like can be used, but the average silver chloride content is preferably from 5 to 100 mol%, more preferably from 20 to 100 mol%.
Mol%.

In the present invention, the silver iodide content of the outermost layer of the silver halide grains is defined as the silver iodide content measured at five or more points at equal intervals in the outermost layer of the silver halide grains. Is obtained for each silver halide grain by averaging the values, which is referred to as B1. Specifically, the following method is used.

The silver halide grains in the silver halide photographic emulsion are decomposed by gelatin using a proteolytic enzyme, taken out, embedded in methacrylic resin, and continuously cut out to a thickness of about 500 mm with a diamond cutter. EPMA method (Electron Probe Micro Ana) which is well known in the art for a silver halide phase from the silver halide grain surface to a depth of 50 ° in the section of
The silver iodide content is measured by a point analysis using a spot diameter of 50 ° or less, preferably 20 ° or less using the Lyzer method.

In the present invention, the average A1 of the silver iodide content of the outermost layer of the silver halide grains is determined by the above method by setting the silver iodide content B1 of the outermost layer of each silver halide grain to 50 or more. It is obtained by obtaining and averaging silver particles.

Specifically, a sample in which silver halide grains are well dispersed so as not to come into contact with each other is prepared, and irradiated with an electron beam while being cooled to -100 ° C. or lower with liquid nitrogen.
By determining the characteristic X-ray intensities of silver and iodine emitted from individual silver halide grains, the silver iodide content of the individual silver halide grains can be determined,
It can be obtained by measuring zero silver halide grains and calculating the average thereof.

In the silver halide photographic emulsion according to the first aspect of the present invention, A1 / A2 <0.8 is preferable, and A1 / A2 <0.6 is more preferable.

In the present invention, the subsurface layer of the silver halide grains means a silver halide phase which is a silver halide phase from the surface of the silver halide grains to a depth of 150 ° and does not include the outermost layer. .

In the present invention, the silver iodide content B2 of the subsurface layer of the silver halide grains is determined in the subsurface layer of the silver halide grains by the EPMA method described above in the depth direction from the surface of the silver halide grains. It is determined for each silver halide grain by averaging the silver iodide content measured at five or more locations at intervals.

In the silver halide photographic emulsion according to the second aspect of the present invention, it is preferred that silver halide grains satisfying B1 / B2 <1.0 account for 70% or more (number).
Further, it is preferable that B1 / B2 <0.8.
It is particularly preferred that /B2<0.6.

In the present invention, the following method is used to determine the silver iodide content of the outermost layer for each of the main plane portion and the side surface portion.

The tabular silver halide grains in the silver halide photographic emulsion are decomposed by gelatin using a proteolytic enzyme, taken out, embedded in methacrylic resin, and continuously cut out to a thickness of about 500 mm with a diamond cutter. Of these sections, those having a tomographic plane perpendicular to the two parallel principal planes of the tabular silver halide grains, including a principal plane surface on the tomographic planes of the tabular silver halide grains. The silver halide phase from the surface parallel to the main plane surface to a depth of 50 ° is referred to as a main plane portion, and the outermost layer of the silver halide crystal, other than the main plane portion, is referred to as a side surface portion. For each of the above-mentioned main plane portion and side surface portion, the spot diameter was reduced to 50 ° or less, preferably 20 ° or less using the EPMA method described above, and the silver iodide content was measured at 5 or more points at equal intervals by point analysis. By measuring and averaging the silver iodide content, I1 and I2 in each silver halide grain were measured.
Is required.

In the silver halide photographic emulsion according to the third aspect of the present invention, when the silver iodide content of the outermost layer of the silver halide grains is I1 in the main plane portion and I2 in the side surface portion,
It is preferred that the ratio of tabular silver halide grains satisfying 1> I2 is 70% or more (number). More preferably, the relationship between I1 and I2 is I1 / I2> 1.3.
Most preferably, 1 / I2> 2.0. I1 is preferably more than 0.5 and less than 30 and more preferably more than 2 and less than 20.

In the present invention, the apex of the tabular silver halide grain is defined as a projection image when the tabular silver halide grain is viewed from a direction perpendicular to the main plane and has a polygonal shape. When the tabular silver halide grains have a rounded shape, a tangent is drawn in contact with the outer periphery, and the intersection of the tangents is defined as the vertex.

In the present invention, the term "in the vicinity of the apex" refers to the tabular silver halide grain in the projected image when the above-mentioned tabular silver halide grain is viewed from a direction perpendicular to the main plane, with the apex obtained as described above as the center. Of the projected area equivalent particle size of
When a circle is drawn with a radius corresponding to / 10, it refers to a region inside the circle.

In the present invention, the fringe portion of a tabular silver halide grain is defined as a portion inside a side in a projected image when the tabular silver halide grain is viewed from a direction perpendicular to a main plane. When a parallel straight line is drawn at a distance equivalent to 1/20 of the projected area circle grain size of the tabular silver halide grains, a region surrounded by the side and the parallel straight line and excluding the vicinity of the apex is excluded. Area.

In the present invention, the silver bromide content ratio at the fringe portion and near the apex can be determined by the following method.

The silver halide grains in the silver halide photographic emulsion are taken out by gelatinization with a protease enzyme and dispersed in ultrapure water. This dispersion is dropped on a mesh with a carbon support film and dried. This was set in a sample holder, and an analytical transmission electron microscope (Ana)
lytical Electron Microsco
pe), acceleration voltage 200 kV, spot diameter 10 n
At m, to prevent damage to the sample due to electron beam irradiation, observe the silver halide grains while cooling with liquid nitrogen, and analyze the silver halide composition at the fringe and near the apex for each silver halide grain. Do.

In the analysis, an EDS (Ener) that separates characteristic X-rays emitted from an electron beam irradiation region by energy is used.
gy Dispersive Spectroscop
y) method is used. The quantitative calculation is performed by the standardless method using the integrated intensity of the Br-K line and the k factor input to the EDS computer.

In the silver halide photographic emulsion according to the fourth aspect of the present invention, it is preferable that silver halide grains satisfying C1 / C2 <1.0 account for 70% or more (number).
Further, it is preferable that C1 / C2 <0.8, and C1
It is particularly preferred that /C2<0.6.

In the production of the silver halide photographic emulsion according to the present invention, a preferred production method is described below.

In the production of the silver halide photographic emulsion according to claim 1, 2, 3 or 4, the silver halide grains may be contained in the outermost layer of the silver halide grains after forming the silver halide base grains. It is preferable to supply silver halide fine grains containing silver chloride.

The silver halide photographic emulsion containing the silver halide base grains is preferably desalted.

The desalting in the present invention can be performed, for example, by Research Disclosure (Research Discl).
Hereafter, it is abbreviated as RD. ) No. 17643, section II.

More specifically, in order to remove unnecessary soluble salts from a precipitate product or an emulsion after physical ripening,
A Noudel water washing method in which gelatin is gelled may be used, and inorganic salts, anionic surfactants, anionic polymers (eg, polystyrene sulfonic acid), or gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin) may be used. The precipitation method used can be used.

In addition, desalination using ultrafiltration described in Chemical Engineering Handbook, Revised 5th Edition (edited by the Society of Chemical Engineers, Maruzen), pages 924 to 954, etc. can be more preferably used.

Regarding the ultrafiltration desalting method, one of the RD
02, 10208 and 131, 13122, or JP-B-59-43727, JP-A-62-27008, JP-A-62-113137, JP-A-57-209823,
No. 59-43727, No. 62-113137, No. 6
1-219948, 62-23035, 63-
No. 40137, No. 63-40039, JP-A-3-14
No. 0946, No. 2-172816, No. 2-17281
7, No. 4-22942, etc. can be referred to.

In the silver halide fine grains containing silver chloride, silver halide, silver iodochloride, silver iodochlorobromide, silver chlorobromide or the like having an arbitrary composition is used as the silver halide depending on the purpose. However, the average silver chloride content is preferably 20 to 100 mol%, more preferably 50 to 10 mol%.
0 mol%. The silver halide fine grains containing silver chloride are preferably desalted by the method described above, and are preferably subjected to ultrafiltration desalting.

The amount of the silver halide fine grains containing silver chloride to be added to the silver halide base grains is preferably 0.1 to 30%, more preferably 1 to 20% of the silver content of the silver halide host grains. It is more preferred that there be.

In the production of the silver halide photographic emulsion of the present invention, the silver halide fine grains containing silver chloride are added to the silver halide photographic emulsion containing silver halide base grains in order to add the fine grains. The method of dispersing and adding silver halide fine particles to an aqueous solution containing a protective colloid is preferably used. The addition of the silver halide fine particles includes:
The addition may be carried out using a funnel or a pump or the like, or may be added in two or more portions. After the addition of the silver halide fine particles, ripening may be performed if necessary.

In the production of the silver halide photographic emulsion of the present invention, when silver halide fine grains containing silver chloride are added, the temperature of the silver halide photographic emulsion containing silver halide base grains is from 40 ° C. to 90 ° C. Is preferred, more preferably 50 ° C. or more and 80 ° C. or less,
The pH is preferably 3.0 or more and 8.0 or less,
More preferably, it is 4.0 or more and 7.0 or less.

The pCl of the silver halide photographic emulsion containing silver halide host grains after the addition of silver halide fine grains containing silver chloride is preferably 0.5 to 3.5, more preferably 1.0 to 3.0.
0 is more preferred.

In the production of the silver halide photographic emulsion according to the first, second or fourth aspect of the present invention, silver chloride is contained in the outermost layer of the silver halide grains by the above-mentioned method using silver halide fine grains containing silver chloride. In addition to the above, it is preferable to use a method of supplying fine silver halide particles to silver halide base particles. The silver halide base grains and the silver halide fine grains are preferably subjected to desalting by the above-mentioned method, and are preferably subjected to ultrafiltration desalting.

The silver halide fine grains include silver bromide, silver chloride, silver iodide, silver iodobromide, silver iodochloride, and silver halide.
Silver iodobromide, silver chlorobromide and the like can be used any of those used for ordinary silver halides.
Silver chlorobromide, silver iodobromide, and silver iodochlorobromide are preferred.

In the production of a silver halide photographic emulsion according to claim 3 of the present invention, the silver halide photographic emulsion described in Japanese Patent Application No. 9-253585 is used as a silver halide base grain, and the silver halide grain is prepared by the above method. It is preferable that silver chloride is contained in the outermost layer of the above.

In the production of the silver halide photographic emulsion according to the first, second, third or fourth aspect of the present invention, Japanese Patent Application No. 9-34 is disclosed.
More preferably, silver halide base grains are produced by appropriately using the method for producing a silver halide photographic emulsion described in No. 9421, and silver chloride is contained in the outermost layer of the silver halide grains by the above method.

The silver halide grains contained in the silver halide photographic emulsion according to claim 1 or 2 of the present invention may have a regular crystal structure such as cubic, octahedral or tetradecahedral. It may have an irregular crystal form such as spherical or tabular, but tabular silver halide grains are preferred. In these particles, the ratio between the (100) plane and the (111) plane can be arbitrarily used. Further, a composite of these crystal forms may be used, or particles of various crystal forms may be mixed. Twin silver halide grains having two opposing parallel twin planes can also be used, but in such a case, tabular silver halide grains are preferred.

The silver halide grains contained in the silver halide photographic emulsion according to claim 3 or 4 of the present invention are tabular silver halide grains, and have twin opposing parallel twin planes. Silver halide particles are preferred.

The twins are silver halide crystals having one or more twin planes in one grain, and the twins are classified according to Klein and Moiser. Spondents (Photographi)
she Korrespondentz) Volume 99
Page 100, p. 57.

When tabular silver halide grains are used in claims 1 and 2 of the present invention, or in claims 3 and 4 of the present invention, silver halide grains contained in the silver halide photographic emulsion of the present invention are used. Preferably, 50% or more of the total projected area is tabular silver halide grains, more preferably 60% or more, and further preferably 80% or more.

When tabular silver halide grains are used in claims 1 and 2 of the present invention, or in claim 3 and 4 of the present invention, tabular silver halide grains having two twin planes parallel to the main plane are used. The ratio of silver particles is preferably 60% or more, more preferably 70% or more, and still more preferably 80% or more in terms of the number of silver halide particles.

In the present invention, tabular silver halide grains mean silver halide grains having an aspect ratio (ratio of diameter to thickness of silver halide grains) of 1.3 or more. The aspect ratio is preferably from 3.0 to 100, and more preferably from 5.0 to 50.

To determine the aspect ratio, first, the diameter and thickness of silver halide grains are determined by the following method. A latex ball having a known particle size as an internal standard and a sample coated such that the main plane was oriented parallel to the support were prepared on the support, and shadowing was performed by a carbon deposition method from a certain direction. Thereafter, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area diameter and thickness of each silver halide grain are determined using an image processing device or the like. In this case, the thickness of the silver halide grains can be calculated from the internal standard and the length of the shadow of the silver halide grains.

The twin planes of silver halide grains can be observed with a transmission electron microscope. The specific method is as follows. First, a sample is prepared by coating a silver halide emulsion on a support so that the main plane of the tabular silver halide grains is oriented substantially parallel to the support. This is cut using a diamond cutter to a thickness of 0.1μ.
Obtain a thin section of about m. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

In the present invention, the average grain size of the silver halide grains is preferably from 0.2 to 10 μm, more preferably from 0.3 to 7.0 μm.
Is more preferable, and 0.4 to 5.0 μm is most preferable.

In the present invention, the average particle size refers to the particle size ri.
The arithmetic mean of However, three significant figures and the least significant figure are rounded off, and the number of measured particles is indiscriminately 1,000 or more.

In the case of tabular silver halide grains, the grain size ri is a diameter obtained by converting a projected image viewed from a direction perpendicular to the main plane into a circular image having the same area. In the case of silver halide grains having a shape other than tabular silver halide grains, the diameter is obtained by converting a projected image of the silver halide grains into a circular image having the same area.

The grain size ri can be obtained by photographing silver halide grains with an electron microscope at a magnification of 10,000 to 70,000, and measuring the grain diameter or the projected area on the print.

In the present invention, any silver halide photographic emulsion such as a polydisperse emulsion having a wide particle size distribution and a monodisperse emulsion having a narrow particle size distribution is used, but a monodisperse emulsion is preferable.

The monodisperse emulsion has a particle size distribution of less than 20%, more preferably less than 16%, when the particle size distribution is defined by the following formula.

Particle size distribution (%) = (standard deviation of particle size / average particle size) × 100 The average particle size and standard deviation are determined from the particle size ri defined above.

In the silver halide photographic emulsion according to claim 1, 2 or 3, the silver halide photographic emulsion comprises:
Silver iodochlorobromide and silver iodochloride can be used as silver halide, and silver iodochlorobromide and silver bromochloride are used as silver halide in the silver halide photographic emulsion according to claim 4 of the present invention. However, silver iodochlorobromide is particularly preferred.

In the present invention, the average silver iodide content of the silver halide grains contained in the silver halide photographic emulsion is 0.5.
To 40 mol%, more preferably 1 to 40 mol%.
~ 20 mol%.

In the present invention, the silver chloride content of the silver halide grains contained in the silver halide photographic emulsion is preferably from 1 mol% to 30 mol%, more preferably 2 mol% or less.
It is at least 20 mol% and not more than 20 mol%.

In the present invention, the silver bromide content of the silver halide grains contained in the silver halide photographic emulsion is preferably from 50 mol% to 99 mol%, more preferably
70 mol% or more and 98 mol% or less.

In the present invention, core / shell type grains are preferably used as silver halide grains contained in a silver halide photographic emulsion. The core / shell type particles are particles composed of a core and a shell covering the core, and the shell is formed by one or more layers. The silver iodide content of the core and the shell are preferably different from each other.

The silver halide grains in the silver halide photographic emulsion of the present invention preferably have dislocation lines therein. There is no particular limitation on the position where the dislocation line exists, but it is preferable that it exists near the outer peripheral portion, near the ridge line, or near the vertex of the silver halide grain. The introduction position of the dislocation lines in the silver halide grains is preferably 50% or less, more preferably 60% or less, of the total silver content of the silver halide grains.
More preferably, it is introduced in an amount of at least 85%. The number of dislocation lines is preferably 30% or more (number) of silver halide grains having 5 or more dislocation lines, more preferably 50% or more, and further preferably 80% or more. preferable. In each case, the number of dislocation lines in one grain is preferably 10 or more, more preferably 20 or more, and 3 or more.
More preferably, the number is zero or more.

The dislocation lines of the silver halide grains are described, for example, in J. Am. F. Hamilton, Photo. Sci.
Eng. 11 (1967) 57 and T.I. Shiozaw
a. Soc. Photo. Sci. Japan35
(1972) 213 can be observed by a direct method using a transmission electron microscope at a low temperature. That is, silver halide grains taken out from the emulsion without paying enough pressure to generate new dislocation lines on the grains are placed on a mesh of an electron microscope to prevent damage (printout, etc.) by the electron beam. The specimen is observed by a transmission method in a cooled state. At this time, the thicker the silver halide grains, the more difficult it is for an electron beam to pass through, so that a clearer observation can be obtained by using a high-pressure electron microscope. From the grain photograph obtained by such a method, the position and number of dislocation lines in each silver halide grain can be determined.

The method for introducing dislocation lines into silver halide grains is not particularly limited. For example, a method in which an aqueous solution of an iodide ion such as potassium iodide and a solution of a water-soluble silver salt are added by a double jet, silver iodide A method of adding fine particles, a method of adding only an iodine ion solution, and JP-A-6-11781.
A dislocation line of a desired position and amount can be introduced into a silver halide grain by a known method such as a method using an iodide ion-releasing compound described in No.

In the production of the silver halide photographic emulsion of the present invention, various methods well known in the art can be used for forming silver halide base grains. That is,
A single jet method, a double jet method, a triple jet method, a silver halide fine particle supply method, or the like can be used in any combination. Further, a method of controlling pH and pAg in a liquid phase in which silver halide is formed in accordance with the growth rate of silver halide can also be used.

For the production of the silver halide photographic emulsion of the present invention, a seed emulsion may be used. When a seed emulsion is used, the silver halide grains in the seed emulsion may have a regular crystal structure such as cubic, octahedral, or tetradecahedral, or may have a spherical or plate-like shape. It may have an irregular crystal form. In these particles, the (100) plane and the (11) plane
1) Any ratio of planes can be used. Further, a composite of these crystal forms may be used, or particles of various crystal forms may be mixed.

In the present invention, whether a seed emulsion is used or a seed emulsion is not used, the conditions for silver halide nucleation and ripening are those known in the art. Can be.

For the production of the silver halide photographic emulsion of the present invention, a silver halide solvent known in the art can be used. Preferably, a silver halide solvent is used at the time of forming base tabular grains. Should be avoided except for ripening after nucleation. Examples of silver halide solvents include:
(A) U.S. Pat. Nos. 3,271,157 and 3,531,
Nos. 289 and 3,574,628, JP-A-54-10
No. 19, 54-158917, and JP-B-58-3
Organic thioethers described in No. 0571 and the like, (b)
Thiourea derivatives described in JP-A-53-82408, JP-A-55-29829 and JP-A-57-77736;
(C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, as described in JP-A-53-144319, and (d) JP-A-54-10
No. 0717, imidazole, (e) sulfite, (f) thiocyanate, (g) ammonia,
(H) ethylenediamines substituted with hydroxylalkyl described in JP-A-57-196228 and the like;
(I) substituted mercaptotetrazoles described in JP-A-57-202531, etc., (j) water-soluble bromide,
(K) Benzimidazole derivatives described in JP-A-58-54333.

For the production of the silver halide photographic emulsion of the present invention, any of an acidic method, a neutral method and an ammonia method can be used, but the acidic method or the neutral method is preferred.

In the production of the silver halide photographic emulsion of the present invention, a halide ion and a silver ion may be mixed simultaneously, or one of them may be mixed in the presence of the other. Also, considering the critical growth rate of silver halide crystals,
PAg and pH in a mixing vessel containing halide ions and silver ions
And can be added sequentially or simultaneously. In any step of silver halide formation, the halogen composition of the silver halide grains may be changed by using a conversion method.

In the production of the silver halide photographic emulsion of the present invention, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt) is formed in the step of forming and / or growing silver halide grains. ), Rhodium salts (including complex salts), salts of iron and other Group VIII metals (including complex salts)
Metal ions can be added using at least one selected from the above, and these metals can be contained inside silver halide grains and / or on the surface of the grains.

In the production of the silver halide photographic emulsion of the present invention, reduction sensitization can be carried out using a method known in the art. Reduction sensitization may be performed during or after silver halide grain formation.

As a more specific method of reduction sensitization, a method known in the art as silver ripening, which comprises ripening and growing at a low pAg by supplying silver ions to silver halide grains, an alkaline compound, and the like. Use to raise the pH and ripen
An arbitrary method or a combination thereof can be used from a method of growing, a method of adding a reducing agent, and the like.

In the present invention, when a reducing agent is used, for example, thiourea dioxide, ascorbic acid and its derivatives, stannous salts, borane compounds, hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines and sulfurous acid Although salts and the like can be used, thiourea dioxide, ascorbic acid and its derivatives, and stannous salts are preferably used.

In the production of the silver halide photographic emulsion of the present invention, an oxidizing agent known in the art can be used.
Examples of the oxidizing agent include hydrogen peroxide (water) and an adduct _{thereof: H 2 O 2, NaBO 2} , H 2 O 2 -3H 2 O, 2NaC
_{O 3 -3H 2 O 2, Na} 4 P 2 O 7 -2H 2 O 2, 2Na 2 SO 4
Such as -H ₂ O ₂ -2H ₂ O. Peroxy acid salt: K ₂ S ₂ O ₃ ,
_{K 2 C 2 O 3, K} 4 P 2 O 3, K 2 [Ti (O) 2 C 2 O 4] -3
H ₂ O, peracetic acid, ozone, thiosulfonic acid compounds and the like can be mentioned.

In the production of the silver halide photographic emulsion of the present invention, the above reduction sensitization and the addition of an oxidizing agent can be carried out in combination.

In the production of the silver halide photographic emulsion of the present invention, desalting is carried out by the above-mentioned method for the purpose of suppressing the progress of physical ripening or removing unnecessary salts during or after the formation of silver halide grains. preferable.

In the preparation of the silver halide photographic emulsion of the present invention, conditions other than those described above are described in JP-A-61-66.
No. 43, No. 61-14630, No. 61-112142
No. 62-157024, No. 62-18556,
63-92942, 63-151618, 6
Nos. 3-163451, 63-220238, 63
-311244, RD 365, 36544, 367
Appropriate conditions can be selected with reference to Vol. 36736, Vol.

In constructing a color photographic material using the silver halide photographic emulsion of the present invention, the silver halide emulsion is
Use those that have been subjected to physical ripening, chemical ripening and spectral sensitization.

The additive used in such a step is R
D17643, page 23, section III to page 24, section VI-M, RD1
8716, pages 648 to 649 and RD308119, 9
It is described in page 96, section III-A to page 1000, section VI-M.

Known photographic additives which can be used in the present invention are also described in RD17643, page 25, VIII-A section to page 27.
Section XIII, RD18716, pages 650 to 651, RD30
8119, page 1003, paragraphs VIII-A to 1012, XXI-E
Those described in the section can be used.

Various couplers can be used in the color light-sensitive material. Specific examples thereof are RD17643, 25
Page VII-C to G, RD308119, page 1001 VII-
It is described in sections C to G.

The additive used in the present invention is RD3081
19, page 1007, section XIV.

In the present invention, the aforementioned RD17643,
Page 28, section XVII, RD 18716, pages 647-8, and RD
The support described in section 308119, page 1009, XVII can be used.

The photosensitive materials described above include RD308119, 1
An auxiliary layer such as a filter layer or an intermediate layer described in section VII-K on page 002 can be provided.

The photosensitive material is RD308119, VII
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section -K can be adopted.

The silver halide photographic emulsion of the present invention can be used for various color light-sensitive materials typified by 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 be preferably applied.

The light-sensitive material according to the present invention uses the RD17
643, pages 28 to 29, section XIX, RD18716, 651
And RD 308119, pages 1010 to 1011, section XIX.

[0113]

The present invention will be specifically described below with reference to examples.
The present invention is not limited to these examples.

Example 1 (Preparation of spherical seed emulsion T-1)
A monodisperse spherical seed emulsion T-1 was prepared.

(A-1 solution) Ossein gelatin 80 g Potassium bromide 47.4 g 10% methanol solution of surfactant (EO-1) 20 mL Water 8.0 L EO-1: HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) (solution B-1) 1200 g of silver nitrate 1.6 L with water (solution C-1) ossein gelatin 32.2 g Potassium bromide 840 g 1.6 L with water (D-1 solution) Ammonia water (28%) 470 mL A-1 solution stirred vigorously at 40 ° C, B-1 solution and C-1 solution
The solution was added by a double jet method in 11 minutes to generate silver halide nuclei. During this time, pBr was kept at 1.6. Thereafter, the temperature was lowered to 30 ° C. over 12 minutes, and
Aging was performed for 8 minutes. Thereafter, solution D-1 was further added for 1 minute, and subsequently ripening was performed for 5 minutes. Thereafter, the pH was adjusted to 6.0, and desalting was immediately performed. When this seed emulsion was observed with an electron microscope, the average grain size (projected area circle equivalent grain size) having two twin planes parallel to each other was 0.43 μm.
m, a monodisperse spherical emulsion having a particle size distribution of 20%.

(Preparation of Comparative Emulsion Em-1) Using the spherical seed emulsion (T-1) and the following solution, a comparative emulsion (Em-1) was prepared.
1) was prepared.

(A-2 solution) 268.2 g of ossein gelatin 10% methanol solution of surfactant (EO-1) 1.5 mL seed emulsion (T-1) 0.341 mol equivalent 28% by weight aqueous ammonia solution 528 mL 56 Weight% aqueous acetic acid solution 795mL 5930mL with water (B-2 solution) 3.5N ammoniacal silver nitrate aqueous solution 2675mL (pH adjusted to 9.0 with ammonium nitrate) (C-2 solution) 4.0% by weight gelatin containing 3 2,675 mL of a 5N aqueous potassium bromide solution (D-2 solution) 0.844 mol of a fine grain emulsion composed of 3.0% by weight of gelatin and silver iodide fine grains (average particle size: 0.05 μm) The preparation method is described below.

6.0 containing 0.06 mol of potassium iodide
An aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide in 5000 mL of a gelatin solution of 2% by weight was used.
000 mL was added at a constant speed over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the addition is completed, p is added using an aqueous solution of sodium carbonate.
H was adjusted to 6.0. 12.53kg finished weight
Met.

(E-2 solution) 1.75N Potassium bromide aqueous solution required amount (F-2 solution) 56% by weight acetic acid aqueous solution required amount A-2 solution kept at 70 ° C. in a reaction vessel, B-2 solution , C
Solution 2 and Solution D-2 were added over 170 minutes by the simultaneous mixing method.

Here, the addition rate of the B-2 solution, C-2 solution and D-2 solution is changed in a function-wise manner with respect to the addition time in consideration of the critical growth rate, and the addition rate of the seed particles other than the seed particles growing is The generation of small particles and the deterioration of the particle size distribution due to Ostwald ripening between growing particles were prevented. The solution D-2 was supplied by changing the rate ratio (molar ratio) with respect to the ammoniacal silver nitrate with respect to the particle size (addition time) as shown in Table 1 to obtain core / shell type silver halide grains having a multiple structure. Was prepared.

The pH and pAg during the crystal growth were controlled as shown in Table 1 using the E-2 solution and the F-2 solution. The pH and pAg were measured according to a conventional method, using a silver sulfide electrode,
This was performed using a glass electrode.

[0122]

[Table 1]

After the particles are formed, desalting is carried out according to the method described in JP-A-5-72658, and then gelatin is added and dispersed, and pAg 8.06 at 40 ° C., pH 5.0.
8 to obtain a comparative emulsion (Em-1).

When the silver halide grains in this emulsion were observed with an electron microscope, the average grain size was 1.35 μm and the grain size distribution was 11%. The silver halide grains had (111) and (100) faces. And comprised 90% of the total number of grains. Its major surface was the (111) plane, which accounted for 80% of the total silver halide grain surface.

(Preparation of Comparative Emulsion Em-2)
In the preparation of m-1), after desalting according to the method described in JP-A-5-72658, the temperature was raised to 60 ° C., and pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution. A 0.42 mol equivalent of silver halide in the following solution G-2 was added in 10 minutes, ripened for 20 minutes, and then subjected to the following ultrafiltration B, and pAg 8.0 at 40 ° C.
6. A comparative emulsion (Em-2) was prepared in the same manner except that the pH was adjusted to 5.8.

(G-2 solution) A method for preparing a fine grain emulsion comprising 3.0% by weight of gelatin and fine grains of silver bromide (average particle size: 0.05 μm) is described below.

6.0 containing 0.06 mol of potassium bromide
2000 mL of an aqueous solution containing 7.06 mol of silver nitrate and 2,000 mL of an aqueous solution containing 7.06 mol of potassium bromide were added at a constant rate over 5000 minutes to 5000 mL of a weight% gelatin solution. The pH during the formation of the fine particles was adjusted to 3.0 using nitric acid.
And the temperature was controlled at 30 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

(Preparation of Comparative Emulsion Em-3)
In the preparation of m-1), after formation of silver halide grains,
The following H-2 solution was prepared by adding 0.3 mole equivalent of silver halide to 5
And aged for 20 minutes.
After desalting according to the method described in No. 658,
After the temperature was raised to 60 ° C. and the pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution, 0.63 mol equivalent of the silver halide in the following liquid I-2 was added in 10 minutes, and the solution was added for 20 minutes. After aging and then performing the following ultrafiltration B operation,
A comparative emulsion (Em-3) was prepared in the same manner except that the pAg was adjusted to 8.06 and the pH to 5.8 at ℃.

(H-2 solution) A method for preparing a fine grain emulsion comprising 3.0% by weight of gelatin and silver iodide fine grains (average grain size: 0.05 μm) is described below.

6.0 containing 0.06 mol of potassium iodide
An aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide in 5000 mL of a gelatin solution of 2% by weight was used.
000 mL was added at a constant speed over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the addition is completed, p is added using an aqueous solution of sodium carbonate.
H was adjusted to 6.0.

(I-2 solution) 3.0% by weight of gelatin and silver chlorobromide fine particles (average particle size 0.07 μm, silver bromide content 5%)
0%) is described below.

5. containing 0.06 mol of sodium chloride
To 5000 mL of a 0% by weight gelatin solution, 2,000 mL of an aqueous solution containing 7.06 mol of silver nitrate and 2,000 mL of an aqueous solution containing 3.53 mol of sodium bromide and 3.53 mol of sodium chloride were added at a constant rate over 10 minutes. During the formation of fine particles, the pH was adjusted to 3.0 using nitric acid, and the temperature was adjusted to 30.
C. was controlled. After the addition was completed, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution, and the following ultrafiltration A was performed.

(Ultrafiltration A) A silver halide emulsion was treated with an ultrafiltration module (manufactured by Asahi Kasei Kogyo Co., Ltd .;
Type AL using 000 polyacrylonitrile membrane
(P-1010), circulating water and concentrating repeatedly to reduce the salt concentration to 1/50.

(Ultrafiltration B) A silver halide emulsion was subjected to an ultrafiltration module (manufactured by Asahi Kasei Kogyo Co., Ltd .;
Type AL using 000 polyacrylonitrile membrane
Water circulation and concentration were repeated while circulating through P-1010) to reduce the salt concentration to 1/80.

(Preparation of Emulsion Em-4 of the Invention) In the preparation of the comparative emulsion (Em-1), after desalting was carried out according to the method described in JP-A-5-72658, the temperature was raised to 60 ° C. After adjusting the pBr to 1.7 with a 2N aqueous potassium bromide solution, the silver halide content of the solution I-2 was 0.63.
A molar equivalent was added in 10 minutes, the mixture was aged for 20 minutes, and then subjected to the above-mentioned ultrafiltration B operation, and then adjusted to pAg 8.06 and pH 5.8 at 40 ° C in the same manner as in the above. Invention emulsion (Em-4) was prepared.

(Preparation of Emulsion Em-5 of the Invention) In the preparation of Comparative Emulsion (Em-1), after desalting was carried out according to the method described in JP-A-5-72658, the temperature was raised to 60 ° C. After adjusting the pBr to 1.7 with a 2N aqueous potassium bromide solution, the amount of silver halide in the following J-2 solution was 0.63.
A molar equivalent was added in 10 minutes, the mixture was aged for 20 minutes, and then subjected to the above-mentioned ultrafiltration B operation, and then adjusted to pAg 8.06 and pH 5.8 at 40 ° C in the same manner as in the above. Invention emulsion (Em-5) was prepared.

(J-2 solution) A method for preparing a fine grain emulsion comprising 3.0% by weight of gelatin and fine silver chloride grains (average grain size: 0.08 μm) is described below.

5. Contain 0.06 mol of sodium chloride
To 5000 mL of a 0% by weight gelatin solution, 2000 mL of an aqueous solution containing 7.06 mol of silver nitrate and 2000 mL of an aqueous solution containing 7.06 mol of sodium chloride were added at a constant rate over 10 minutes. During the formation of fine particles, the pH was controlled at 3.0 using nitric acid, and the temperature was controlled at 30 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution, and the ultrafiltration A was performed.

When the silver halide composition of the silver halide grains contained in the emulsions Em-1 to Em-5 was confirmed by X-ray diffraction, it was found that the silver halide grains contained in the emulsions Em-3 to Em-5 contained: It was confirmed that silver chloride was contained.

Emulsions Em-1 to Em-5 were used in the following sample formulations, in the tenth layer, denoted as silver iodobromide g. These emulsions Em-1 to Em-5 were used after being optimally subjected to color sensitization and chemical sensitization by the method described in the following sample formulation.

(Preparation of color light-sensitive material) On a triacetyl cellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side to prepare multilayer color light-sensitive material samples 101 to 105. . The amount of each material added is expressed in grams per 1 m ^2. However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV Absorber UV-1 0.3 Colored Magenta Coupler CM-1 0.123 Colored Cyan Coupler CC-1 0.044 High Boiling Solvent OIL-1 0.167 Gelatin 1.33 Second layer (intermediate layer) Stain inhibitor AS-1 0.16 High boiling point solvent OIL-1 0.20 Gelatin 0.69 Third layer (Low sensitivity red-sensitive layer) Silver halide a 0.12 silver iodobromide b 0.29 sensitizing dye SD-1 2.37 × 10 ^-5 sensitizing dye SD-2 1.2 × 10 ^-4 sensitizing dye SD-3 2.4 × ^10-4 sensitizing dye SD-4 2.4 × ^10-6 Cyan coupler C-1 0.32 Colored cyan coupler CC-1 0.038 High boiling point solvent OIL-2 0.28 Stain inhibitor AS-2 0.0. 002 Gelatin 0.73 No. 4 layers (medium-speed red-sensitive layer) silver iodobromide c 0.10 silver iodobromide d 0.86 sensitizing dye SD-1 4.5 × 10 ^-5 sensitizing dye SD-2 2.3 × 10 ^-4 sensitizing dye SD-3 4.5 × 10 ^-4 cyan coupler C-2 0.52 colored cyan coupler CC-1 0.06 DIR compound DI-1 0.047 high boiling point solvent OIL-2 0.46 Antifouling agent AS-2 0.004 Gelatin 1.30 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.18 Sensitizing dye SD-1 3.0 × 10 ^-5 sensitizing dye SD-2 1.5 × 10 ^-4 sensitizing dye SD-3 3.0 × 10 ^-4 cyan coupler C-2 0.047 cyan coupler C-3 0.09 colored cyan coupler CC -1 0.036 DIR compound DI-1 0.024 High boiling point solvent OIL-2 0.27 Pollution prevention AS-2 0.006 Gelatin 1.28 6th layer (intermediate layer) High boiling point solvent OIL-1 0.29 Stain inhibitor AS-1 0.23 Gelatin 1.00 7th layer (Low sensitivity green color sensitive layer) ) Silver iodobromide a 0.19 Silver iodobromide b 0.062 Sensitizing dye SD-4 3.6 × 10 ^-4 Sensitizing dye SD-5 3.6 × 10 ^-4 Magenta coupler M-10 18 Colored magenta coupler CM-1 0.033 High boiling solvent OIL-1 0.22 Stain inhibitor AS-2 0.002 Stain inhibitor AS-3 0.05 Gelatin 0.61 Eighth layer (intermediate layer) High boiling point Solvent OIL-1 0.26 Antifouling agent AS-1 0.054 Gelatin 0.80 Ninth layer (medium-speed green-sensitive layer) Silver iodobromide e 0.54 Silver iodobromide f 0.54 Sensitization dyes SD-6 3.7 × 10 sensitized ^-4 dye SD-7 7.4 × 10 ^-5 sensitization Containing SD-8 5.0 × ^{10 -5} Magenta coupler M-1 0.17 Magenta Coupler M-2 0.33 Colored magenta coupler CM-1 0.024 Colored magenta coupler CM-2 0.029 DIR compound DI-2 0.024 DIR compound DI-3 0.005 High boiling point solvent OIL-1 0.73 Stain inhibitor AS-2 0.003 Stain inhibitor AS-3 0.035 Gelatin 1.80 10th layer (high sensitivity green feeling) Coloring layer) Silver iodobromide g 1.19 Sensitizing dye SD-6 4.0 × 10 ^-4 Sensitizing dye SD-7 8.0 × 10 ^-5 Sensitizing dye SD-8 5.0 × 10 ^{− 5} Magenta coupler M-1 0.065 Colored magenta coupler CM-1 0.022 Colored magenta coupler CM-2 0.026 DIR compound DI-2 0.003 DIR compound DI- 3 0.003 High boiling solvent OIL-1 0.19 High boiling solvent OIL-2 0.43 Stain inhibitor AS-2 0.014 Stain inhibitor AS-3 0.017 Gelatin 1.23 11th layer (yellow filter Layer) Yellow colloidal silver 0.05 High boiling point solvent OIL-1 0.18 Stain inhibitor AS-1 0.16 Gelatin 1.00 12th layer (Low-sensitivity blue-sensitive layer) Silver iodobromide a 0.08 Silver iodobromide b 0.22 Sensitizing dye SD-9 6.5 × 10 ^-4 Sensitizing dye SD-10 2.5 × 10 ^-4 Yellow coupler Y-1 0.77 DIR compound DI-4 0.017 High boiling point solvent OIL-1 0.31 Stain inhibitor AS-2 0.002 Gelatin 1.29 13th layer (highly sensitive blue-sensitive layer) Silver iodobromide h 0.41 Silver iodobromide i 0.61 Sensitizing dye SD-9 4.4 × 10 ^-4 Sensitizing dye SD- 10 1.5 × 10 ^-4 Yellow coupler Y-1 0.23 High boiling point solvent OIL-1 0.10 Stain inhibitor AS-2 0.004 Gelatin 1.20 14th layer (first protective layer) iodobromide Silver j 0.30 UV absorber UV-1 0.055 UV absorber UV-2 0.110 High boiling point solvent OIL-2 0.30 Gelatin 1.32 15th layer (second protective layer) Polymer PM-10 .15 Polymer PM-2 0.04 Slip agent WAX-1 0.02 Dye D-1 0.001 Gelatin 0.55 The characteristics of the above silver iodobromide are shown below (the average particle size is:
It refers to the length of one side of a cube of the same volume).

Emulsion No. Average grain size (μm) Average AgI content (mol%) Diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 Silver iodobromide b 0.40 8.0 1.4 Silver iodobromide c 0.60 7.0 3.1 Silver iodobromide d 0.74 7.0 5.0 Silver iodobromide e 0.60 7.0 4,1 Silver iodobromide f 0.65 8.7 6. 5 Silver iodobromide h 0.65 8.0 1.4 Silver iodobromide i 1.00 8.0 2.0 2.0 Silver iodobromide j 0.05 2.0 1.0 The preferred halogen of the present invention Production examples of silver iodobromide d and f will be described below as examples of forming silver iodide grains. Regarding silver iodobromide j, JP-A-1-183417 and 1-1.
No. 83644, No. 1-183645, No. 2-1664
It was prepared with reference to the description relating to No. 42.

First, seed crystal emulsion-1 was prepared.

(Preparation of Seed Crystal Emulsion-1) JP-B-58-58
No. 288 and No. 58-58289, a silver nitrate aqueous solution (1.161 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (iodide) were added to the following solution A11 adjusted to 35 ° C. Potassium 2 mol%) was added over 2 minutes by the simultaneous mixing method while keeping the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV to perform nucleation. . Subsequently, the liquid temperature was raised to 60 ° C. over a period of 60 minutes, the pH was adjusted to 5.0 with an aqueous sodium carbonate solution, and then an aqueous silver nitrate solution (5.
902 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (2 mol% of potassium iodide) were added over 42 minutes by a simultaneous mixing method while keeping the silver potential at 9 mV.
After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side length ratio (maximum side ratio of each grain) of 90% or more of the total projected area of silver halide grains. The emulsion was composed of hexagonal tabular grains having a ratio of a side length to a minimum side length of 1.0 to 2.0. This emulsion is referred to as seed emulsion-1.

(Solution A11) Ossein gelatin 24.2 g Potassium bromide 10.8 g 10% ethanol solution of surfactant (EO-1) 6.78 ml 10% nitric acid 114 ml Water 9657 ml (silver iodide fine grain emulsion SMC-1 Preparation) While stirring vigorously 5 L of a 6.0% by weight aqueous gelatin solution containing 0.06 mol of potassium iodide, 7.0 L of an aqueous solution of silver nitrate and 2 L of a 7.06 mol of aqueous solution of potassium iodide were added. Was added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the preparation of the particles, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution. The average particle size of the obtained silver iodide fine particles is 0.05 μm.
Met. This emulsion is designated as SMC-1.

(Preparation of silver iodobromide d) 4.5% by weight of an emulsion containing 0.178 mol of seed crystal emulsion-1 and 0.5 ml of a 10% ethanol solution of a surfactant (SU-1). 700 ml of the active gelatin aqueous solution was kept at 75 ° C., and the pAg was 8.
4. After adjusting the pH to 5.0, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure.

1) 3.093 mol of an aqueous silver nitrate solution and
287 mol of SMC-1 and aqueous potassium bromide solution were added to p
Ag was added while keeping the pH at 8.4 and the pH at 5.0.

2) Subsequently, the solution was cooled to 60 ° C.
Was adjusted to 9.8. Then, 0.071 mol of SMC
-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

3) 0.959 mol silver nitrate aqueous solution and 0.1 mol
03 mol of SMC-1 and an aqueous solution of potassium bromide were added to pA
g while maintaining the pH at 9.8 and the pH at 5.0.

Throughout the particle formation, each solution was added at an optimum rate so as to prevent the formation of new nuclei and Ostwald ripening between particles.

After the completion of the addition, the mixture was washed with water at 40 ° C. using a usual flocculation method, and then gelatin was added to redisperse it. The pAg was adjusted to 8.1 and the pH was adjusted to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Tabular grains having a halogen composition having a side length of 0.75 μm, an average aspect ratio of 5.0, and a silver iodide content of 2 / 8.5 / X / 3 mol% (X is a dislocation line introduction position) from the inside of the grains. Emulsion. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed in both the fringe portion and the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 6.7 mol%.

(Preparation of silver iodobromide f) In the preparation of silver iodobromide d, in step 1), pAg was 8.8, the amount of silver nitrate added was 2.077 mol, and the amount of SMC-1 was 0. .218
Silver iodobromide f was prepared in exactly the same manner as silver iodobromide d except that the amount of silver nitrate added in step 3) was 0.91 mol and the amount of SMC-1 was 0.079 mol. .

The obtained emulsion had a particle size (cubic 1 of the same volume).
Tabular grains having a halogen composition having a side length of 0.65 μm, an average aspect ratio of 6.5, and a silver iodide content of 2 / 9.5 / X / 8 mol% (where X is a dislocation line introduction position) from the inside of the grains. Emulsion. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed in both the fringe portion and the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 11.9 mol%.

After the above-mentioned sensitizing dyes are added to each of the above emulsions and ripened, triphenylphosphine selenide, sodium thiosulfate, chloroauric acid, and potassium thiocyanate are added to optimize the fog-sensitivity relationship. Chemical sensitization was applied.

Silver bromoiodides a, b, c, e, g, h and i were also subjected to spectral sensitization and chemical sensitization in accordance with the above-mentioned silver bromoiodides d and f.

[0159] In addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-1 (polyvinylpyrrolidone, weight average molecular weight: 1)
000), AF-2 (polyvinyl pyrrolidone, weight average molecular weight: 1,100,000), inhibitor AF-3,
AF-4, AF-5, hardeners H-1, H-2 and preservative Ase-1 were added.

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

SU-1: C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH
_{2 COOK SU-2: C 8} F 17 SO 2 NH (CH 2) 3 N + (CH 3) 3
Br ^- SU-3: sodium di (2-ethylhexyl) sulfosuccinate SU-4: sodium tri-i-propylnaphthalenesulfonate ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene ST-2: Adenine AF-3: 1-Phenyl-5-mercaptotetrazole AF-4: 1- (4-Carboxyphenyl) -5-mercaptotetrazole AF-5: 1- (3- acetamidophenyl) -5-mercaptotetrazole H-1: _{[(CH 2 = CHSO 2 CH 2} ) 3 CCH 2 SO 2 C
H ₂ CH ₂ ] ₂ NCH ₂ CH ₂ SO ₃ K H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium OIL-1: tricresyl phosphate OIL-2: di (2-ethylhexyl) Phthalate AS-1: 2,5-bis (1,1-dimethyl-4-hexyloxycarbonylbutyl) hydroquinone AS-2: Dodecyl gallate AS-3: 1,4-bis (2-tetradecyloxycarbonylethyl) Piperazine

[0162]

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[0163]

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The samples 101 to 105 obtained were subjected to the following color development processing.

(Processing step) Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2. 0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 1 minute 55 ± 5.0 ° C.-* The replenishing amount is a value per 1 m ² of the photosensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developing solution and color developing replenishing solution Developer replenishing solution Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium bicarbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g iodide Potassium 1.2 mg-Hydroxylamine sulfate 2.5 g 3.1 g Sodium chloride 0.6 g-4-Amino-3-methyl-N-ethyl-N-([beta] -hydroxylethyl) aniline sulfate 4.5 g 6.3 g Diethylenetriaminepentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Add water to make 1 liter, and add potassium hydroxide or 20%
The color developing solution is adjusted to pH 10.06 and the replenisher is adjusted to pH 10.18 using sulfuric acid.

Bleach and Bleach Replenisher Bleach Replenisher Water 700 ml 700 ml 1,3-diaminopropanetetraacetate ammonium (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g 56 g water To 1 liter, and adjust the pH of the bleaching solution to 4.4 and the pH of the replenishing solution to 4.0 using ammonia water or glacial acetic acid.

Fixing Solution and Fixing Replenisher Fixing Solution Replenisher Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Aqueous solution using ammonia water or glacial acetic acid, pH 6.2
Then, the pH of the replenisher is adjusted to 6.5, and then water is added to make 1 liter.

Stabilizing solution and stabilizing replenishing solution Water 900 ml p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g siloxane (UCC L-77) 0.1 g ammonia water 0.5 ml water was added to make up to 1 liter.
Adjust to pH 8.5 with% sulfuric acid.

<< Evaluation of Sensitivity and Granularity >> Samples 101 to 10
5 was subjected to a step wedge exposure at 1/2200 second and 3.2 CMS using white light, and immediately thereafter, the above-mentioned color development processing was performed to obtain a characteristic curve.

As for the sensitivity, the green sensitivity (the reciprocal of the exposure amount that gives a density of fog density + 0.10) was determined by setting the value of sample 101 to 100.
The relative values are shown below.

The granularity was determined by the RMS granularity (fog density +
A density of 0.30 was scanned with a microdensitometer having an aperture scanning area of 250 μm ² , and the change of the density value (1000 times as large) was measured.

Table 2 shows the evaluation results of the samples 101 to 105.

[0179]

[Table 2]

Table 2 shows that the emulsions Em-4 and Em-
Coating samples 104 and 105 using No. 5 are comparative emulsions Em.
Excellent sensitivity and granularity were exhibited with respect to coating samples 101 to 103 using -1 to Em-3.

Example 2 (Preparation of Seed Emulsion T-2) A seed emulsion T-2 having two parallel twin planes was prepared by the following method.

(E-3 solution) Deionized alkali-treated gelatin (average molecular weight: 15,000) 244.0 g Potassium bromide 156.6 g 10% methanol solution of surfactant (EO-1) 0.48 mL with water 0 L (F-3 liquid) Silver nitrate 1200 g 3716 mL with water (G-3 liquid) Deionized alkali-treated gelatin (average molecular weight 15,000) 31.6 g Potassium bromide 906.0 g Water 4.0 L (H-3 liquid) Ammonia water (28%) 299 mL (I-3 solution) Water 8.0 L (J-3 solution) Ossein gelatin 400.0 g With water 4832 mL (K-3 solution) Potassium bromide 69.2 g Water 386 mL (L- Liquid 3) 56% by weight acetic acid aqueous solution 1000 mL Using a stirring device described in JP-A-62-160128, 3
Solution I-3 was added to solution E-3 which was vigorously stirred at 0 ° C., and then solution F-3 and solution G-3 were mixed by double jet method.
Per minute to produce silver halide nuclei.

Thereafter, the J-3 solution was added, the temperature was raised to 68 ° C. over 41 minutes, the H-3 solution was further added, and aging was performed for 5 minutes. Thereafter, the K-3 solution was further added, and one minute later, the pH was adjusted to 4.7 using the L-3 solution, and immediately desalting was performed by a conventional method. When this seed emulsion was observed with an electron microscope, the average grain size (grain size in terms of projected area circle) having two twin planes parallel to each other was 0.31 μm, and the grain size distribution was 16%.
Was obtained.

(Preparation of Comparative Emulsion Em-11) Seed Emulsion T-
Using No. 2 and the following solutions, Comparative Emulsion Em-11 was prepared.

(H-4 solution) Ossein gelatin 223.6 g 10% methanol solution of surfactant (EO-1) 3.6 mL seed emulsion T-1 0.774 mol equivalent Water 5904 mL with water (I-4 solution) 3.5N silver nitrate aqueous solution 7265 mL (J-4 solution) Potassium bromide 367 g Potassium iodide 104.6 g Water 9000 mL (L-4 solution) 1.75 N potassium bromide aqueous solution Required amount (M-4 solution) 56% by weight acetic acid Aqueous solution required amount Add H-4 solution into the reaction vessel and, with vigorous stirring,
Solution I-4 and solution J-4 were added by a simultaneous mixing method according to the combination shown in Table 3, and a seed crystal was grown.
A tabular silver halide emulsion was prepared.

Here, the addition rates of the liquids I-4 and J-4 are changed in a function-wise manner with respect to the addition time in consideration of the critical growth rate, and the generation of small particles other than the seed particles that are growing. And
The degradation of the particle size distribution due to Ostwald ripening between the growing particles was prevented.

In the crystal growth, first, the first addition was performed while controlling the solution temperature in the reaction vessel to 75 ° C. and the pAg to 8.8, and then the solution temperature in the reaction vessel was reduced to 60 ° C. in 15 minutes. Two additions were made. The second addition was performed while controlling the solution temperature in the reaction vessel to 60 ° C., the pAg to 9.8, and the pH to 5.8. For control of pAg and pH, L-4 solution and M-4 solution were added as needed.

[0188]

[Table 3]

After the formation of the particles, desalting was carried out according to the method described in JP-A-5-72658, and gelatin was added and dispersed. Thereafter, the temperature was raised to 60 ° C., the pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution, and 1.31 mol equivalent of the silver halide in the following J-5 solution was added in 10 minutes. After aging for 20 minutes, the above operation of ultrafiltration B was performed, and then pAg 8.06, pH 5.0 at 40 ° C.
8 to prepare a comparative emulsion (Em-11).

(J-5 solution) A method for preparing a fine particle emulsion comprising 3.0% by weight of gelatin and fine particles of silver bromide (average particle size: 0.05 μm) is described below.

6.0 containing 0.06 mol of potassium bromide
2000 mL of an aqueous solution containing 7.06 mol of silver nitrate and 2,000 mL of an aqueous solution containing 7.06 mol of potassium bromide were added at a constant rate over 5000 minutes to 5000 mL of a weight% gelatin solution. The pH during the formation of the fine particles was adjusted to 3.0 using nitric acid.
And the temperature was controlled at 30 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution, and the ultrafiltration A was performed.

When the silver halide grains in this emulsion were observed by an electron microscope, hexagonal tabular monodispersed silver halide grains having an average particle size of 1.40 μm and a particle size distribution of 16% and an average aspect ratio of 9.0 were obtained. It accounted for 92% of the number of particles.

(Preparation of Comparative Emulsion Em-12) In the preparation of Comparative Emulsion (Em-11), the following J-6 solution was replaced with 1.3 mol equivalent of silver halide in the following J-6 solution. A comparative emulsion (Em-12) was prepared in the same manner except that the above procedure was repeated.

(J-6 solution) 3.0% by weight of gelatin and silver iodobromide fine particles (average particle size: 0.05 μm, silver iodide content: 1)
(0 mol%) is described below.

6.0 containing 0.06 mol of potassium bromide
2000 mL of an aqueous solution containing 7.06 mol of silver nitrate in 5000 mL of a weight% gelatin solution, and 20 an aqueous solution containing 6.35 mol of potassium bromide and 0.71 mol of potassium iodide
00 mL was added at a constant speed over 10 minutes. During the formation of fine particles, the pH was controlled at 3.0 using nitric acid, and the temperature was controlled at 30 ° C. After the addition is completed, p is added using an aqueous solution of sodium carbonate.
H was adjusted to 6.0, and the above ultrafiltration A was performed.

(Preparation of Comparative Emulsion Em-13) Comparative Emulsion E
In the preparation of m-11, after forming the particles,
According to the method described in No. 2658, desalting treatment was performed, and gelatin was added and dispersed. Thereafter, the temperature was raised to 60 ° C., and the pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution.
And then ripening for 30 minutes, then adding the above solution I-2 in an amount equivalent to 2.1 moles of silver halide in 10 minutes, aging for 20 minutes, and performing the above-mentioned ultrafiltration B operation. After that, a comparative emulsion (Em-13) was prepared in the same manner except that the pAg was adjusted to 8.06 and the pH to 5.8 at 40 ° C.

(Preparation of Emulsion Em-14 of the Present Invention) In the preparation of Comparative Emulsion Em-11, after grain formation, the emulsion
A desalting treatment was performed according to the method described in No. 72658, and gelatin was added and dispersed. Thereafter, the temperature was raised to 60 ° C. and 2N
After adjusting the pBr to 1.7 with an aqueous potassium bromide solution, 0.5 mol equivalent of the silver halide in the J-6 solution was adjusted to 1%.
0 minutes, aged for 10 minutes, and then the above I-2
The solution was added in an amount of 2.6 moles equivalent to the amount of silver halide in 10 minutes, aged for 20 minutes, subjected to the operation of ultrafiltration B, and adjusted to pAg 8.06 and pH 5.8 at 40 ° C. The emulsion of the present invention (Em-14)
Was prepared.

(Preparation of Emulsion Em-15 of the Invention) In the preparation of Comparative Emulsion Em-11, after the grain formation, the emulsion
A desalting treatment was performed according to the method described in No. 72658, and gelatin was added and dispersed. Thereafter, the temperature was raised to 60 ° C. and 2N
After adjusting the pBr to 1.7 with an aqueous potassium bromide solution, 0.5 mol equivalent of the silver halide in the J-6 solution was adjusted to 1%.
0 minutes, aged for 10 minutes, then J-2
The solution was added in an amount of 2.6 moles equivalent to the amount of silver halide in 10 minutes, aged for 20 minutes, subjected to the operation of ultrafiltration B, and adjusted to pAg 8.06 and pH 5.8 at 40 ° C. The emulsion of the present invention (Em-15)
Was prepared.

When the silver halide composition of the silver halide grains contained in the emulsions Em-11 to Em-15 was confirmed by X-ray diffraction, the silver halide grains contained in the emulsions Em-13 to Em-15 were: It was confirmed that silver chloride was contained.

Using the emulsions Em-11 to Em-15, multilayer color light-sensitive material samples 111 to 115 were prepared in the same manner as in Example 1 and evaluated. Table 4 shows the results.

[0201]

[Table 4]

Table 4 shows that the emulsions Em-14 and Em of the present invention were obtained.
The coated samples 114 and 115 using -15 were coated samples 111 to 11 using comparative emulsions Em-11 to Em-13.
3 showed excellent sensitivity and granularity.

Example 3 (Preparation of seed emulsion T-3) A seed emulsion T-3 having two parallel twin planes was prepared by the following method.

(A-6 solution) Ossein gelatin 38.0 g Potassium bromide 11.7 g 34.0 L with water (B-6 solution) Silver nitrate 810.0 g Water 3815 mL (C-6 solution) Potassium bromide 567. 315 mL with water 3815 mL (D-6 solution) 163.4 g Ossein gelatin 10% methanol solution of surfactant (EO-1) 5.5 mL 3961 mL with water (E-6 solution) Sulfuric acid (10%) 91.1 mL ( F-6 solution) 56% acetic acid aqueous solution required amount (G-6 solution) ammonia water (28%) 105.7 mL (H-6 solution) Potassium hydroxide aqueous solution (10%) required amount (I-6 solution) bromide 208.3 g of potassium 1000 ml of water using a stirrer described in JP-A-62-160128.
Solution E-6 was added to solution A-6 which was vigorously stirred at 0 ° C., and then solution B-6 and solution C-6 were added at a constant rate of 279 mL each for 1 minute by a double jet method to obtain silver halide nuclei. Was generated.

Thereafter, the solution D-6 was added, the temperature was raised to 60 ° C. over 31 minutes, the solution G-6 was further added, the pH was adjusted to 9.3 with the solution H-6, and the solution was heated for 6.5 minutes. Aging was performed. Thereafter, the pH was adjusted to 5.8 with F-6 solution, and then the remaining B-6 solution and C-6 solution were mixed by the double jet method to 37.
Min, and desalted immediately by a conventional method. When this seed emulsion was observed with an electron microscope, two parallel
Average grain size with two twin planes (projected area circle equivalent grain size)
This was a monodisperse tabular seed emulsion having a particle size distribution of 72 μm and a particle size distribution of 16%.

(Preparation of Comparative Emulsion Em-21) Seed emulsion T-
Using No. 3 and the following solutions, Comparative Emulsion Em-21 was prepared.

(A-7 solution) Ossein gelatin 519.9 g 10% methanol solution of surfactant (EO-1) 4.5 mL seed emulsion T-3 5.3 mol equivalent 18.0 L with water (B-7 Liquid) 3.5N silver nitrate aqueous solution 2787 mL (C-7 liquid) Potassium bromide 1020 g Potassium iodide 29.1 g Water 2500 mL (D-7 liquid) Potassium bromide 618.5 g Potassium iodide 8.7 g Water 1500 mL (E −7 solution) Potassium bromide 208.3 g 1000 mL with water (F-7 solution) 56% acetic acid aqueous solution Required amount (G-7 solution) Potassium bromide 624.8 g 1500 mL with water (H-7 solution) 3.0 weight % Of gelatin and 0.672 mol of a fine grain emulsion comprising silver iodide fine grains (average grain size: 0.05 μm) The preparation method is described below.

4. Containing 0.254 mol of potassium iodide
To 9942 mL of a 0% gelatin solution, 3092 mL of an aqueous solution containing 10.59 mol of silver nitrate and 10.59 mol of potassium iodide were added at a constant speed over 35 minutes to form fine particles. The temperature during the formation of fine particles was controlled at 40 ° C, and the pH,
The EAg was established.

(Liquid K-7) 10% Potassium hydroxide aqueous solution Required Amount Liquid A-7 was added to the reaction vessel, and while stirring vigorously at 75 ° C., liquid B-7, liquid C-7, and liquid D-7 The seven liquids were added by the simultaneous mixing method according to the combination shown in Table 5,
Seed crystals were grown to prepare comparative emulsion Em-31.

Here, the addition rates of the B-7 solution, C-7 solution and D-7 solution were changed in a function-wise manner with respect to the addition time in consideration of the critical growth rate. The generation of small particles and the deterioration of the particle size distribution due to Ostwald ripening between growing particles were prevented.

First, the first growth was carried out by controlling the solution temperature in the reaction vessel to 75 ° C., the pAg to 9.4, and the pH to 5.8. In this first addition, 6 of solution B-7
5.8% was added. Thereafter, the solution temperature in the reaction vessel was lowered to 40 ° C. in 30 minutes, and the pAg was adjusted to 10.3,
The whole amount of the H-7 solution was added at a constant speed for 2 minutes, and the second addition was immediately performed. In the second addition, the solution temperature in the reaction vessel was set at 40 ° C.
The pAg was controlled at 10.3 and the pH at 5.0, and the rest of the B-7 solution was added. pAg and pH
For control, E-7 solution and F-7 as needed
Solution and K-7 solution were added.

[0212]

[Table 5]

After the formation of the particles, desalting was performed according to the method described in JP-A-5-72658, and gelatin was added and dispersed. Thereafter, the temperature was raised to 60 ° C., and pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution. Then, 1.56 mol equivalent of silver halide in the following J-7 solution was added in 10 minutes. After aging for 20 minutes, the above operation of ultrafiltration B was performed, and then pAg 8.06, pH 5.0 at 40 ° C.
8 to prepare a comparative emulsion (Em-21).

(J-7 solution) 3.0% by weight of gelatin and silver iodobromide fine particles (average particle size: 0.05 μm, silver iodide content: 5%)
(Mol%) is described below.

6.0 containing 0.06 mol of potassium bromide
2,000 mL of an aqueous solution containing 7.06 mol of silver nitrate in 5000 mL of a weight% gelatin solution and 20 of an aqueous solution containing 6.71 mol of potassium bromide and 0.35 mol of potassium iodide
00 mL was added at a constant speed over 10 minutes. During the formation of fine particles, the pH was controlled at 3.0 using nitric acid, and the temperature was controlled at 30 ° C. After the addition is completed, p is added using an aqueous solution of sodium carbonate.
The H was adjusted to 6.0, the ultrafiltration A was performed, and the pAg was adjusted to 8.0 at 40 ° C. with a 2N aqueous potassium bromide solution.

When the silver halide grains in this emulsion were observed with an electron microscope, hexagonal tabular monodispersed silver halide grains having an average grain size of 1.55 μm, a grain size distribution of 16% and an average aspect ratio of 8.0 were obtained. The number of particles was 90%.

(Preparation of Comparative Emulsion Em-22) In the preparation of Comparative Emulsion (Em-21), the method of JP-A-5-72658 was used.
The ultrafiltration B operation was performed instead of performing the desalting treatment according to the method described in (1). Thereafter, the temperature was raised to 60 ° C., the pBr was adjusted to 2.0 with a 2N aqueous solution of potassium bromide, and the following amount of silver halide in the J-8 solution was added in an amount of 0.79 mol in 10 minutes. And then pBr was adjusted to 1.0 with 2N aqueous potassium bromide solution.
-5 solution was added in an amount of 1.26 mol in terms of silver halide in 10 minutes, and the mixture was aged for 30 minutes.
At 40 ° C., pAg 8.06, pH
A comparative emulsion (Em) was prepared in the same manner except that it was adjusted to 5.8.
-22) was prepared.

(J-8 solution) 3.0% by weight of gelatin and silver iodobromide fine particles (average particle size: 0.05 μm, silver iodide content: 7)
(Mol%) is described below.

6.0 containing 0.06 mol of potassium bromide
2000 mL of an aqueous solution containing 7.06 mol of silver nitrate in 5000 mL of a weight% gelatin solution, and 20 an aqueous solution containing 6.57 mol of potassium bromide and 0.49 mol of potassium iodide
00 mL was added at a constant speed over 10 minutes. During the formation of fine particles, the pH was controlled at 3.0 using nitric acid, and the temperature was controlled at 30 ° C. After the addition is completed, p is added using an aqueous solution of sodium carbonate.
H was adjusted to 6.0, and the operation of ultrafiltration A was performed subsequently.

(Preparation of Emulsion Em-23 of the Present Invention) In the preparation of a comparative emulsion (Em-21), the method of JP-A-5-72658 was used.
The ultrafiltration B operation was performed instead of performing the desalting treatment according to the method described in (1). Thereafter, the temperature was raised to 60 ° C., the pBr was adjusted to 2.0 with a 2N aqueous potassium bromide solution, and 0.79 mol equivalent of the silver halide in the above J-8 solution was added in 10 minutes. And then pBr adjusted to 1.0 with a 2N aqueous potassium bromide solution to adjust the above I
-2. An amount equivalent to 1.58 mol of silver halide in liquid was added in 10 minutes, ripened for 30 minutes, and then subjected to ultrafiltration B as described above.
At 40 ° C., pAg 8.06, pH
Except for adjusting to 5.8, the emulsion of the present invention (E
m-23) was prepared.

(Preparation of Emulsion Em-24 of the Present Invention) In the preparation of the comparative emulsion (Em-21), the method of JP-A-5-72658 was used.
The ultrafiltration B operation was performed instead of performing the desalting treatment according to the method described in (1). Thereafter, the temperature was raised to 60 ° C., the pBr was adjusted to 2.0 with a 2N aqueous potassium bromide solution, and 0.79 mol equivalent of the silver halide in the above J-8 solution was added in 10 minutes. And then pBr was adjusted to 1.0 with 2N aqueous potassium bromide solution.
-2 A solution equivalent to 1.1 mol of silver halide in liquid was added in 10 minutes, ripened for 30 minutes, and then subjected to the operation of ultrafiltration B at 40 ° C at a pAg of 8.06 and a pH of 5.0.
8 in the same manner as the emulsion of the present invention (Em-
24) was prepared.

(Preparation of Emulsion Em-25 of the Present Invention) In the preparation of the comparative emulsion (Em-21), the method of JP-A-5-72658 was used.
The ultrafiltration B operation was performed instead of performing the desalting treatment according to the method described in (1). Thereafter, the temperature was raised to 60 ° C., the pBr was adjusted to 1.0 with a 2N aqueous potassium bromide solution, and 0.79 mol equivalent of the amount of silver halide in the J-2 solution was added in 10 minutes. After aging for 10 minutes, the above operation of ultrafiltration B was performed, and pAg 8.0 at 40 ° C.
6. An emulsion of the present invention (Em-25) was prepared in the same manner except that the pH was adjusted to 5.8.

When the silver halide composition of the silver halide grains contained in the emulsions Em-21 to Em-25 was confirmed by X-ray diffraction, it was found that the silver halide grains contained in the emulsions Em-23 to Em-25 contained: It was confirmed that silver chloride was contained.

Using the emulsions Em-21 to Em-25, multilayer color light-sensitive material samples 121 to 125 were prepared in the same manner as in Example 1, and evaluated. Table 6 shows the results.

[0225]

[Table 6]

Table 6 shows that the emulsions Em-23 to Em-
Coating Samples 123 to 125 using No. 25 are comparative emulsions Em.
Samples 121 and 12 using -21 and Em-22
2 showed excellent sensitivity and granularity.

Example 4 (Preparation of Comparative Emulsion Em-31) In the preparation of Comparative Emulsion (Em-21) in Example 3, the method of JP-A-5-7265 was used.
Instead of desalting according to the method described in No. 8,
The above operation of ultrafiltration B was performed. Thereafter, the temperature was raised to 50 ° C., the pBr was adjusted to 3.0 with a 2N aqueous potassium bromide solution, and 0.1 mol equivalent of the silver halide in the J-5 solution was added in 10 minutes. After aging for 10 minutes, the above operation of ultrafiltration B was performed, and pAg 8.0 at 40 ° C.
6. A comparative emulsion (Em-31) was prepared in the same manner except that the pH was adjusted to 5.8.

(Preparation of Comparative Emulsion Em-32) In the preparation of Comparative Emulsion (Em-21) in Example 3, after the silver halide grains were formed, the pAg was adjusted to 10.0 and ripened for 20 minutes. Thereafter, instead of performing the desalting treatment according to the method described in JP-A-5-72658, the above-mentioned operation of ultrafiltration B was performed. Thereafter, the temperature was raised to 50 ° C., pBr was adjusted to 2.5 with a 2N aqueous potassium bromide solution, and 0.08 mol equivalent of the amount of silver halide in the J-6 solution was added in 10 minutes. After aging for 10 minutes, the operation of the above ultrafiltration B was carried out, and a comparative emulsion (Em-32) was prepared in the same manner except that the pAg was adjusted to 8.06 and the pH was adjusted to 5.8 at 40 ° C.
Was prepared.

(Preparation of Comparative Emulsion Em-33) In the preparation of Comparative Emulsion (Em-21) in Example 3, the pAg was adjusted to 10.0 after silver halide grains were formed, followed by ripening for 20 minutes. Thereafter, instead of performing the desalting treatment according to the method described in JP-A-5-72658, the above-mentioned operation of ultrafiltration B was performed. Thereafter, the temperature was raised to 50 ° C., pBr was adjusted to 2.5 with a 2N aqueous potassium bromide solution, and 0.08 mol equivalent of the amount of silver halide in the J-6 solution was added in 10 minutes. Aged for 60 minutes, then heated to 60 ° C.
Was adjusted to 2.0, 0.79 mol equivalent of silver halide in the J-2 solution was added in 10 minutes, ripened for 20 minutes, and then subjected to the operation of the ultrafiltration B described above. Comparative emulsion (Em-33) was prepared in the same manner except that pAg was adjusted to 8.06 and pH 5.8 at 40 ° C.

(Preparation of Emulsion Em-34 of the Present Invention) Example 3
In the preparation of the comparative emulsion (Em-21), the above-described operation of ultrafiltration B was performed instead of performing the desalting treatment according to the method described in JP-A-5-72658. Thereafter, the temperature was raised to 60 ° C., and pBr was added with a 2N aqueous potassium bromide solution.
Was adjusted to 2.0, and 1.57 mol equivalent of the silver halide in the above-mentioned liquid I-2 was added in 10 minutes, ripened for 20 minutes, and then cooled to 50 ° C., and pBr was added. The solution was adjusted to 0, 0.15 mol equivalent of silver halide in the J-5 solution was added in 10 minutes, ripened for 20 minutes, and then subjected to the above-mentioned ultrafiltration B operation. At pAg 8.0
6. An emulsion of the present invention (Em-34) was prepared in the same manner except that the pH was adjusted to 5.8.

(Preparation of Emulsion Em-35 of the Present Invention) Example 3
In the preparation of the comparative emulsion (Em-21), the above-described operation of ultrafiltration B was performed instead of performing the desalting treatment according to the method described in JP-A-5-72658. Thereafter, the temperature was raised to 60 ° C., and pBr was added with a 2N aqueous potassium bromide solution.
Was adjusted to 2.0, and an amount equivalent to 1.1 mol in terms of the amount of silver halide in the J-2 solution was added in 10 minutes, and the mixture was ripened for 20 minutes.
Thereafter, the temperature was lowered to 50 ° C., and pBr was adjusted to 3.0.
0.15 mol equivalent of silver halide in the above J-5 solution was added in 10 minutes, ripened for 20 minutes, and then subjected to the above-mentioned ultrafiltration B, and pAg 8.06 at 40 ° C.
An emulsion of the present invention (Em-35) was prepared in the same manner except that the pH was adjusted to 5.8.

When the silver halide composition of the silver halide grains contained in the emulsions Em-31 to Em-35 was confirmed by X-ray diffraction, it was found that the silver halide grains contained in the emulsions Em-33 to Em-35 contained: It was confirmed that silver chloride was contained.

Using the emulsions Em-31 to Em-35, multilayer color light-sensitive material samples 131 to 135 were prepared in the same manner as in Example 1 and evaluated. Table 7 shows the results.

[0234]

[Table 7]

From Table 7, it can be seen that the emulsions Em-34 and Em of the present invention were obtained.
The coated samples 134 and 135 using -35 were coated samples 131 to 13 using the comparative emulsions Em-31 to Em-33.
3 showed excellent sensitivity and granularity.

Example 5 (Preparation of Comparative Emulsion Em-41) In the preparation of Comparative Emulsion (Em-1) in Example 1, solutions B-2, C-2,
Comparative emulsion (E) was prepared in the same manner except that addition of Solution D-2 and control of pH and pAg were performed as shown in Table 8.
m-41) was prepared.

[0237]

[Table 8]

When the silver halide grains in this emulsion were observed with an electron microscope, the average grain size was 1.38 μm, the grain size distribution was 13%, and the surface of the silver halide grains was almost (1).
11) Octahedral twin silver halide grains composed of planes and accounted for 90% of the number of grains.

(Preparation of Comparative Emulsion Em-42) In the preparation of Comparative Emulsion (Em-41), JP-A-5-72658 was used.
After desalination according to the method described in
, The pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution, 0.42 mole equivalent of the silver halide in the above-mentioned G-2 solution was added in 10 minutes, and the mixture was aged for 20 minutes. afterwards,
The above operation of ultrafiltration B was performed, and pAg
A comparative emulsion (Em-42) was prepared in the same manner except that the pH was adjusted to 8.06 and pH 5.8.

(Preparation of Comparative Emulsion Em-43) In the preparation of Comparative Emulsion (Em-41), after the silver halide grains were formed, the above H-2 solution was treated in an amount equivalent to 0.3 mol of silver halide for 5 minutes. And aged for 20 minutes.
After desalting according to the method described in US Pat. No. 72658, the temperature was raised to 60 ° C., and pB
After adjusting r to 1.7, 0.63 mol equivalent of the silver halide in the above-mentioned liquid I-2 was added in 10 minutes, ripened for 20 minutes, and then the operation of the ultrafiltration B was carried out. After applying
A comparative emulsion (Em-43) was prepared in the same manner except that the pAg was adjusted to 8.06 and the pH to 5.8 at 40 ° C.

(Preparation of Emulsion Em-44 of the Present Invention) In the preparation of a comparative emulsion (Em-41), the preparation of JP-A-5-72658 was carried out.
After desalination according to the method described in
And the pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution.
A 3 mol equivalent was added in 10 minutes, aged for 20 minutes, and then subjected to the operation of the ultrafiltration B, and then adjusted to pAg 8.06 and pH 5.8 at 40 ° C. in the same manner. An emulsion of the present invention (Em-44) was prepared.

(Preparation of Emulsion Em-45 of the Present Invention) In the preparation of the comparative emulsion (Em-41), the preparation of JP-A-5-72658 was carried out.
After desalination according to the method described in
And adjusted the pBr to 1.7 with a 2N aqueous potassium bromide solution.
A 3 mol equivalent was added in 10 minutes, aged for 20 minutes, and then subjected to the operation of the ultrafiltration B, and then adjusted to pAg 8.06 and pH 5.8 at 40 ° C. in the same manner. An emulsion of the present invention (Em-45) was prepared.

When the silver halide composition of the silver halide grains contained in the emulsions Em-41 to Em-45 was confirmed by X-ray diffraction, the silver halide grains contained in the emulsions Em-43 to Em-45 were: It was confirmed that silver chloride was contained.

Using the emulsions Em-41 to Em-45, multilayer color light-sensitive material samples 141 to 145 were prepared and evaluated in the same manner as in Example 1. Table 9 shows the results.

[0245]

[Table 9]

Table 9 shows that the emulsions Em-44 and Em of the present invention were obtained.
The coated samples 144 and 145 using -45 were coated samples 141 to 14 using the comparative emulsions Em-41 to Em-43.
3 showed excellent sensitivity and granularity.

Example 6 (Preparation of Comparative Emulsion Em-51) In the preparation of Comparative Emulsion (Em-1) in Example 1, Solution B-2, Solution C-2,
A comparative emulsion (Em-51) was prepared in the same manner except that the addition of Solution D-2 and the control of pH and pAg were controlled as shown in Table 10.

[0248]

[Table 10]

When the silver halide grains in this emulsion were observed with an electron microscope, the average grain size was 1.03 μm, the grain size distribution was 10%, and the surface of the silver halide grains was almost (1).
It was a hexahedral twin silver halide grain composed of (00) planes, and accounted for 90% of the number of grains.

(Preparation of Comparative Emulsion Em-52) In the preparation of Comparative Emulsion (Em-51), JP-A-5-72658 was used.
After desalination according to the method described in
, The pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution, 0.42 mole equivalent of the silver halide in the above-mentioned G-2 solution was added in 10 minutes, and the mixture was aged for 20 minutes. afterwards,
The above operation of ultrafiltration B was performed, and pAg
A comparative emulsion (Em-52) was prepared in the same manner except that the pH was adjusted to 8.06 and the pH was adjusted to 5.8.

(Preparation of Comparative Emulsion Em-53) In the preparation of Comparative Emulsion (Em-51), after the silver halide grains were formed, the H-2 solution was treated with a 0.3 mol equivalent of silver halide for 5 minutes. And aged for 20 minutes.
After desalting according to the method described in US Pat. No. 72658, the temperature was raised to 60 ° C., and pB
After adjusting r to 1.7, 0.63 mol equivalent of the silver halide in the above-mentioned liquid I-2 was added in 10 minutes, ripened for 20 minutes, and then the operation of the ultrafiltration B was carried out. After applying
A comparative emulsion (Em-53) was prepared in the same manner except that the pAg was adjusted to 8.06 and the pH to 5.8 at 40 ° C.

(Preparation of Emulsion Em-54 of the Present Invention) In the preparation of the comparative emulsion (Em-51),
After desalination according to the method described in
And the pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution.
A 3 mol equivalent was added in 10 minutes, aged for 20 minutes, and then subjected to the operation of the ultrafiltration B, and then adjusted to pAg 8.06 and pH 5.8 at 40 ° C. in the same manner. An emulsion of the present invention (Em-54) was prepared.

(Preparation of Emulsion Em-55 of the Present Invention) In the preparation of the comparative emulsion (Em-51),
After desalination according to the method described in
And adjusted the pBr to 1.7 with a 2N aqueous potassium bromide solution.
A 3 mol equivalent was added in 10 minutes, aged for 20 minutes, and then subjected to the operation of the ultrafiltration B, and then adjusted to pAg 8.06 and pH 5.8 at 40 ° C. in the same manner. An emulsion of the present invention (Em-55) was prepared.

When the silver halide composition of the silver halide grains contained in the emulsions Em-51 to Em-55 was confirmed by X-ray diffraction, the silver halide grains contained in the emulsions Em-53 to Em-55 were found to have the following composition: It was confirmed that silver chloride was contained.

Using the emulsions Em-51 to Em-55, multilayer color light-sensitive material samples 151 to 155 were prepared and evaluated in the same manner as in Example 1. Table 11 shows the results.

[0256]

[Table 11]

Table 11 shows that the emulsions Em-54 and E of the present invention
Coating samples 154 and 155 using m-55 were coated samples 151 to 1 using comparative emulsions Em-51 to Em-53.
The sample exhibited excellent sensitivity and granularity with respect to No. 53.

Example 7 (Preparation of Comparative Emulsion Em-61) In the preparation of Comparative Emulsion (Em-41) in Example 5, after grain formation, desalting treatment was carried out according to the method described in JP-A-5-72658. And gelatin was added and dispersed. Thereafter, the temperature was raised to 60 ° C., the pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution, and 1.31 mol equivalent of the silver halide in the J-5 solution was added in 10 minutes. After aging for 20 minutes and then performing the operation of ultrafiltration B, pA at 40 ° C.
g 8.06 and pH 5.8, and the comparative emulsion (Em-6)
1) was prepared.

When the silver halide grains in this emulsion were observed with an electron microscope, the average grain size was 1.40 μm, the grain size distribution was 13%, and the surface of the silver halide grains was almost (1).
11) Octahedral twin silver halide grains composed of planes and accounted for 90% of the number of grains.

(Preparation of Comparative Emulsion Em-62) In the preparation of Comparative Emulsion (Em-61), 1.3 mol equivalent of the silver halide of the above-mentioned J-6 solution was used in place of J-5 solution. A comparative emulsion (Em-62) was prepared in the same manner except that the above procedure was repeated.

(Preparation of Comparative Emulsion Em-63) Comparative Emulsion E
In the preparation of m-61, after forming the particles,
According to the method described in No. 2658, desalting treatment was performed, and gelatin was added and dispersed. Thereafter, the temperature was raised to 60 ° C., and the pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution.
And then ripening for 30 minutes, then adding the above solution I-2 in an amount equivalent to 2.1 moles of silver halide in 10 minutes, aging for 20 minutes, and performing the above-mentioned ultrafiltration B operation. After that, a comparative emulsion (Em-63) was prepared in the same manner except that the pAg was adjusted to 8.06 and the pH to 5.8 at 40 ° C.

(Preparation of emulsion Em-64 of the present invention)
A desalting treatment was performed according to the method described in No. 72658, and gelatin was added and dispersed. Thereafter, the temperature was raised to 60 ° C. and 2N
After adjusting the pBr to 1.7 with an aqueous potassium bromide solution, 0.5 mol equivalent of the silver halide in the J-6 solution was adjusted to 1%.
0 minutes, aged for 10 minutes, and then the above I-2
The solution was added in an amount equivalent to 2.6 moles of silver halide in 10 minutes, aged for 20 minutes, and subjected to the above-mentioned ultrafiltration B operation, and then adjusted to pAg 8.06 and pH 5.8 at 40 ° C. The emulsion of the present invention (Em-64)
Was prepared.

(Preparation of Emulsion Em-65 of the Present Invention) In the preparation of Comparative Emulsion Em-61, after the formation of the grains,
A desalting treatment was performed according to the method described in No. 72658, and gelatin was added and dispersed. Thereafter, the temperature was raised to 60 ° C. and 2N
After adjusting the pBr to 1.7 with an aqueous potassium bromide solution, 0.5 mol equivalent of the silver halide in the J-6 solution was adjusted to 1%.
0 minutes, aged for 10 minutes, then J-2
The solution was added in an amount of 2.6 moles equivalent to the amount of silver halide in 10 minutes, aged for 20 minutes, subjected to the operation of ultrafiltration B, and adjusted to pAg 8.06 and pH 5.8 at 40 ° C. The emulsion of the present invention (Em-65)
Was prepared.

When the silver halide composition of the silver halide grains contained in the emulsions Em-61 to Em-65 was confirmed by X-ray diffraction, the silver halide grains contained in the emulsions Em-63 to Em-65 were: It was confirmed that silver chloride was contained.

Using the emulsions Em-61 to Em-65, multilayer color photographic material samples 161 to 165 were prepared and evaluated in the same manner as in Example 1. Table 12 shows the results.

[0266]

[Table 12]

Table 12 shows that the emulsions Em-64 and E of the present invention
Coating samples 164 and 165 using m-65 were coated samples 161-1 using comparative emulsions Em-61 to Em-63.
With respect to 63, excellent sensitivity and granularity were exhibited.

Example 8 (Preparation of Comparative Emulsion Em-71) In the preparation of Comparative Emulsion (Em-51) in Example 6, after grain formation, desalting treatment was performed according to the method described in JP-A-5-72658. And gelatin was added and dispersed. Thereafter, the temperature was raised to 60 ° C., the pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution, and 1.31 mol equivalent of the silver halide in the J-5 solution was added in 10 minutes. After aging for 20 minutes and then performing the operation of ultrafiltration B, pA at 40 ° C.
g 8.06 and pH 5.8, and the comparative emulsion (Em-7)
1) was prepared.

When the silver halide grains in this emulsion were observed with an electron microscope, the average grain size was 1.05 μm, the grain size distribution was 9%, and the surface of the silver halide grains was almost (10%).
It was a hexahedral twin silver halide grain composed of 0) planes, and accounted for 90% of the number of grains.

(Preparation of Comparative Emulsion Em-72) In the preparation of Comparative Emulsion (Em-71), 1.3 mol equivalents of the silver halide in the above J-6 solution were used in place of J-5 solution. A comparative emulsion (Em-72) was prepared in the same manner except that the above procedure was repeated.

(Preparation of Comparative Emulsion Em-73) Comparative Emulsion E
In the preparation of m-71, after forming the particles,
According to the method described in No. 2658, desalting treatment was performed, and gelatin was added and dispersed. Thereafter, the temperature was raised to 60 ° C., and the pBr was adjusted to 1.7 with a 2N aqueous potassium bromide solution.
And then ripening for 30 minutes, then adding the above solution I-2 in an amount equivalent to 2.1 moles of silver halide in 10 minutes, aging for 20 minutes, and performing the above-mentioned ultrafiltration B operation. After that, a comparative emulsion (Em-73) was prepared in the same manner except that the pAg was adjusted to 8.06 and the pH to 5.8 at 40 ° C.

(Preparation of emulsion Em-74 of the present invention)
A desalting treatment was performed according to the method described in No. 72658, and gelatin was added and dispersed. Thereafter, the temperature was raised to 60 ° C. and 2N
After adjusting the pBr to 1.7 with an aqueous potassium bromide solution, 0.5 mol equivalent of the silver halide in the J-6 solution was adjusted to 1%.
0 minutes, aged for 10 minutes, and then the above I-2
The solution was added in an amount of 2.6 moles equivalent to the amount of silver halide in 10 minutes, aged for 20 minutes, subjected to the operation of ultrafiltration B, and adjusted to pAg 8.06 and pH 5.8 at 40 ° C. The emulsion of the present invention (Em-74)
Was prepared.

(Preparation of Emulsion Em-75 of the Present Invention) In the preparation of Comparative Emulsion Em-71, after the formation of the grains,
A desalting treatment was performed according to the method described in No. 72658, and gelatin was added and dispersed. Thereafter, the temperature was raised to 60 ° C. and 2N
After adjusting the pBr to 1.7 with an aqueous potassium bromide solution, 0.5 mol equivalent of the silver halide in the J-6 solution was adjusted to 1%.
0 minutes, aged for 10 minutes, then J-2
The solution was added in an amount equivalent to 2.6 moles of silver halide in 10 minutes, aged for 20 minutes, and subjected to the above-mentioned ultrafiltration B operation, and then adjusted to pAg 8.06 and pH 5.8 at 40 ° C. The emulsion of the present invention (Em-75)
Was prepared.

When the silver halide composition of the silver halide grains contained in the emulsions Em-71 to Em-75 was confirmed by X-ray diffraction, the silver halide grains contained in the emulsions Em-73 to Em-75 were found to have the following composition: It was confirmed that silver chloride was contained.

Using the emulsions Em-71 to Em-75, multilayer color light-sensitive material samples 171 to 175 were prepared and evaluated in the same manner as in Example 1. Table 13 shows the results.

[0276]

[Table 13]

Table 13 shows that the emulsions Em-74 and E of the present invention
The coated samples 174 and 175 using m-75 were coated samples 171 to 1 using comparative emulsions Em-71 to Em-73.
No. 73, excellent sensitivity and granularity were exhibited.

[0278]

According to the present invention, by making it possible to separately create optimum sites for chemical sensitization and color sensitization on the surface of silver halide grains, a sensitivity which cannot be achieved by the prior art. Thus, a silver halide photographic emulsion having improved fog level and a silver halide photographic light-sensitive material using the silver halide photographic emulsion could be provided.

Claims (5)

[Claims] In a silver halide photographic emulsion containing a dispersion medium and silver halide grains, the silver halide grains contain silver chloride in the outermost layer and the silver iodide in the outermost layer of the silver halide grains. A1 / A2 <1.0, where A1 is the average ratio of the silver halide grains and A2 is the average silver halide content of the silver halide grains.
A silver halide photographic emulsion, characterized in that: 2. In a silver halide photographic emulsion containing a dispersion medium and silver halide grains, the silver halide grains contain silver chloride in the outermost layer and the silver iodide in the outermost layer of the silver halide grains. Silver halide grains wherein the ratio of B1 / B2 <1.0 is 50% or more (number) when the ratio is B1 and the silver iodide content of the subsurface layer is B2. . 3. A silver halide photographic emulsion containing a dispersion medium and silver halide grains, wherein said silver halide grains contain silver chloride in the outermost layer and silver iodide in the outermost layer of said silver halide grains. When the ratio is I1 in the main plane portion and I2 in the side surface portion, 50% of tabular silver halide grains satisfying I1> I2.
A silver halide photographic emulsion characterized by the above (number). 4. A silver halide photographic emulsion containing a dispersion medium and silver halide grains, wherein the silver halide grains contain silver chloride in the outermost layer, and the silver bromide content ratio of the silver halide grains is determined by fringe. A silver halide photographic emulsion characterized in that C1 / C2 <1.0 is 50% or more (number) of tabular silver halide grains, where C1 is C1 in the portion and C2 is near the vertex. 5. A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion according to claim 1 in at least one silver halide emulsion layer on a support. .