JP3508068B2 - Silver halide photographic emulsion and silver halide photographic material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion and a silver halide photographic light-sensitive material using the same, and more specifically to a silver halide photographic light-sensitive material excellent in sensitivity and graininess. The present invention relates to a photographic emulsion and a silver halide photographic light-sensitive material using the same.

[0002]

2. Description of the Related Art The spread of photography equipment such as cameras has been increasing in recent years, and the opportunity for photography using silver halide photographic light-sensitive materials has been increasing.

The demands for higher sensitivity and higher image quality are increasing.

[0004] One of the dominant factors for high sensitivity and high image quality of silver halide photographic light-sensitive materials is silver halide grains. Silver halide aiming at higher sensitivity and higher image quality The development of particles has been promoted in the art in the past.

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

A technique for improving the sensitivity / size ratio per silver halide grain has been researched in order to further improve the sensitivity and the image quality. One of them is a tabular silver halide grain. The technology of using is Japanese Patent Laid-Open No. 58-111935
Issue 58-111936, Issue 58-111937, Issue 58-113927,
No. 59-99433, etc.

When these tabular silver halide grains are compared with so-called normal crystal silver halide grains such as octahedron, decahedron or hexahedron, when the volume of the silver halide grains is the same, the surface area is large and therefore There is an advantage that more sensitizing dye can be absorbed on the surface of the silver halide grain and the sensitivity can be further enhanced.

Further, JP-A-63-92942 discloses a technique of providing a core having a high silver iodide content inside a tabular silver halide grain, and JP-A-63-151618 discloses a hexagonal tabular silver halide grain. Are used, and their effects on sensitivity and graininess are shown.

Further, JP-A-63-106746 discloses a tabular silver halide grain having a substantially layered structure in a direction parallel to two principal planes facing each other. Have a layered structure divided by planes substantially parallel to the two opposing main planes, and the average silver iodide content of the outermost layer is the average silver iodide content of the entire silver halide grains. The technique using tabular silver halide grains each having a ratio of at least 1 mol% or more is described.

In addition to this, Japanese Patent Application Laid-Open No. 1-183644 discloses a technique using tabular silver halide grains characterized in that the silver iodide containing silver iodide has a completely uniform silver iodide distribution. There is.

There are also several reports on the technique relating to parallel twin planes in tabular silver halide grains. For example, in JP-A-63-163451, a tabular halogen having a ratio (b / a) of the longest distance (a) between two or more parallel twin planes to the grain thickness (b) of 5 or more. A technique using silver halide grains and a technique in which the number of dislocation lines are also defined are disclosed in JP-A-1-201649, and effects on sensitivity, graininess and sharpness are reported.

Further, in WO91 / 18320, the technique of using tabular silver halide grains in which the distance between at least two twin planes is less than 0.012 micron is disclosed in Japanese Patent Application No. 3-353043. Techniques using core / shell type twinned silver halide grains having an average distance between 10 and 100Å have been reported, and improvement effects on sensitivity, graininess or sharpness, pressure characteristics and graininess are described respectively. .

Regarding dislocation lines, in the prior art, for example, in JP-A-63-220238, a technique using a silver halide emulsion containing tabular silver halide grains in which the number of dislocation lines is specified is disclosed in JP-A-3- No. 175440, photographic performances relating to sensitivity and pressure resistance are improved by using the technology using silver halide photographic emulsions containing tabular silver halide grains in which dislocations are concentrated near the apexes of grains. Has been reported.

In addition, a technique for controlling carriers by metal doping is also known.

Metal doping is a technique for improving photographic characteristics by mainly incorporating a polyvalent metal compound in silver halide grains.

Techniques for doping Ir compounds into Japanese Patent Laid-Open Nos. 62-7042 and 1-105940 are disclosed in Japanese Patent Laid-Open No. 1-121844.
Techniques for doping Fe compounds are disclosed respectively.

In JP-A-3-196135 and JP-A-3-89641, a silver halide photographic emulsion produced in the presence of an oxidizing agent for silver and a silver halide photographic light-sensitive material using the same were used. The sensitivity and the effect on fogging are disclosed.

Further, for example, in JP-A-63-220238, a technique using a silver halide emulsion containing tabular silver halide grains in which the number of dislocation lines is specified is disclosed in JP-A-3-175440.
In Japanese Patent Publication No. 3-18695, a technique using a silver halide emulsion containing tabular silver halide grains in which dislocations are concentrated near the apex of the grain is disclosed. Japanese Patent Publication No. 3-31245 discloses a technique using a silver halide grain having a core / shell, and a technique relating to a silver halide grain having a three-layer core / shell structure has been studied as a technique for increasing sensitivity.

[0019]

However, these prior arts have a limit in achieving both high sensitivity and high image quality, and are not sufficient to obtain the sensitivity and image quality required in recent light-sensitive materials. Yes, the development of better technology is desired.

Therefore, an object of the present invention is to provide a silver halide photographic emulsion which gives a silver halide photographic light sensitive material having high sensitivity and excellent graininess, and a silver halide photographic light sensitive material using the same.

[0021]

The above-mentioned object of the present invention can be achieved by any of the constituents described below.

1] In a silver halide photographic emulsion containing silver halide grains and a dispersion medium, a tabular halogen in which the silver halide grains contained in the silver halide photographic emulsion have twin planes parallel to the main plane. In the tabular silver halide grains, the tabular silver halide grains are silver halide grains, and the tabular silver halide grains have a dislocation line number of 10 or more per grain in a proportion of 50% or more (number). The dislocation line has a distance x from a twin plane parallel to the main plane to the closest main plane, and a region A is formed between the twin plane parallel to the main plane and the main plane.
Is more than 50% (the number) of dislocation lines existing in the region A, the distance x / from the twin plane parallel to the main plane.
A silver halide photographic emulsion characterized by being present in the vicinity of a twin plane parallel to the main plane within 2.

2) The silver halide photographic emulsion as described in 1) above, wherein the tabular silver halide grains have two twin planes substantially parallel to the principal plane.

[ 3] The silver halide photographic emulsion as described in the above [ 1] or [ 2 ], wherein the tabular silver halide grains are monodisperse.

4] In a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, at least one of the silver halide photographic emulsion layers has the above 1) , 2) or 3]. 2. A silver halide photographic light-sensitive material comprising the silver halide photographic emulsion as described in the above item. 5] A silver halide photographic emulsion containing silver halide grains and a dispersion medium, wherein the silver halide grains contained in the silver halide photographic emulsion have tabular silver halide grains having twin planes parallel to the main plane. And the tabular silver halide grains have a dislocation line ratio of 10 or more per grain of 50% or more (the number), and the tabular silver halide grains have dislocation lines When the distance from the twin plane parallel to the principal plane to the closest principal plane is x and the area between the twin plane parallel to the principal plane and the principal plane is the area A, the area A More than 50% (number) of dislocation lines existing in
The principal plane within a distance x / 3 from a twin plane parallel to the principal plane
A silver halide photographic emulsion characterized by being present in the vicinity of a twin plane parallel to . 6] The silver halide described in 1) or 5) above, wherein the silver halide grains contained in the silver halide photographic emulsion are monodisperse emulsions of 15% or less when represented by the following formula. Photographic emulsion. Range of distribution (%) = (standard deviation / average particle size) x 100

The present invention will be described in detail below.

The silver halide grains contained in the silver halide photographic emulsion of the present invention are tabular silver halide grains having twin planes parallel to the principal plane. The tabular silver halide grains are crystallographically classified as twins.

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

In the present invention, the proportion of tabular silver halide grains in the total projected area of silver halide grains is preferably 50% or more, more preferably 60% or more, still more preferably 80%.

In the tabular silver halide grain in the present invention, the average value of the ratio of grain size to grain thickness (also referred to as aspect ratio) is preferably 1.3 or more and less than 5.0, more preferably 1.5 or more and less than 4.5, further It is more preferably 2.0 or more and less than 4.0. The average aspect ratio is obtained by averaging the ratio of grain size to thickness of all tabular grains.

The tabular silver halide grain in the present invention preferably has two twin planes parallel to the principal plane, and more preferably the tabular silver halide grain has two twin planes parallel to the principal plane. The ratio of silver halide grains
60% or more (number), more preferably 70% or more,
Most preferably, it is 80% or more.

In the present invention, the tabular silver halide grain having two twinning planes substantially parallel to the principal plane means that the silver halide grain having two twinning planes parallel to the principal plane. The ratio is 80% or more (number).

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

The average grain size of the tabular silver halide grains of the present invention is preferably 0.1 μm or more and 5.0 μm or less, more preferably
0.2 μm or more and 4.0 μm or less, most preferably 0.3 μm or more and 3.0
It is less than μm.

In the present invention, the average particle size is defined as the particle size ri when ni × ri ³ between the frequencies ni and ri ^{3 of} particles having the particle size ri is maximum. (3 significant digits and 5 digits are rounded down to the nearest digit.) (The number of measured grains is indiscriminately 1,000 or more.) The grain size ri here is the tabular silver halide grain. Is the diameter when a projected image when viewed from a direction perpendicular to the main plane is converted into a circular image of the same area.

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

The thickness of tabular silver halide grains is
Similarly, it can be obtained by actually measuring the thickness of particles on a photographed print from a direction parallel to the principal plane.

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

A monodisperse emulsion means that when the breadth of the distribution is defined by the breadth of the distribution (%) = (standard deviation / average grain size) × 100, the breadth of the distribution is 20%.
It is the following, and more preferably 15% or less.

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

For the silver halide photographic emulsion of the present invention, any silver halide such as silver iodobromide, silver iodochloride, silver chloroiodobromide and the like used in ordinary silver halide emulsions can be used. However, silver iodobromide and silver chloroiodobromide are particularly preferred.

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

In the present invention, when silver iodobromide is used,
The silver iodide content is preferably 2 mol% or more and 15 mol% or less, more preferably 3 mol% or more and 12 mol% or less, as an average silver iodide content in the entire silver halide grains. , Particularly preferably 4 mol% or more and 12 mol% or less.

The silver halide grains contained in the silver halide photographic emulsion of the present invention have a silver halide phase having a high silver iodide content inside the grains, but the silver iodide is concentrated inside the so-called core / It may be shell type particles.

When the core / shell type particles are used,
It is a particle composed of a core that serves as a core and a shell that covers the core, and the shell is formed by one or more layers. The silver iodide content of the core and shell is
Each is preferably different.

In the present invention, the inside of the tabular silver halide grains means the inside of the grain size corresponding to 80% by volume of the silver halide grains, preferably 70% inside, and more preferably 60%. More inside.

In the present invention, the silver halide phase having a high silver iodide content is a silver halide phase having an average silver iodide content of 5 mol% or more and a solid solution limit or less, and preferably 7
It is not less than mol% and not more than the solid solution limit, more preferably not less than 10 mol% and not more than the solid solution limit.

In the present invention, the solid solution limit is represented by the maximum mol% of iodide which can exist as a solid solution in silver halide. Specifically, “The Theory of Photo” edited by TH James
Graphic Process ”, 4th edition (published by Macmillan), can be determined by the method described on page 4. In the case of silver iodobromide, Imax (mol%) = 34.5 + 0.165 (t-25) (t is It can be calculated by the temperature (Celsius).

In the present invention, the content of silver iodide in the grain can be measured by the X-ray microanalysis method.

The X-ray microanalysis method will be described. Disperse silver halide grains in an electron microscope observation grid equipped with an energy dispersive X-ray analyzer on an electron microscope, and set the magnification so that one grain enters the CRT field by liquid nitrogen cooling, and AgLα and The intensity of ILα rays is integrated. The silver iodide content can be calculated using the intensity ratio of ILα / AgLα and a calibration curve prepared in advance.

The average silver iodide content near the surface of silver halide grains contained in the silver halide photographic emulsion of the present invention is 4.0
It is preferably not more than mol%, more preferably 3.5
It is at most mol%, most preferably at most 3.0 mol%.

The average silver iodide content in the vicinity of the surface of the silver halide grains contained in the silver halide grains contained in the silver halide photographic emulsion of the present invention is specifically determined by cooling the silver halide grain sample with liquid nitrogen. However, X-ray photoelectron spectroscopy (XPS
Method).

The XPS method used here is as follows.

Prior to measurement by the XPS method, the emulsion is pretreated as follows. First, a 0.05% by weight aqueous solution of proteolytic enzyme (pronase) is added to the emulsion, and gelatin is decomposed by stirring at 45 ° C for 30 minutes. Next, the emulsion particles are settled by centrifugation and the supernatant liquid is removed. Then, distilled water is added to disperse the emulsion particles in distilled water, and the mixture is centrifuged to remove the supernatant liquid. The emulsion particles are then redispersed in distilled water.
This is thinly applied on a mirror-polished silicon wafer to obtain a measurement sample.

XPS was performed using the sample thus prepared.
The average silver iodide content near the outermost surface of the silver halide grain was measured by. In order to prevent the sample from being destroyed by the above-mentioned X-ray irradiation, the sample was cooled to −110 to −120 ° C. using liquid nitrogen or liquid helium in the XPS measurement chamber.
As probe X-rays, Mg-Kα rays were irradiated at an X-ray source voltage of 15 KV and an X-ray power source current of 40 mA.

Ag3d, Br3d, and I3d3 / 2 electrons were detected to determine the halide composition near the outermost surface of the silver halide grain.
The composition ratio was calculated by correcting the integrated intensity of each measured peak with a sensitivity factor (Sensitivity Factor), and calculating the average silver iodide content near the outermost surface of the silver halide grain from these intensity ratios.

The dislocation line of the tabular silver halide grain according to the present invention is, for example, JF Hamilton, Phot.Sci.Eng., 11, 57 (1
967), T. Shiozawa, J.Soc.Phot.Sci.Japan, 35, 213 (1
It can be observed by a direct method using a transmission electron microscope at low temperature described in 972). That is, the silver halide grains taken out carefully so as not to apply pressure to the grains causing dislocations on the emulsion are placed on the mesh for electron microscope observation, and the sample to prevent damage (printout etc.) due to electron beam In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to observe more clearly using a high-voltage electron microscope (200 KV or more for particles with a thickness of 0.25 μm). .

The position and number of dislocation lines for each grain can be determined from the photograph of the grain obtained by such a method.

The position of the dislocation line of the tabular silver halide grain according to the present invention is preferably in the region of 0.40 L to L from the center of the silver halide grain toward the outer surface. It is preferably generated in the region of 0.50 L to 0.98 L. The direction of the dislocation line is approximately from the center to the outer surface, but it often meanders.

In the present invention, the center of a silver halide grain means that silver halide microcrystals are dispersed in a methacrylic resin in the same manner as in the method described in Inoue et al. Then, solidify it, make it into an ultrathin section with a microtome, and pay attention to the section sample with the maximum cross-sectional area and the cross-sectional area of 90% or more, and draw the circumscribed circle that is the minimum with respect to the section. It is the center of the circle when.

In the present invention, the distance L from the center to the outer surface is defined as the distance between the center of the circle and the point intersecting the outer circumference of the particle when a straight line is drawn from the center of the circle to the outside.

The tabular silver halide grains according to the present invention are
The ratio of the number of dislocation lines per grain being 10 or more is 50% or more (number), more preferably 60% or more, further preferably 70% or more, and most preferably 1 grain The ratio of dislocation lines being 20 or more is 70% or more (number).

In the present invention, the number of dislocation lines of silver halide grains is 10,000 or less per silver halide grain.
It is difficult to confirm the number of regions in the area of more than 10,000 and the photographic characteristics are not improved.

The tabular silver halide grain according to the present invention is characterized in that the dislocation line exists in the vicinity of the twin plane substantially parallel to the principal plane.

In the present invention, the dislocation lines are present in the vicinity of twin planes substantially parallel to the principal plane in the cross section passing through the center of the tabular silver halide grain according to the present invention and perpendicular to the principal plane. If the distance from the twin plane parallel to the principal plane to the closest principal plane is x and the area between the twin plane parallel to the principal plane and the principal plane is the area A, it exists in the area A. More than 50% (number) of dislocation lines are present within a distance x / 2 from a twin plane parallel to the principal plane, and preferably x
Within / 3.

In the present invention, the dislocation line being present in the region A means that the entire dislocation line from one end to the other end is present in the region A, and is not included in the region A. If a part of the dislocation line exists, the dislocation line is not considered to exist in the region A.

In the present invention, more than 50% (number) of dislocation lines existing in the region A exist within the distance x / 2 from the twin plane parallel to the principal plane, that is, the dislocation lines existing in the region A. For more than 50% (number) of the dislocation lines, the whole from the one end to the other end of the dislocation lines is within the distance x / 2 from the twin plane parallel to the principal plane.

The presence of dislocation lines in the vicinity of twin planes parallel to the main plane is that the silver halide photographic emulsion of the present invention is gelatinized with proteolytic oxygen,
The tabular silver halide grains contained in the silver halide photographic emulsion were embedded with methacrylic resin, a 800 Å-thick section was prepared with a diamond cutter, and observed with a transmission electron microscope. This can be confirmed by arbitrarily selecting 100 or more tabular silver halide grains showing a cut cross section and examining the number of dislocation lines and the region where they exist.

The silver halide grains contained in the silver halide photographic emulsion of the present invention are prepared by preliminarily allowing an aqueous solution containing a protective colloid and seed grains, if necessary, to be present in a reaction vessel, and if necessary silver ions, halogen ions or It is obtained by supplying fine silver halide grains to form silver halide nuclei and then growing crystals, or by growing seed grains, but it is preferable to use seed grains. Here, the seed particles can be prepared by a single jet method, a control double jet method or the like well known in the art. The halogen composition of the seed grains is arbitrary, silver bromide,
It may be any of silver iodide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, and silver chloroiodobromide, with silver bromide and silver iodobromide being preferred.

The seed particles used in the present invention may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or an irregular crystal form such as a sphere or a plate. It may be one. In these particles, {100} planes and {111} planes
Any surface ratio can be used. Further, those having a composite form of these crystal forms may be used, and particles of various crystal forms may be mixed, but it is preferable to use twin seed particles described in Japanese Patent Application No. 3-341164.

As the means for forming the silver halide photographic emulsion according to the present invention, various methods well known in the art can be used. That is, the single jet method,
The double jet method, the triple jet method and the like can be used in any combination.

The silver halide photographic emulsion of the present invention can be produced by any of the acidic method, the neutral method and the ammonia method, but it is preferable to use the acidic method or the neutral method, most preferably the neutral method. Method is used.

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

In the silver halide photographic emulsion of the present invention,
In order to control the silver iodide content inside and on the surface of tabular silver halide grains, avoid a growth environment in which silver halide grains grow only in the main plane direction or in the lateral direction. The growth conditions are such that the shell growth is relatively even in the plane direction and the side direction, and the recrystallization that inhibits the shell from covering the high silver iodide content phase inside the silver halide grain is prevented. It can be selected appropriately.

In the production of silver halide grains contained in the silver halide photographic emulsion of the present invention, the concentration of the additive solution containing halide ions, silver ions or silver halide fine particles in the growth of the silver halide grains and the growth pAg It is important to select the concentration of gelatin in the aqueous solution in which the silver halide grains are grown and the growth temperature. The concentration of the additive liquid containing halide ions and silver ions is preferably 0.5 to 4 mol / l, more preferably 1.5 to 3.5 mol / l. The concentration of the addition liquid containing fine silver halide grains is preferably 0.3 to 2.0 ml / l, more preferably 0.5 to 1.5 mol / l. Growth pAg is 7.8
Is preferably 9.7, more preferably 8.0 to 9.4, and even more preferably 8.2 to 9.2. The gelatin concentration in the aqueous solution in which silver halide grains are grown is preferably 0.5 to 4.0%. The growth temperature is preferably 60 to 90 ° C, more preferably 70 to 80 ° C.

In the present invention, during growth from seed grains, silver iodide is controlled by appropriately controlling the flow rate balance of an aqueous solution containing halide ions, an aqueous solution containing silver ions, and an additive solution containing fine silver halide grains. It is preferred that the formation of a silver halide phase containing is carried out.

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

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

In the silver halide photographic emulsion of the present invention,
In order to introduce dislocations into the silver halide grains, for example, a method of providing a specific high iodine phase inside the silver halide grains can be used. In this case, the high iodine phase is silver iodide,
Silver iodobromide and silver chloroiodobromide are preferable, silver iodide or silver iodobromide is more preferable, and silver iodide is particularly preferable.

As a method for this, for example, a conversion method by adding an iodide salt alone, or, for example, JP-A-58-58
-108526, 59-133540 and 59-162540 may be used.

When the conversion method is carried out by adding the iodide salt alone, the addition amount of the iodide salt is 1
The amount is preferably 10 ^-6 to 10 ^-1 mol, and more preferably 3 × 10 ^{-5 to} 3 × 10 ^-2 mol per mol. The addition can be performed using a funnel or a pump, but the addition time is preferably within 10 minutes, more preferably within 5 minutes. The timing of addition can be arbitrarily set depending on the position where the dislocation line is desired to be introduced.

The present invention grows dislocations laterally by growing tabular silver halide grains having a high aspect ratio while introducing dislocations relatively early in the production of tabular silver halide grains. After that, unnecessary iodide ions are removed by washing with water and desalting, and then the tabular silver halide grains washed with water and desalted are
This could be achieved by applying isotropic core / shell growth.

In the present invention, more specifically, in the production of tabular silver halide grains, the total amount of silver nitrate used is 30%.
%, Preferably 20% or less, at a relatively early stage of silver halide grain growth using the aforementioned iodide salt conversion method to introduce dislocations and thereafter less than 50% of the total amount of silver nitrate used, preferably Up to 30% of tabular silver halide grains are preferably pAg without using silver halide solvent
It is grown at 8.8 to 9.7, more preferably 9.0 to 9.4, and then washed with water and desalted, which is a known method, for example, Research Disclosure 176.
It was carried out by the method described in No. 43, section II.

Thereafter, the tabular silver halide grains are further supplied with a water-soluble silver salt and / or a water-soluble alkali halide and / or silver halide fine particles in an aqueous solution containing a protective colloid so as to correspond to the rest of the total amount used. It was possible to form tabular silver halide grains having dislocations substantially in the vicinity of twin planes by performing growth using silver nitrate. The growth pAg in this growth process is 7.8 to 9.0.
Is preferable, and more preferably 8.2 to 8.8.

The silver halide photographic emulsion of the present invention can be subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research Disclosure No.17643, No.18716 and No.308119 (respectively,
(Hereinafter referred to as RD17643, RD18716 and RD308119). The following shows the locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-A-A, B, C, D, H, I, J Item 23-24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Silver halide of the present invention Known photographic additives that can be used in the construction of color photographic light-sensitive materials using photographic emulsions are also described in Research Disclosure below. Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, XIII C Item 25 to 26 Light absorber 1003 VIII 25 to 26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25 to 26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricants 1006 XII 27 650 Activators / coating aids 1005 XI 26 to 27 650 Matte agents 1007 XVI Developer (included in light-sensitive material) 1011 XXB Item Color photographic light-sensitive using the silver halide photographic emulsion of the present invention Various couplers may be used in constructing the material, specific examples of which are described in Research Disclosure below.

The following are relevant description points.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VIIC-G item Magenta coupler 1001 VII-D item VIIC-G item Cyan coupler 1001 VII-D item VIIC-G item Colored coupler 1002 Item VII-G Item VIIG Item DIR coupler 1001 VII-F item VIIF item BAR coupler 1002 VII-F item Other useful residues Release coupler 1001 VII-F item Alkali soluble coupler 1001 VII-E item Silver halide photograph of the present invention Additives used in constructing a color photographic light-sensitive material using an emulsion can be added by the dispersion method described in RD308119XIV.

When a silver halide photographic emulsion of the present invention is used to construct a color photographic light-sensitive material, the above-mentioned RD17643 28 is used.
The supports described on page RD18716 pp. 647-8 and RD308119 XVII can be used.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can be provided with auxiliary layers such as the filter layer and the intermediate layer described in the above item RD308119VII-K.

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention can have various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above item RD308119VII-K.

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

The color photographic light-sensitive material using the silver halide photographic emulsion of the present invention is described in RD17643, pages 28 to 29, RD18716 61.
Development can be carried out by a usual method described on page 5 and XIX of RD308119.

[0095]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 (Preparation of twinned seed emulsion TI) By the method shown below,
A seed emulsion having two parallel twin planes was prepared.

A. Ocein gelatin 80.0 g Potassium bromide 47.4 g 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) in 20 wt% methanol Make up to 8000.0 ml with 0.24 ml distilled water.

[0098] B.   Silver nitrate 1200.0 g Make up to 1600.0 ml with distilled water.

[0099] C.   Ossein gelatin 32.2g   Potassium bromide 790.0 g   70.34 g of potassium iodide Make up to 1600.0 ml with distilled water.

D. Ammonia water 470.0 ml Solution A and solution C were vigorously stirred at 40 ° C., and solution B and solution C were added by the double jet method in 7.7 minutes to generate nuclei. During this time, pBr was kept at 1.60.

Thereafter, the temperature was lowered to 20 ° C. over 30 minutes. Furthermore, the D liquid was added in 1 minute, and the aging was continued for 5 minutes. The KBr concentration during aging was 0.03 mol / l, and the ammonia concentration was 0.66 mol / l.

After completion of aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. A 10% by weight aqueous gelatin solution was added to the desalted emulsion, and the mixture was stirred and dispersed at 60 ° C. for 30 minutes, and distilled water was added to the emulsion to give an emulsion of 5360 g.

When the seed emulsion grains were observed with an electron microscope, they had two twin planes parallel to each other.

The average grain size of this seed emulsion grain is 0.217 μm, 2
The number of grains having parallel twin planes was 75% (number ratio) of all grains.

(Preparation of Comparative Emulsion (Em-1)) A comparative emulsion (Em-1) was prepared using the following 5 kinds of solutions.

(Solution A-1) Ocein gelatin 66.5 g Distilled water 3227.0 ml 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) 10% by weight methanol solution 2.50 ml Seed emulsion (T-1) 98.5 g Make up to 3500.0 ml with distilled water.

[0107] (Solution B-1)   3.5N silver nitrate aqueous solution 4702.0ml (Solution C-1)   Potassium bromide 2499.0 g Make up to 6000 ml with distilled water.

(Solution D-1) Fine grain emulsion (*) consisting of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) 1897.0 g * 0.06 mol of potassium iodide whose preparation method is shown below is used. 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 2000 ml of 7.06 mol of potassium iodide were added to 5000 ml of a 6.0 wt% gelatin solution containing the mixture over 10 minutes. The temperature during fine particle formation was controlled at 40 ° C. The finished weight was 12.53 kg.

(Solution E-1) 1.75N Potassium Bromide Aqueous Solution Required amount of Solution A-1 was added to a reaction vessel, and while vigorously stirring,
Solution B-1 to solution D-1 were added according to the combination shown in Table 1 by the simultaneous mixing method to grow a seed crystal to prepare a core / shell type silver halide emulsion.

Here, (1) solution B-1, solution C-1 and solution D-1 addition rates, (2) solution B-1 and solution C
The addition rate of -1 was changed in a function-like manner with respect to time so as to correspond to the critical growth rate of silver halide grains, and small grains were generated in addition to growing seed crystals and polydispersion was achieved by Ostwald ripening. The addition rate was controlled appropriately so that the above phenomenon would not occur.

Further, the temperature of the solution in the reaction vessel was controlled at 75 ° C. and pAg was controlled at 9.0 over the entire area of the crystal growth. pA
Solution E-1 was added as needed for g control. The pH was not controlled but remained in the pH 6.0 range throughout grain growth.

The amount of silver added at that time with respect to the addition time of the addition solution and the silver iodide content of the silver halide phase during formation are also shown in Table 1.

After grain growth, desalting treatment was carried out according to the method described in Japanese Patent Application No. 4-59351, 1.19 l of a 20% by weight aqueous gelatin solution was added, and the mixture was dispersed at 50 ° C for 30 minutes and then at 40 ° C. The pH was adjusted to 5.80 and the pBr was adjusted to 3.55.

The silver halide grains contained in the obtained silver halide emulsion were monodisperse tabular silver halide grains having an average grain size of 1.34 μm (projected area equivalent circle diameter), an average aspect ratio of 2.6 and a grain size distribution of 18%. Met.

[0115]

[Table 1]

(Preparation of Comparative Emulsion (Em-2)) Comparative Emulsion (Em-2)
In the preparation of m-1), a comparative emulsion (Em-2) was prepared in the same manner except that the following solution L-1 was added in 30 seconds when the amount of added silver was 50%.

(Solution L-1) 100 ml of an aqueous solution containing 0.005 mol of potassium iodide per mol of emulsion (Em-1) (Preparation of silver halide emulsion (Em-3) of the present invention) A silver halide emulsion (Em-3) of the present invention was prepared using the solution.

(Solution A-2) Ocein gelatin 67.0 g Distilled water 3176.0 ml HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 20% by weight methanol solution of 9.77) 1.25 ml of seed emulsion (T-1) 0.268 mol Distilled water to make 3500.0 ml.

[0119] (Solution B-2)   0.5N silver nitrate aqueous solution 991 ml (Solution C-2)   58.96 g of potassium bromide   Oscein gelatin 39.64g Make up to 991 ml with distilled water.

[0120] (Solution D-2)   3.5N silver nitrate aqueous solution 4538ml (Solution E-2)   Potassium bromide 2082.5g   Ocein gelatin 200g Make up to 5000 ml with distilled water.

[0121] (Solution F-2)   Consists of 3% by weight of gelatin and silver iodide grains (average grain size 0.05 μm)     Fine grain emulsion (*) 2100.6 g * The preparation method is shown below.

6.0% by weight containing 0.06 mol of potassium iodide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added to 5000 ml of the gelatin solution of 10 ml over 10 minutes. The pH during fine particle formation is 2.0 using nitric acid.
The temperature was controlled at 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. The finished weight was 12.53 kg.

(Solution G-2) 1.75N potassium bromide aqueous solution (Solution L-2) Emulsion (Em-3) 100 ml aqueous solution containing 0.005 mol of potassium iodide per mol (Solution M-2) Ocein gelatin 180.0 g Distilled water 7300 ml 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) 10% by weight methanol solution 2.5 ml Distilled water 7500 ml To finish.

Solution A-2 was added to the reaction vessel, and while vigorous stirring, Solution B-2 to Solution F-2 were added according to the combination shown in Table 2 by the simultaneous mixing method to grow a seed crystal. .

At the time when the addition of the amount of silver used was 10%, Solution L-2 was added for 30 seconds, and the growth was continued.
When the addition of 20% of the amount of silver to be used was completed, the addition was temporarily stopped, desalting and dispersion were carried out by the method described in Japanese Patent Application No. 4-59351, and then this emulsion was transferred to the solution (M-2). The suspended solution B-2 to solution F-2 was restarted and the core /
A silver halide photographic emulsion containing shell type silver halide grains was prepared.

Here, (1) solution B-2, solution C-2 and solution F-2 addition rates, (2) solution D-2, solution E-
2 and solution F-2 addition rates, and (3) solution D-2 and solution E-2 addition rates were changed in a function-like manner with respect to time to generate small particles in addition to growing seed crystals. The addition rate was controlled according to Table 2 so that polydispersion due to Ostwald ripening did not occur.

The solution temperature in the reaction vessel was maintained at 75 ° C. throughout the entire crystal growth, and pAg was controlled according to Table 2. G-1 was added as needed for pAg control.

Table 2 shows the grain size at that time with respect to the addition time of the reaction vessel, and the silver iodide content of the silver halide phase forming the surface.

After grain growth, desalting treatment was carried out according to the method described in Japanese Patent Application No. 4-59351, and then 1.19 l of 20% by weight gelatin aqueous solution was added, followed by dispersion at 50 ° C for 30 minutes and at 40 ° C.
The H was adjusted to 5.80 and the pBr was adjusted to 3.55.

[0130]

[Table 2]

(Preparation of Silver Halide Emulsion (Em-4) of the Present Invention) Solutions B-1 and C were prepared in the preparation of comparative emulsion (Em-1).
Addition of -1, D-1 and pAg are performed according to Table 3 below, and at the time when the amount of added silver is 10%, the following solution L-3 is added for 30 seconds and the growth is continued. Then, the addition was temporarily stopped, and desalting and dispersion were carried out by the method described in Japanese Patent Application No. 4-59351. Then, this emulsion was transferred to the following solution (M-3) and suspended, Solution B-1 to Solution E. The addition of -1 was restarted to prepare a silver halide photographic emulsion containing core / shell type silver halide grains.

(Solution L-3) Emulsion (Em-1) Aqueous solution containing 0.01 mol of potassium iodide per mol 150 ml (Solution M-3) Ocein gelatin 180.0 g Distilled water 7300 ml HO (CH ₂ CH ₂ O) 10% by weight methanol solution of _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 2.5 ml Distilled water to 7500 ml

[0133]

[Table 3]

(Preparation of Silver Halide Emulsion (Em-5) of the Present Invention) Solutions B-1 and C were prepared in the preparation of comparative emulsion (Em-1).
-1, D-1 was added and pAg was performed according to the following Table 4, and at the time when the amount of added silver was 6%, the following solution L-4 was added for 30 seconds, and the growth was continued. Then, the addition was temporarily stopped, and desalting and dispersion were carried out by the method described in Japanese Patent Application No. 4-59351. Then, this emulsion was transferred to the following solution (M-4) and suspended, Solution B-1 to Solution E. The addition of -1 was restarted to prepare a silver halide photographic emulsion containing core / shell type silver halide grains.

(Solution L-4) Emulsion (Em-1) Aqueous solution containing 0.005 mol of potassium iodide per mol 100 ml (Solution M-4) Ocein gelatin 150.0 g Distilled water 6900 ml HO (CH ₂ CH ₂ O) 10% by weight methanol solution of _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 2.5 ml Make up to 7,000 ml with distilled water

[0136]

[Table 4]

(Preparation of Silver Halide Emulsion (Em-6) of the Present Invention) Solutions B-1 and C were prepared in the preparation of comparative emulsion (Em-1).
-1, D-1 was added and pAg was performed according to Table 5 below, and at the time when the amount of added silver was 10%, the following solution L-5 was added for 30 seconds, and the growth was continued. Then, the addition was temporarily stopped, and desalting and dispersion were carried out by the method described in Japanese Patent Application No. 4-59351. Then, this emulsion was transferred to the following solution (M-5) and suspended, Solution B-1 to Solution E. The addition of -1 was restarted to prepare a silver halide photographic emulsion containing core / shell type silver halide grains.

(Solution L-5) Emulsion (Em-1) Aqueous solution containing 0.005 mol of potassium iodide per mol 150 ml (Solution M-5) Ocein gelatin 100.0 g Distilled water 5800 ml HO (CH ₂ CH ₂ O) 20 wt% methanol solution of _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 2.5 ml Distilled water to 6000 ml

[0139]

[Table 5]

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

A-II ossein gelatin 80.0 g potassium bromide 47.4 g 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) 20% by weight methanol solution of 0.24 ml Make up to 8000.0 ml with distilled water.

[0142] B-II   Silver nitrate 1200.0 g Make up to 1600.0 ml with distilled water.

[0143] C-II   Ossein gelatin 32.2g   Potassium bromide 790.0 g   70.34 g of potassium iodide Make up to 1600.0 ml with distilled water.

D-II Ammonia water 470.0 ml To the A-II solution vigorously stirred at 40 ° C., the B-II solution and the C-II solution were added by the double jet method in 7.7 minutes to generate nuclei. During this period, pBr was kept at 1.70.

Thereafter, the temperature was lowered to 20 ° C. over 30 minutes. Further, the D-II solution was added for 1 minute, and then the mixture was aged for 5 minutes.

After completion of aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. A 10% by weight aqueous gelatin solution was added to the desalted emulsion, and the mixture was stirred at 60 ° C. for 30 minutes, and then distilled water was added to complete an emulsion of 5360 g.

When the seed emulsion grains were observed with an electron microscope, they had two twin planes parallel to each other.

The average grain size of this seed emulsion grain is 0.214 μm, 2
The number of grains having parallel twin planes was 84% (number ratio) of all grains.

(Preparation of Silver Halide Emulsion (Em-7) of the Present Invention) In preparation of comparative emulsion (Em-1), seed emulsion (T-I) was used instead of seed emulsion (T-I) in solution A-1. II) is used, addition of solutions B-1, C-1, and D-1 and pAg are performed according to the above Table 3, and at the time when the amount of added silver is 10%, the solution L-3 is added for 30 seconds, Growth continued, and the addition was temporarily suspended when the amount of added silver was 25%.
Desalting and dispersion were carried out by the method described in No. 351, then, this emulsion was transferred into the above solution (M-3), and the suspended addition of Solution B-1 to Solution E-1 was restarted. A silver halide photographic emulsion containing shell type silver halide grains was prepared.

(Preparation of Comparative Silver Halide Emulsion (Em-8)) A comparative silver halide emulsion (Em-8) was prepared using the following 9 kinds of solutions.

(Solution A-8) Ocein gelatin 67.0 g Distilled water 3176.0 ml HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 20% by weight methanol solution of 9.77) 1.25 ml of seed emulsion (T-1) 0.268 mol Distilled water to make 3500.0 ml.

[0152] (Solution B-8)   0.5N silver nitrate aqueous solution 991 ml (Solution C-8)   58.96 g of potassium bromide   Oscein gelatin 39.64g Make up to 991 ml with distilled water.

[0153] (Solution D-8)   3.5N silver nitrate aqueous solution 4538ml (Solution E-8)   Potassium bromide 2082.5g   Ocein gelatin 200g Make up to 5000 ml with distilled water.

[0154] (Solution F-8)   Consists of 3% by weight of gelatin and silver iodide grains (average grain size 0.05 μm)     Fine grain emulsion (*) 2100.6 g * The preparation method is shown below.

6.0% by weight containing 0.06 mol of potassium iodide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added to 5000 ml of the gelatin solution of 10 ml over 10 minutes. The pH during fine particle formation is 2.0 using nitric acid.
The temperature was controlled at 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. The finished weight was 12.53 kg.

(Solution G-8) 1.75N potassium bromide aqueous solution Required amount (solution L-8) Emulsion (Em-8) Aqueous solution containing 0.001 mol potassium iodide per mol 100 ml (Solution M-8) Ocein Gelatin 180.0 g Distilled water 7300 ml 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) 10% by weight methanol solution 2.5 ml Distilled water Make up to 7500 ml.

Solution A-8 was added to the reaction vessel, and while vigorous stirring, Solution B-8 to Solution F-8 were added according to the combination shown in Table 6 by the simultaneous mixing method to grow a seed crystal. .

At the time when the addition of the amount of silver used was 10%, the solution L-8 was added for 30 seconds, and the growth was continued.
When the addition of 20% of the amount of silver used was completed, the addition was suspended, desalting and dispersing were carried out by the method described in Japanese Patent Application No. 4-59351, and then this emulsion was transferred to a solution (M-8). The suspended addition of Solution B-8 to Solution F-8 was restarted to prepare a silver halide photographic emulsion containing core / shell type silver halide grains.

Here, (1) addition rates of solution B-8, solution C-8 and solution F-8, (2) solution D-8, solution E-
8 and solution F-8, and (3) solution D-8 and solution E-8 were added in a function-like manner with respect to time to generate small particles in addition to growing seed crystals. The addition rate was controlled according to Table 6 so that polydispersion due to Ostwald ripening did not occur.

In addition, the solution temperature in the reaction vessel was kept at 75 ° C. over the entire area of crystal growth, and pAg was controlled according to Table 6. G-8 was added as needed for pAg control.

Table 6 shows the grain size at that time with respect to the addition time of the reaction vessel, and the silver iodide content of the silver halide phase forming the surface.

After grain growth, desalting treatment was carried out according to the method described in Japanese Patent Application No. 4-59351, then 1.19 l of a 20% by weight gelatin aqueous solution was added, and the mixture was dispersed at 50 ° C. for 30 minutes and then at 40 ° C.
The H was adjusted to 5.80 and the pBr was adjusted to 3.55.

[0163]

[Table 6]

(Preparation of Comparative Emulsion (Em-9)) Comparative Emulsion (E
m-8) was prepared in the same manner except that the following solution L-9 was used instead of the solution L-8.
9) was prepared.

(Solution L-9) Emulsion (Em-9) 100 ml aqueous solution containing 0.0025 mol of potassium iodide per mol (Preparation of silver halide emulsion (Em-10) of the present invention) Comparative emulsion (Em-8 In the preparation of ()), the emulsion (Em-10) of the present invention was prepared in the same manner except that the following solution L-8 was used instead of the solution L-8.

(Solution L-10) 100 ml of an aqueous solution containing 0.004 mol of potassium iodide per mol of emulsion (Em-10) (Preparation of twinned seed emulsion T-III) Two parallel emulsions were prepared by the following method. A seed emulsion having twin planes was prepared.

A-III Ocein gelatin 80.0 g Potassium bromide 47.4 g 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) 20% by weight methanol solution of 0.24 ml Make up to 8000.0 ml with distilled water.

[0168] B-III   Silver nitrate 1200.0 g Make up to 1600.0 ml with distilled water.

[0169] C-III   Ossein gelatin 32.2g   Potassium bromide 790.0 g   70.34 g of potassium iodide Make up to 1600.0 ml with distilled water.

D-III Ammonia water 470.0 ml A-III solution which was vigorously stirred at 40 ° C. was added with B-III solution and C-II.
Liquid I was added by the double jet method for 7.7 minutes to generate nuclei. During this period, pBr was kept at 1.70.

Thereafter, the temperature was lowered to 20 ° C. over 30 minutes. Further, D-III solution was added over 1 minute, and then 3
Aged for a minute.

After completion of aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. A 10% by weight aqueous gelatin solution was added to the desalted emulsion, and the mixture was stirred and dispersed at 60 ° C. for 30 minutes, and distilled water was added to the emulsion to give an emulsion of 5360 g.

When the seed emulsion grains were observed with an electron microscope, they had two twin planes parallel to each other.

The average grain size of this seed emulsion grain is 0.198 μm, 2
The number of grains having parallel twin planes was 83% (number ratio) of all grains.

(Preparation of Silver Halide Emulsion (Em-11) of the Present Invention) In the preparation of the comparative emulsion (Em-1), the seed emulsion (T-1) was replaced with the seed emulsion (T- III) is used, and solutions B-1, C-1, and D-1 are added and
pAg was carried out in accordance with the following Table 7 and at the time when the amount of added silver was 10%, the solution L-3 was added for 30 seconds, and then the growth was continued. -
Desalting and dispersion were carried out by the method described in No. 59351, and thereafter, this emulsion was transferred into the above solution (M-3) and the interrupted addition of solution B-1 to solution E-1 was restarted. A silver halide photographic emulsion containing shell type silver halide grains was prepared.

[0176]

[Table 7]

(Preparation of Comparative Emulsion (Em-12)) Comparative Emulsion (Em-12)
In the preparation of m-1), a comparative emulsion (Em-12) was prepared in the same manner except that the following solution L-12 was added for 30 seconds when the amount of added silver was 50%.

(Solution L-12) 100 ml of an aqueous solution containing 0.002 mol of potassium iodide per mol of emulsion (Em-12) The characteristics of silver halide emulsions (Em-1) to (Em-12) are shown in Table 8. .

[0179]

[Table 8]

Silver halide emulsions (Em-1) to (Em-12)
To each of them was optimally chemically sensitized. These emulsions were designated as (Emulsion D) in the following sample formulations to prepare multilayer color light-sensitive material samples Nos. 101 to 112.

On the triacetyl cellulose film support, layers having the following compositions were sequentially formed from the support side.

First layer Alumina sol AS-100 (aluminum oxide) 0.8 g (manufactured by Nissan Chemical Industries, Ltd.) Second layer diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg (silver halide color light-sensitive material) Preparation) Each layer having the composition shown below was provided on the above-mentioned transparent support to prepare samples 101 to 112 which are multilayer color light-sensitive materials.

[0183] The coating amount (Composition of photosensitive layer) The silver halide and colloidal silver, the amount expressed in terms of metallic silver in the unit of g / m ^2, also, the coupler, the additive g / m ²
The amount expressed in units is also shown for the sensitizing dye in terms of the number of moles per mole of silver halide in the same layer.

Sample 1st layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High boiling point Solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: Low sensitivity red sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0 × 10 ^-4 Sensitizing dye (SD -2) 1.4 × 10 ^-4 sensitizing dye (SD-3) 1.4 × 10 ^-5 sensitizing dye (SD-4) 0.7 × 10 ^-4 cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) 0.04 DIR compound (D-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 Fourth layer: medium-sensitive red-sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-1) ) 1.7 × 10 ^-4 sensitizing dye (SD-2) 0.86 × 10 ^-4 sensitizing dye (SD-3) 1.15 × 10 ^-5 sensitizing dye (SD-4) ) 0.86 × 10 ^-4 Cyan coupler (C-1) 0.33 Colored cyan coupler (CC-1) 0.013 DIR compound (D-1) 0.02 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Fifth layer: High sensitivity red sensitivity Layer Emulsion D 0.95 Sensitizing dye (SD-1) 1.0 × 10 ^-4 Sensitizing dye (SD-2) 1.0 × 10 ^-4 Sensitizing dye (SD-3) 1.2 × 10 ^-5 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 6th layer: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 7th layer: Low Sensitive green sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.38 Sensitizing dye (SD-4) 4.6 × 10 ^-5 Sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta coupler (M-1 ) 0.14 Magenta coupler (M-2) 0.14 Colored magenta coupler (CM-1) 0.06 High boiling point solvent (OIL-4 ) 0.34 Gelatin 0.70 Eighth layer: Intermediate layer Gelatin 0.41 Ninth layer: Medium sensitivity green sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-6) 1.2 × 10 ^-4 sensitization Dye (SD-7) 1.2 × 10 ^-4 Sensitizing Dye (SD-8) 1.2 × 10 ^-4 Magenta Coupler (M-1) 0.04 Magenta Coupler (M-2) 0.04 Colored Magenta Coupler (CM-1) 0.017 DIR Compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (OIL-4) 0.12 Gelatin 0.50 Layer 10: High sensitivity green sensitive layer Emulsion D 0.95 Sensitizing dye (SD-6) 7.1 × 10 ^{− 5} Sensitizing dye (SD-7) 7.1 × 10 ^-5 Sensitizing dye (SD-8) 7.1 × 10 ^-5 Magenta coupler (M-1) 0.09 Colored magenta coupler (CM-1) 0.011 High boiling point solvent (OIL-) 4) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling solvent (OIL-2) 0.19 Gelatin 1.10 12th layer: Low sensitivity blue sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitizing dye (SD-9) 6.3 × 10 ^-5 Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 High boiling point solvent (OIL-2) 0.42 Gelatin 1.40 13th layer: High sensitivity blue sensitive layer Silver iodobromide emulsion C 0.15 Silver iodobromide emulsion E 0.80 Sensitizing dye (SD-9) 8.0 × 10 ^-5 Sensitizing dye (SD-11) 3.1 × 10 ^-5 Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, iodide) Silver halide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Latin 0.65 15th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating Auxiliary agent Su-1, Dispersion agent Su-
2. Viscosity modifier, Hardener H-1, H-2, Stabilizer ST-
1, antifoggant AF-1, two kinds of AF-2 having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and a preservative DI-1
Was added.

The emulsions used in the above samples are as follows. The average particle size is shown as a particle size converted into a cube.
Further, each emulsion was optimally subjected to gold / sulfur sensitization.

[0186]

[Table 9]

[0187] The sample was applied by a multi-slide hopper type coater at the first time, and the first to eighth layers were simultaneously applied, and at the second time, the ninth to 16th layers were simultaneously applied thereon.
Sample 101 had a silver coating amount of 6.25 g / m ² , a dry film thickness of 18 μm, and a specific photographic sensitivity of 420.

[0188]

[Chemical 1]

[0189]

[Chemical 2]

[0190]

[Chemical 3]

[0191]

[Chemical 4]

[0192]

[Chemical 5]

[0193]

[Chemical 6]

[0194]

[Chemical 7]

[0195]

[Chemical 8]

[0196]

[Chemical 9]

[0197]

[Chemical 10]

[0198]

[Chemical 11]

These samples were exposed to white light for sensitometry and processed in the following processing steps to obtain sensitivity and RM.
S granularity was evaluated.

[Treatment process (38 ° C)] Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water wash 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water wash 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry The composition of the processing liquid used in the processing step is as follows.

[0201] [Color developer]   4-amino-3-methyl-N-ethyl-     N- (β-hydroxyethyl) -aniline ・ sulfate 4.75g   Anhydrous sodium sulfite 4.25g   Hydroxylamine 1/2 sulfate 2.0g   Anhydrous potassium carbonate 37.5g   Sodium bromide 1.3g   Nitrilotriacetic acid / trisodium salt (monohydrate) 2.5 g   1.0 g of potassium hydroxide Add water to make 1 liter and adjust to pH = 10.0.

[Bleach] Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter and pH was adjusted with ammonia water.
Adjust to 6.0.

[Fixer] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

[0204] [Stabilizer]   Formalin (37% aqueous solution) 1.5 ml   Conidax (manufactured by Konica Corporation) 7.5 ml Add water to make 1 liter.

The sensitivity (S) is a relative value of the reciprocal of the amount of received light which gives a density of fog density + 0.1, and the green sensitivity of the sample 101 is 100.

The RMS granularity is 1000 times the standard deviation of the fluctuation of the density value that occurs when the density of the minimum density +1.0 is scanned by a microdensitometer with an aperture scanning area of 250 μm ² , and the RMS value of sample 101 is The relative value when 100 is shown.

Table 10 shows the evaluation results of the sensitivity and RMS granularity of the coated samples Nos. 101 to 112 using (Em-1) to (Em-12) as relative values.

[0208]

[Table 10]

From Table 10, sample Nos. 103 to 107, 110 and 111 using the silver halide photographic emulsions (Em-3) to (Em-7), (Em-10) and (Em-11) of the present invention are shown. Are comparative emulsions (Em-1), (Em-2), (Em-8), (Em-9), (Em
-12) was superior to the sample Nos. 101, 102, 108, 109 and 112, and the RMS value was also better than that of the comparative emulsion.

Example 2 Coating samples Nos. 101 to 112 used in Example 1 were prepared as follows:
After each storage under the conditions described above, exposure for sensitometry was performed with white light, and similarly, the sensitivity and the RMS granularity were relatively evaluated by setting the value of Sample No. 101 in Condition A to 100 ° C., and the results are shown in Table 9. It was shown to.

(Conditions) A: 40 ° C., 70% RH for 3 days B: 60 ° C., 55% RH for 3 days The sensitivity (S) is the reciprocal of the amount of received light that gives a density of fog density +0.1. Relative value of the sample under condition A (No. 11)
The green sensitivity is shown as a relative value when the green sensitivity is 100.

[0212] The RMS particle degree is 1000 times the fluctuation of the density value that occurs when the density of the minimum density + 1.0 is scanned by a microdensitometer with an aperture scanning area of 250 µm ² , and the sample under condition A (No. 11) The RMS value is shown as a relative value when the RMS value is 100.

Table 11 shows the evaluation results of the sensitivity and RMS granularity of the coated samples (No. 101) to (No. 112) using (Em-1) to (Em-12).

[0214]

[Table 11]

From Table 11, the silver halide photographic emulsion of the present invention
Samples using (Em-3) to (Em-7), (Em-10), (Em-11)
(No. 103) to (No. 107), (No. 110), and (No. 111) are comparative emulsions (Em-1), ((Em-1), () even when stored under A or B conditions. Em-2), (Em-8), (Em-9),
It was superior to Sample Nos. 101, 102, 108, 109 and 112 using (Em-12), and the RMS granularity was also better than that of using the comparative emulsion.

[0216]

According to the present invention, it is possible to provide a silver halide photographic emulsion which gives a silver halide photographic light sensitive material having high sensitivity and excellent graininess, and a silver halide photographic light sensitive material using the same.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI G03C 7/00 530 G03C 7/00 530 (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/035

Claims (6)

(57) [Claims] 1. A silver halide photographic emulsion comprising silver halide grains and a dispersion medium, wherein the silver halide grains contained in the silver halide photographic emulsion are tabular halogen having twin planes parallel to the main plane. It is a silver halide grain and the tabular silver halide grain has 10 dislocation lines per grain.
In the tabular silver halide grains, the ratio of which is equal to or more than 50% (the number), and the dislocation lines in the tabular silver halide grains, the distance from the twin plane parallel to the principal plane to the nearest principal plane is x, When the area between the twin planes parallel to the main plane is the area A, more than 50% (the number) of dislocation lines existing in the area A are twins parallel to the main plane. A silver halide photographic emulsion characterized by being present in the vicinity of a twin plane parallel to the principal plane within a distance x / 2 from the plane . 2. A silver halide photographic emulsion according to claim 1, wherein the tabular silver halide grains have two twin planes substantially parallel to the principal plane. 3. The silver halide photographic emulsion according to claim 1 or 2, wherein the tabular silver halide grains are monodisperse. 4. A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, wherein at least one of said silver halide photographic emulsion layers has a halogenated structure according to claim 1. A silver halide photographic light-sensitive material comprising a silver photographic emulsion. 5. A silver halide photographic emulsion containing silver halide grains and a dispersion medium, wherein the silver halide grains contained in the silver halide photographic emulsion are tabular halogen having twin planes parallel to the principal plane. It is a silver halide grain and the tabular silver halide grain has 10 dislocation lines per grain.
In the tabular silver halide grains, the ratio of which is equal to or more than 50% (the number), and the dislocation lines in the tabular silver halide grains, the distance from the twin plane parallel to the principal plane to the nearest principal plane is x, When the area between the twin planes parallel to the main plane is the area A, more than 50% (the number) of dislocation lines existing in the area A are twins parallel to the main plane. A silver halide photographic emulsion characterized by being present in the vicinity of a twin plane parallel to the principal plane within a distance x / 3 from the plane . 6. The silver halide according to claim 1, wherein the silver halide grains contained in the silver halide photographic emulsion are a monodisperse emulsion of 15% or less when represented by the following formula. Photographic emulsion. Range of distribution (%) = (standard deviation / average particle size) x 100