JP2002055412A - Silver halide color negative photographic sensitive material and photographic product with built-in silver halide color negative photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material having high sensitivity, good graininess and high saturation in color reproduction and capable of suppressing the increase of fog, the lowering of sensitivity and the deterioration of graininess caused by exposure to environmental radiation in storage after production. SOLUTION: The silver halide color photographic sensitive material has at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one blue-sensitive silver halide emulsion layer on the base and has an ISO sensitivity of >=640 and 3.0-9.0 g/m2 total silver content. Each of the color-sensitive silver halide emulsion layers comprises two or more silver halide emulsion layers different from each other in sensitivity and the silver content of the maximum sensitivity one of the two or more emulsion layers is 0.3-1.3 g/m2. Flat platy silver halide grains having an average aspect ratio of >=8 occupy >=50% of the total projected area of all silver halide grains contained in at least two of the maximum sensitivity layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-sensitivity color negative photographic light-sensitive material and a photographic product having a built-in high-sensitivity color negative photographic light-sensitive material and provided with an exposure function. A color negative photographic light-sensitive material for high-sensitivity photography in which the color reproduction has a high saturation, and an increase in fog over time from the production of the photosensitive material until use thereof, a decrease in sensitivity, and an improvement in granular deterioration are improved; The present invention relates to a photographic product having a built-in photosensitive material provided with an exposure function and incorporating a color negative photographic photosensitive material.

[0002]

2. Description of the Related Art In recent years, high-sensitivity photosensitive materials have been put on the market one after another due to advances in the technology of photosensitive materials for photography. The shooting area has been expanded by increasing the sensitivity of the photosensitive material, such as shooting without a strobe in a dark room, shooting with a high-speed shutter using a telephoto lens in sports photography, and so on.

Further, a photographic product with a built-in photosensitive material provided with an exposure function for incorporating a color negative photographic photosensitive material (so-called,
(Film with lens) is widely used for its convenience, but in order to supply it at a low cost, the function is limited even if the shutter speed and aperture are fixed and the flash is attached. There are many. To compensate for this, a high-sensitivity color negative is often used as a built-in color negative photographic light-sensitive material.

In order to increase the sensitivity of a light-sensitive material, it is common practice in the art to produce a high-speed light-sensitive material by using a method of increasing the size of silver halide emulsion grains in combination with other techniques. Has become. Increasing the size of silver halide emulsion grains increases sensitivity to some extent,
As long as the silver halide content is kept constant, there is a great disadvantage that the number of silver halide emulsion grains is inevitably reduced, and thus the number of development starting points is reduced, and the graininess is greatly impaired.

In order to increase the size of silver halide emulsion grains and to increase the number of development starting points even slightly, high-sensitivity color negative photosensitive materials are allowed to have various performances such as desilvering during bleach-fix processing. Designs have been made in which the content of silver halide emulsion grains, that is, the amount of coated silver, is increased within the range.

Japanese Patent Application Laid-Open No. 63-226650 discloses that the photosensitive material of high sensitivity and high image quality produced as described above has the following disadvantages.

That is, there is a problem in that the photographic performance deteriorates such as an increase in fogging, a decrease in sensitivity, and a granular deterioration before the photosensitive material is manufactured and used. This performance degradation
The main factor is the exposure of photosensitive silver halide emulsion grains to natural radiation such as gamma rays and cosmic rays emitted from building materials and the ground. It is known that the performance of photosensitive materials is deteriorated by X-rays or high-energy radiation.
In the case of a high-sensitivity color negative photosensitive material having an SO sensitivity of 640 or more, the deterioration of the performance was unexpectedly large even by naturally existing extremely weak radiation. To prevent this, for example, Research Disclosure Magazine 2561
As described in No. 0 (August 1985), a method of cutting radiation by using a material having a high absorption coefficient of radiation represented by lead in a packaging material or a storage of photosensitive material is considered. However, in order to fully implement this method, it is not possible to achieve the purpose unless heavy metals such as lead are made to a considerable thickness, and it is impossible to supply ordinary consumers easily and cheaply. near. JP-A-63-22665
No. 0 discloses a technique for improving the performance deterioration due to natural radiation by reducing the total silver content of the color negative photosensitive material and the silver content of the high-sensitivity layer. Therefore, when the size of the silver halide emulsion grains is increased, as long as the content of silver halide is kept constant, the number of silver halide emulsion grains necessarily decreases, and thus the number of development starting points decreases. No specific solution has been proposed for the problem of the great disadvantage that the graininess is greatly impaired.

On the other hand, as a technique for improving the graininess of a high-sensitivity photosensitive material, it is known that silver halide grains having a high aspect ratio may be used.
(U.S. Pat.) 4,434,226 and the like.

Although the invention is effective for achieving both high sensitivity and granularity, the present inventors have studied that, when a silver halide grain having an aspect ratio of 8 or more is used in a color negative photosensitive material, It has been found that, since the silver halide grains have a large surface area as compared with conventional silver halide grains, the development inhibitors released from the DIR couplers are excessively captured, and a phenomenon that the layering effect is hardly exerted occurs. As a result, it has been found that a serious problem occurs for a color negative photosensitive material in which the saturation of color reproduction is greatly reduced.

[0010] The problem of the decrease in the color saturation of the color reproduction is caused by using a large amount of silver coated on the high-speed emulsion layer in order to improve the graininess. According to the present inventors, the use of grains having an aspect ratio of 8 or more in the high-sensitivity emulsion layer causes a greater problem, because the larger the grain size, the larger the increase in surface area due to the aspect ratio of 8 or more. Was found.

In recent years, it has been found that a selenium sensitizer is preferably used in combination with a gold sensitizer and a sulfur sensitizer in order to increase the sensitivity of a silver halide emulsion. As a result of investigations by the present inventors, it has been found that the use of this technique makes it possible to reduce the size of silver halide grains required to obtain the same sensitivity, and thus makes it less susceptible to environmental radiation. However, at the same time, it was also found that a problem that the saturation of color reproduction was lowered occurred.

In order to compensate for the decrease in the color saturation of the color reproduction,
Although it is sufficient to use a large amount of DIR coupler, not only does this increase the cost, but also an excessive development inhibitor is released from the DIR coupler during the development of the emulsion in the medium- and low-speed emulsion layers, Since the sensitivity is lowered, there arises a problem that the total coated silver amount of the photosensitive material must be increased.

In order to produce a high-sensitivity color negative photosensitive material excellent in all of the above-mentioned improvements in performance degradation due to environmental radiation, improvement in graininess immediately after coating, and improvement in color reproduction chroma, it is completely impossible with conventional techniques. It was possible.

In order to incorporate a compound capable of reacting with an oxidized form of an aromatic primary amine-based color developing agent to release a bleaching accelerator into a photographic light-sensitive material, it is necessary to promote desilvering during development processing. It is widely known that changes in sensitivity and graininess due to the inclusion in color negative photographic materials, especially the granularity caused by exposure to environmental radiation when contained in high-sensitivity color negative photographic materials. Little was known about the effects on gender changes until discovered by the present inventors.

In order to concretely form the electron trapping zone in the silver halide grains, reference should be made to the knowledge of doping with a metal ion dopant, for example, the descriptions in JP-A-2-20854 and JP-A-7-72569. it can. However, in addition to the above, when tabular silver halide grains having an electron capture zone are used in a high-sensitivity layer of a high-sensitivity color negative photographic light-sensitive material, the effect on photographic changes due to exposure to environmental radiation, particularly The effect of changing the silver content in the material was largely unknown until discovered by the present inventors.

[0016]

SUMMARY OF THE INVENTION The present invention provides high sensitivity, good granularity, high color reproducibility, high saturation, and increased fog caused by exposure to environmental radiation during storage after production, and reduced sensitivity. It is an object of the present invention to provide a high-sensitivity color negative photographic material in which the deterioration of graininess is minimized, and a photographic product with a built-in light-sensitive material provided with an exposure function for incorporating the high-sensitivity color negative photographic material.

[0017]

SUMMARY OF THE INVENTION As a result of diligent efforts, the present inventors have found that the objects of the present invention can be achieved by the following means.

(1) At least one each on the support
A silver halide color negative photographic material having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, and having an ISO sensitivity of 640 or more. The silver halide emulsion layers having the same color sensitivity have a silver content of not less than 3.0 g / m ^{2 and not} more than 9.0 g / m ² , and at least two halogens having different sensitivities; A silver halide emulsion layer, wherein the silver content of the highest sensitive emulsion layer among the two or more emulsion layers having the same color sensitivity is 0.3 g / m ² or more and 1.3 g / m ² or less; Among the two or more emulsion layers having the same color sensitivity, at least 50% or more of the total projected area of the silver halide grains contained in at least two of the most sensitive layers are composed of tabular silver halide grains. The average aspect ratio of the tabular silver halide grains is 8 or more. The silver halide color negative photographic light-sensitive material characterized.

(2) Among the two or more emulsion layers having the same color sensitivity, the silver content of the highest sensitivity layer is 0.3 g / m ² or more and 1.2 g / m ² or less. The silver halide color negative photographic material as described in (1) above.

(3) At least one of the silver halide emulsion layers containing an emulsion in which the tabular silver halide grains occupy 50% or more of the total projected area is contained per mole of silver contained in the emulsion layer. The silver halide color negative photographic light-sensitive material as described in (1) or (2), further comprising 2 × 10 ^-6 mol or more and 5 × 10 ^-6 mol or less of a selenium sensitizer.

(4) At least one each on the support
A silver halide color negative photographic material having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, and having an ISO sensitivity of 640 or more. The silver halide emulsion layers having the same color sensitivity have a silver content of not less than 3.0 g / m ^{2 and not} more than 9.0 g / m ² , and at least two halogens having different sensitivities; The total silver content of the highest-sensitive emulsion layer among two or more emulsion layers having the same color sensitivity is 1.5 g / m ² or more and 3.5 g / m ² or less. And at least 50% of the total projected area of the silver halide grains contained in at least two of the two or more emulsion layers having the same color sensitivity are tabular silver halide grains, The average aspect ratio of the tabular silver halide grains is 8 or more. The silver halide color negative photographic light-sensitive material characterized and.

(5) The total silver content of the highest-sensitivity emulsion layer of two or more emulsion layers having the same color sensitivity is 1.5 g /
The silver halide color negative photographic light-sensitive material according to (4) that m is ² or more 3.0 g / m ² or less.

(6) At least one of the silver halide emulsion layers containing an emulsion in which the tabular silver halide grains occupy 50% or more of the total projected area is contained per mole of silver contained in the emulsion layer. The silver halide color negative photographic light-sensitive material as described in (4) or (5), further comprising 2 × 10 ^-6 mol or more and 5 × 10 ^-6 mol or less of a selenium sensitizer.

(7) The color photographic light-sensitive material of the present invention is characterized in that at least one layer contains a compound which reacts with an oxidized aromatic primary amine-based color developing agent to release a bleaching accelerator ( The silver halide color negative photographic material according to any one of 1) to (6).

(8) An emulsion containing tabular silver halide grains having an average aspect ratio of 8 or more contained in at least two of the two or more emulsion layers having the same color sensitivity. The silver halide color negative photographic material according to any one of (1) to (7), wherein at least one of the silver halide grains contains tabular silver halide grains having an electron capture zone.

(9) In a photographic product having a built-in color photographic light-sensitive material and provided with an exposure function, the color photographic light-sensitive material described in any one of (1) to (8) above, A photographic product with a built-in photosensitive material provided with an exposure function, which is a photosensitive material.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
It has long been known that the sensitivity to γ-rays and X-rays can be increased by increasing the amount of silver halide emulsion grains coated. H. By Herz The Photogr
aphic Action of Ionizing
Radiation (Viley-Intersiege
nce, 1969). However, as described above, in a high-sensitivity color photographic light-sensitive material, if the silver content is increased to a certain level or more, the so-called natural radiation such as extremely weak γ-rays present in our living environment causes a realistic storage period. During the exposure, performance deterioration such as an increase in fogging and deterioration in graininess occurred, and the performance deterioration was larger than expected.

The color negative photographic light-sensitive material of the present invention (hereinafter, referred to as “color negative photographic material”)
"Color photographic materials" and "photo-sensitive materials")
Having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer on a support;
A color photographic light-sensitive material having a sensitivity of 640 or more, wherein each silver halide emulsion is composed of two or more silver halide emulsion layers having different sensitivities.

In a color photographic light-sensitive material, when an emulsion layer of the same color-sensitive layer is composed of two or more emulsion layers having different sensitivities, a so-called granular disappearance effect is utilized. It was common sense to obtain a high-quality color photographic light-sensitive material by designing with a high silver content. However, in a high-sensitivity color photographic light-sensitive material having an ISO sensitivity of 640 or more, increasing the silver content in the emulsion layer having a higher sensitivity is more effective than increasing the silver content in the emulsion layer having a lower sensitivity. Deterioration of deterioration is large, so the silver content of the emulsion layer with the highest sensitivity of the same color sensitivity is kept low so that the performance of high-sensitivity color photographic materials after storage due to the influence of natural radiation is practically used. It is preferable because it can be suppressed to a level that does not cause a problem. In one embodiment of the present invention, the silver content of the most sensitive emulsion layer of each of the red-sensitive layer, green-sensitive layer and blue-sensitive layer of the color photographic light-sensitive material of the present invention is 0.3 g / m ² or more and 1 g / m ² or more. .
It is 3 g / m ² or less, more preferably 0.3 g / m ² or more and 1.2 g / m ² or less. In another embodiment of the present invention, the total silver content of the most sensitive emulsion layers of the red-sensitive layer, green-sensitive layer and blue-sensitive layer of the color photographic light-sensitive material of the present invention is 1.5 g / g. m ^{2 to} 3.5 g / m ² , more preferably 1.5 g / m ^{2 to} 3.0 g
/ M ² or less. The content of all silver contained in the color photographic light-sensitive material of the present invention is 3.0 g / m ² or more and 9.0 g.
/ M ² or less, and more preferably 3.0 g / m ² or more and 8.0 g / m ² or less.

The silver content referred to here is a value obtained by converting all silver contents such as silver halide and metallic silver into silver. Several methods are known for analyzing the silver content of the photosensitive material, and any method may be used. For example, elemental analysis using a fluorescent X-ray method is simple.

The color photographic light-sensitive material of the present invention has an ISO sensitivity of 640 or more, more preferably 800 or more.

The emulsion which can be used in the light-sensitive material of the present invention preferably relates to a silver iodobromide or silver chloroiodobromide tabular grain emulsion. The tabular silver halide grains in the present invention are silver halide grains having two or more twin planes in parallel and having a tabular morphology.

In tabular silver halide grains (hereinafter also referred to as tabular grains), the aspect ratio means the ratio of the diameter to the thickness of silver halide. That is, it is a value obtained by dividing the diameter of each silver halide grain by the thickness. Here, the diameter refers to the diameter of a circle having an area equal to the projected area of the silver halide grains when the grains are observed with a microscope or an electron microscope.

The color photographic light-sensitive material of the present invention has a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer on a support. And at least two silver halide emulsion layers having the highest sensitivity among the two or more silver halide emulsion layers (preferably, two or more silver halide emulsion layers).
At least 50% of the total projected area of the silver halide grains contained in the highest green-sensitive layer and the highest red-sensitive layer) is tabular silver halide grains, and the average aspect ratio is 8%.
Or more, more preferably 10 or more, and most preferably 12 or more. The upper limit of the aspect ratio is preferably 50.

As in the present invention, natural radiation coverage is improved by reducing the silver content of the sensitive layer, and a high aspect ratio flat plate having an average aspect ratio of 8 or more is used for the sensitive layer. Thus, even if the silver content of the sensitive layer was reduced, deterioration of the graininess could be prevented. Further, by reducing the silver content of the high-sensitivity layer containing the high aspect ratio flat plate, the problem that the multi-layer effect due to the use of the high aspect ratio flat plate becomes difficult to be obtained was solved.

In the present invention, the average aspect ratio is the average of the aspect ratios of all tabular grains in the emulsion. As an example of the method of measuring the aspect ratio, there is a method of obtaining a circle equivalent diameter and thickness of each particle by taking a transmission electron micrograph by a replica method. In this case, the thickness is calculated from the length of the shadow of the replica.

The shape of the tabular grains in the present invention is usually
Hexagon. The hexagonal shape means that the shape of the main plane of the tabular grain is hexagonal and the adjacent side ratio (maximum side length / minimum side length) is 2 or less. Preferably, the adjacent side ratio is 1.6 or less, more preferably, the adjacent side ratio is 1.
2 or less. It goes without saying that the lower limit is 1.0. Particularly in high aspect ratio grains, triangular tabular grains increase in tabular grains. Triangular tabular grains appear when Ostwald ripening has progressed too much. In order to substantially obtain hexagonal tabular grains, it is preferable to shorten the time for ripening as much as possible. For that purpose, it is necessary to devise a method of increasing the ratio of tabular grains by nucleation. As described in JP-A-63-11928 by Saito, when silver ions and bromide ions are added to a reaction solution by a double jet method, silver ions must be added to the reaction solution in order to increase the probability of generation of hexagonal tabular grains. Preferably, one or both of the aqueous solution and the aqueous bromide ion solution contains gelatin.

The hexagonal tabular grains used in the present invention have nucleation and
It is formed by the Ostwald ripening and growing process. Each of these steps is important in suppressing the spread of the particle size distribution, but since it is impossible to narrow the spread of the size distribution generated in the above-described step in a subsequent step, the size is not increased in the first nucleation step. Care must be taken that the distribution does not spread. An important point in the nucleation process is the relationship between the nucleation time at which silver ions and bromide ions are added to the reaction solution by the double jet method to cause precipitation, and the temperature of the reaction solution. JP-A 63-63 by Saito
No. 92942 describes that the temperature of the reaction solution during nucleation is preferably in the range of 20 to 45 ° C. in order to improve the monodispersibility. Further, Japanese Patent Laid-Open Publication No.
No. 40 states that the preferred temperature during nucleation is 60 ° C. or less.

In order to obtain monodisperse tabular grains having a large aspect ratio, gelatin may be additionally added during grain formation. At this time, the gelatin used is disclosed in
-148897 and -NH ₂ group of the chemically modified gelatin (gelatin as described in JP-A 11-143002 when chemically modified, newly -COOH group at least 2
It is preferable to use gelatin which has been introduced individually. This chemically modified gelatin is a gelatin characterized in that at least two or more carboxyl groups are newly introduced when an amino group in the gelatin is chemically modified, and it is preferable to use trimellitized gelatin. It is also preferred to use succinated gelatin. This gelatin is preferably added before the growth step, and more preferably immediately after the nucleation. The addition amount is 60% or more, preferably 80% or more, and particularly preferably 90% or more, based on the weight of the entire dispersion medium during the formation of the particles.

The tabular grain emulsion comprises silver iodobromide or silver chloroiodobromide. Although silver chloride may be contained, the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less, or 0 mol%. Regarding the silver iodide content, the coefficient of variation of the grain size distribution of the tabular grain emulsion is preferably 30% or less, so that the silver iodide content was 20 mol%.
The following is preferred. By reducing the silver iodide content, it becomes easy to reduce the variation coefficient of the distribution of the equivalent circle diameter of the tabular grain emulsion. In particular, the coefficient of variation of the grain size distribution of the tabular grain emulsion is preferably 20% or less, and the silver iodide content is preferably 10 mol% or less.

It is preferable that the tabular grain emulsion has a structure in the grains with respect to silver iodide distribution. In this case, the structure of the silver iodide distribution may be a double structure, a triple structure, a quadruple structure, or even a higher structure.

In the present invention, the tabular grains are preferably
It has a dislocation line. Dislocation lines of tabular grains are described, for example, in J. Am. F.
Hamilton, Photo. Sci. Eng. , 1
1, 57, (1967); Shiozawa, J .;
Soc. Photo. Sci. Japan, 3,5,21
3, (1972) can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocation lines on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by the electron beam. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, a clearer image can be observed by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.

The number of dislocation lines in the tabular grains of the present invention is preferably 10 or more per grain on average. More preferably, the average is 20 or more per particle. When dislocation lines are densely present or when dislocation lines are observed to intersect each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count to about 10, 20, or 30 pieces, and it can be clearly distinguished from the case where there are only a few pieces. The average number of dislocation lines per particle is determined as a number average by counting the number of dislocation lines for 100 particles or more. Hundreds of dislocation lines may be observed.

The dislocation lines can be introduced, for example, near the outer periphery of the tabular grains. In this case, the dislocation is almost perpendicular to the outer periphery, and a dislocation line is generated from the position of x% of the length from the center of the tabular grain to the side (outer periphery) to the outer periphery. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape formed by connecting the start positions of the dislocation lines is similar to the particle shape, but may not be a perfect similar shape and may be distorted. This type of dislocation number is not found in the central region of the grain.
The direction of the dislocation lines is approximately (211) crystallographically, but often meanders, and may intersect each other.

The tabular grains may have dislocation lines almost uniformly over the entire area on the outer periphery, or may have dislocation lines at local positions on the outer periphery. That is, in the case of a hexagonal tabular silver halide grain as an example, dislocation lines may be limited only near six vertices, or dislocation lines may be limited only near one of the vertices. Conversely, dislocation lines may be limited to only sides excluding the vicinity of the six vertices.

Further, dislocation lines may be formed over a region including the centers of two parallel main planes of the tabular grains. When dislocation lines are formed over the entire area of the main plane, the direction of the dislocation lines may be approximately (211) crystallographically when viewed from a direction perpendicular to the main plane, but may be in the (110) direction or In some cases, the dislocation lines are formed randomly, and the length of each dislocation line is also random. In some cases, the dislocation lines are observed as short lines on the main plane, and in other cases, they are observed as long lines reaching the side (outer circumference). is there. Dislocation lines are sometimes straight or meandering. They also often intersect with each other.

As described above, the position of the dislocation line may be limited to the outer periphery, the main plane, or a local position, or may be formed by combining these.
That is, they may exist simultaneously on the main plane on the outer periphery.

The introduction of dislocation lines into tabular grains can be achieved by providing a specific high silver iodide phase inside the grains.
In this case, a high silver iodide phase may be provided with a high silver iodide region discontinuously. Specifically, the high silver iodide phase inside the grains is obtained by preparing a base grain, providing a high silver iodide phase, and covering the outside with a phase having a lower silver iodide content than the high silver iodide phase. Can be The silver iodide content of the tabular grains of the base is lower than that of the high silver iodide phase, and is preferably 0% based on the silver halide of the base.
-20 mol%, more preferably 0-15 mol%.

The high silver iodide phase inside the grains means a silver halide solid solution containing silver iodide. As silver halide in this case, silver iodide, silver iodobromide and silver chloroiodobromide are preferable, but silver iodide or silver iodobromide (iodide relative to silver halide contained in the high silver iodide phase) is preferable. The silver halide content is more preferably 10 to 40 mol%). The high silver iodide phase inside the grain (hereinafter, referred to as the internal silver iodide high phase) is defined on the side, corner,
It is desirable to control the conditions for forming the base grains, the conditions for forming the internal silver iodide-rich phase, and the conditions for forming the phase covering the outside thereof, in order to selectively exist at any place on the surface. The conditions for forming the base particles are pA
The important factors are g (the logarithm of the reciprocal of silver ion concentration) and the presence, type, amount and temperature of the silver halide solvent. By controlling the pAg during the growth of the base grains to 8.5 or less, more preferably 8 or less, the internal high silver iodide phase is formed in the vicinity of the apex of the base grains or at the surface when the internal high silver iodide phase is formed later. It can be selectively present above. On the other hand, by performing the pAg at the time of growing the base grains at 8.5 or more, more preferably at 9 or more,
An internal silver iodide-rich phase can be present on the side of the base grain. These threshold values of pAg change up and down depending on the temperature and the presence / absence, type and amount of the silver halide solvent. When, for example, thiocyanate is used as the silver halide solvent, the threshold value of the pAg shifts toward a higher value.

Particularly important as the pAg at the time of growth is the pAg at the end of the growth of the base particle. On the other hand, even when the pAg at the time of growth does not satisfy the above value, it is possible to control the selected position of the internal silver iodide-rich phase by adjusting the pAg after the growth of the base grains and ripening. is there. At this time, ammonia, amine compounds, thiourea derivatives, and thiocyanate salts are effective as silver halide solvents. The formation of the internal silver iodide-rich phase can use a so-called conversion method. In this method, during the grain formation, there is a method of adding a halogen ion having a lower solubility of a salt for forming a silver ion than a halogen ion forming a grain or a vicinity of the surface of the grain at that time. In the present invention, it is preferable that the amount of the added halogen ions having low solubility is not less than a certain value (related to the halogen composition) with respect to the surface area of the particles at that time. For example, it is preferable to add a certain amount or more of KI to the surface area of the silver halide grains at that time during grain formation. Specifically, it is preferable to add 8.2 × 10 ⁻⁵ mol / m ² or more of iodide salt.

A more preferred method of forming an internal silver iodide-rich phase is to add an aqueous silver salt solution simultaneously with the addition of an aqueous halide salt solution containing an iodide salt.

For example, AgNO is added simultaneously with the addition of the KI aqueous solution.
₃ Add the aqueous solution by double jet. At this time, the addition start time and the addition end time of the KI aqueous solution and the AgNO ₃ aqueous solution may be shifted from each other and may be changed. The addition molar ratio of the AgNO ₃ aqueous solution to the KI aqueous solution is preferably 0.1 or more, more preferably 0.5 or more. More preferably, it is 1 or more. The total added molar amount of the AgNO ₃ aqueous solution may be in the silver excess region with respect to the halogen ions and the added iodine ions in the system. It is preferable that the pAg at the time of addition of the halide aqueous solution containing iodide ions and the addition of the silver salt aqueous solution by the double jet decrease with the addition time by the double jet. The pAg before the start of addition is
It is preferably 6.5 or more and 13 or less. More preferably 7.0
It is preferably 11 or more and 11 or less. The pAg at the end of the addition is 6.5
More preferably, it is at most 10.0.

In carrying out the above method, it is preferred that the solubility of the mixed silver halide is as low as possible. Therefore, the temperature of the mixed system for forming a high silver iodide phase is preferably 30 ° C. or more and 80 ° C. or less, more preferably 30 ° C. or more and 7 ° C. or less.
0 ° C. or less.

More preferably, the formation of the internal high silver iodide phase can be carried out by adding fine grain silver iodide, fine grain silver iodobromide, fine grain silver chloroiodide or fine grain silver chloroiodobromide. In particular, it is preferable to add fine grain silver iodide.
These fine particles usually have a particle size of 0.01 μm or more and 0.1 μm or less, but 0.01 μm or less or 0.1 μm or less.
Fine particles having a particle size of m or more can also be used.
The methods for preparing these fine silver halide grains are described in JP-A-1-183417, JP-A-2-44335,
No. 183644, No. 1-183645, No. 2-435
No. 34 and No. 2-43535 can be referred to. An internal high silver iodide phase can be provided by adding and ripening these fine grain silver halides. When the fine particles are dissolved by ripening, the above-mentioned silver halide solvent can be used. It is not necessary that all of the added fine particles dissolve and disappear immediately, and it is sufficient that the fine particles dissolve and disappear when the final particles are completed.

The position of the internal silver iodide-rich phase is measured from the center of a hexagon or the like on which the grains are projected, and preferably exists in a range of 5 mol% or more and less than 100 mol% with respect to the silver amount of the whole grains. More preferably, it is in the range of 20 mol% or more and less than 95 mol%, and particularly preferably in the range of 50 mol% or more and less than 90 mol%. The amount of silver halide forming these internal silver iodide-rich phases is represented by the amount of silver and is 50 mol% of the total amount of silver in the grains.
Or less, more preferably 20 mol% or less. These high silver iodide phases are the prescription values for the production of silver halide emulsions, not the values obtained by measuring the halogen composition of the final grains by various analytical methods. The internal silver iodide-rich phase often disappears in the final grain due to recrystallization or the like in the shelling process, and the above-mentioned silver content is all related to the prescribed value.

Therefore, in the final grain, dislocation lines can be easily observed by the above-mentioned method. However, in the internal silver iodide phase introduced for introducing dislocation lines, the silver iodide composition at the boundary changes continuously. For this reason, it is often not possible to confirm it as a clear phase. Regarding the halogen composition of each part of the grain, X-ray diffraction, EPMA (also known as XMA) method (a method of detecting silver halide composition by scanning silver halide grains with an electron beam), and ESCA (also known as XPS) ) Method (a method of irradiating X-rays and dispersing photoelectrons coming out of the particle surface) and the like.

The outer phase covering the inner high silver iodide phase is lower than the silver iodide content of the high silver iodide phase, and preferably the silver iodide content is contained in the outer phase to be covered. 0 to 30 mol%, more preferably 0 to 30 mol% based on the amount of silver halide
It is 20 mol%, most preferably 0 to 10 mol%.

The temperature and pAg at the time of forming the outer phase covering the inner silver iodide-rich phase are arbitrary, but the preferred temperature is 3 p.
0 ° C. or higher and 80 ° C. or lower. Most preferably, it is 35 ° C or more and 70 ° C or less. Preferred pAg is 6.5 or more and 1
1.5 or less. In some cases, it is preferable to use the above-mentioned silver halide solvent, and the most preferable silver halide solvent is a thiocyanate salt.

Further, as another method for introducing dislocation lines into tabular grains, there is a method using an iodide ion releasing agent as described in JP-A-6-11782, which is preferably used. It is also possible to introduce a dislocation line by appropriately combining the method of introducing a dislocation line and the above-described method of introducing a dislocation line.

The variation coefficient of the intergranular iodine distribution of the silver halide grains used in the present invention is preferably 20% or less. It is more preferably at most 15%, particularly preferably at most 10%. If the coefficient of variation of the iodine content distribution of each silver halide is greater than 20%, it is not preferable because the contrast does not become high and the sensitivity decreases when pressure is applied.

The method for producing silver halide grains having a narrow intergranular iodine distribution used in the present invention may be any of the known methods, for example, a method of adding fine particles as disclosed in JP-A-1-183417 and the like. A method using an iodide ion releasing agent as described in JP-A-2-68538 can be used alone or in combination.

The silver halide grains of the present invention preferably have a coefficient of variation of iodine distribution between grains of not more than 20%. The most preferred method for monodispersing the iodine distribution between grains is described in JP-A-3-213845. The method described can be used. That is, fine silver halide grains containing 95 mol% or more of silver iodide are mixed with an aqueous solution of a water-soluble silver salt and a water-soluble halide (95 mol% or more of iodine) in a mixer provided outside the reaction vessel. (I.e., containing an ion) is formed by mixing, and is supplied into the reaction vessel immediately after the formation, whereby a monodispersed interparticle iodine distribution can be achieved. Here, the reaction vessel refers to a vessel that causes nucleation and / or crystal growth of tabular silver halide grains.

As described in JP-A-3-213845, the following three techniques can be used for a method of adding a mixture prepared in a mixer and a preparation means used therefor. Immediately after the microparticles are formed in the mixer, they are added to the reaction vessel. Powerful and efficient stirring is performed in the mixer. Injection of the aqueous protective colloid solution into the mixer.

The protective colloid used above may be injected into the mixer alone, or may be mixed with an aqueous halide salt solution or an aqueous silver nitrate solution containing the protective colloid and injected into the mixer. The concentration of the protective colloid is 1% by weight or more, preferably 2 to 5% by weight. Examples of the polymer compound having a protective colloid action on silver halide grains used in the present invention include polyacrylamide polymer, amino polymer, polymer having thioether group, polyvinyl alcohol, acrylic acid polymer, polymer having hydroxyquinoline, and cellulose. , Starch, acetal, polyvinylpyrrolidone, terpolymer and the like, but it is preferable to use low molecular weight gelatin. The molecular weight of the low molecular weight gelatin is preferably 40,000 or less, more preferably 30 or less.
000 or less.

The grain formation temperature in preparing fine silver halide grains is preferably 35 ° C. or lower, particularly preferably 25 ° C. or lower. The temperature of the reaction vessel to which the fine silver halide grains are added is 50 ° C. or higher, preferably 60 ° C. or higher,
More preferably, it is 70 ° C. or higher.

The grain size of the fine silver halide grains used in the present invention can be confirmed by a transmission electron microscope as it is after placing the grains on a mesh. The size of the fine particles of the present invention is 0.3 μm or less, preferably 0.1 μm or less, particularly preferably 0.01 μm or less. The fine silver halide may be added at the same time as the addition of other halide ions and silver ions, or only the fine silver halide may be added. Fine silver halide grains are mixed in an amount of 0.005 to 20 mol%, preferably 0.01 to 10 mol%, based on the total silver halide.

The silver iodide content of each grain can be measured by analyzing the composition of each grain using an X-ray microanalyzer. The coefficient of variation of the intergranular iodine distribution is defined as the standard deviation of the silver iodide content and the average iodine content when the silver iodide content of at least 100, more preferably 200 and particularly preferably 300 or more emulsion grains is measured. Relational expression using silver halide content (standard deviation / average silver iodide content) × 100
= Value defined by the coefficient of variation. The measurement of the silver iodide content of the individual grains is described, for example, in EP 147,868. Silver iodide content Yi (mol%) of individual grains
There is a case where there is a correlation between and and a sphere equivalent diameter Xi (micron) of each particle, but it is desirable that there is no correlation. Regarding the structure relating to the silver halide composition of the grains of the present invention, for example, X-ray diffraction, EPMA (also referred to as XMA) method (scanning silver halide grains with an electron beam,
Method for detecting silver halide composition), ESCA (XPS
The method can also be confirmed by a combination of the following methods (a method of irradiating X-rays and dispersing photoelectrons emitted from the particle surface). When measuring the silver iodide content in the present invention, the grain surface means a region having a depth of about 5 nm from the surface, and the inside of the grain means a region other than the above-mentioned surface. Such a halogen composition on the particle surface can be usually measured by the ESCA method.

The silver halide emulsion of the present invention is preferably selenium-sensitized. As the selenium sensitizer used in the present invention, a selenium compound disclosed in a conventionally known patent can be used. Usually, the unstable selenium compound and / or the non-unstable selenium compound is used by adding the selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-1348.
9, JP-A-4-25832, JP-A-4-10924
It is preferable to use the compounds described in No. 0 or the like.

Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids ( For example, 2-selenopropionic acid, 2-
Selenobutyric acid), selenoesters, diacylselenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, and colloidal metal selenium.

While the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. Speaking of an unstable selenium compound as a sensitizer of a photographic emulsion, the structure of the compound is not very important as long as selenium is unstable, and the organic portion of the selenium sensitizer molecule carries selenium, It is generally understood by those skilled in the art that it has no role other than to be present in the emulsion in an unstable form. In the present invention, an unstable selenium compound having such a broad concept is advantageously used.

The non-labile selenium compounds used in the present invention include JP-B-46-4553 and JP-B-52-3.
No. 4,492, and JP-B-52-34491. As a non-labile selenium compound,
For example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinthione and these Derivatives.

Of these selenium compounds, the following general formulas (A) and (B) are preferred.

[0073]

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In the formula, Z ₁ and Z ₂ may be the same or different and each represents an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), an alkenyl group (eg, vinyl, propenyl) Aralkyl group (eg, benzyl, phenethyl), aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), heterocyclic group (eg, 2-pyridyl, 3-thienyl, 2-furyl, 2-imidazolyl), -NR ₁ (R ₂ ), -OR ₃ or -SR ₄
Represents

R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group or an acyl group. Alkyl group, an aralkyl group, the aryl group or heterocyclic group, the same examples as Z ₁ and the like. However, R ₁ and R ₂ are a hydrogen atom or an acyl group (for example,
Acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl).

[0076] In formula (A), preferably, Z ₁ represents an alkyl group, an aryl group, or -NR ₁ a (R _2), Z ₂
Represents -NR ₅ (R _6). R ₁ , R ₂ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group.

The formula (A) is more preferably N, N
-Dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, N-
Represents an alkyl-N-aryl-arylselenoamide.

[0078]

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In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group,
—OR ₇ , —NR ₈ (R ₉ ), —SR ₁₀ , —SeR ₁₁ ,
X represents a hydrogen atom.

R ₇ , R ₁₀ and R ₁₁ are an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group,
R ₈ and R ₉ represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heterocyclic group or a hydrogen atom, and X represents a halogen atom.

In the general formula (B), Z ₃ , Z ₄ , Z ₅ ,
The alkyl group, alkenyl group, alkynyl group and aralkyl group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group ( For example, methyl, ethyl, n
-Propyl, isopropyl, t-butyl, n-butyl,
n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3
-Pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl).

In the general formula (B), Z ₃ , Z ₄ , Z ₅ ,
The aryl group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (for example, phenyl,
Pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl, 4-methylphenyl).

In the general formula (B), Z ₃ , Z ₄ , Z ₅ ,
The heterocyclic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Heterocyclic groups (eg, 2-pyridyl, 3-thienyl, 2-
Furyl, 2-thiazolyl, 2-imidazolyl, 2-benzimidazolyl) and may be condensed.

In the general formula (B), the cation represented by R ₇ , R ₁₀ and R ₁₁ represents an alkali metal atom (such as potassium or sodium) or ammonium. Also,
The halogen atom represented by X represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the general formula (B), preferably,
Z ₃ , Z ₄ or Z ₅ represents an alkyl group, an aryl group, or —OR ₇ , and R ₇ represents an alkyl group or an aryl group.

The formula (B) more preferably represents a trialkylphosphine selenide, a triarylphosphine selenide, a trialkylselenophosphate or a triarylselenophosphate.

Specific examples of the compounds represented by formulas (A) and (B) are shown below, but the present invention is not limited thereto.

[0088]

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[0089]

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[0090]

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[0091]

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These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent, and added during chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is 1
The selenium sensitizer is not limited to the species, and two or more of the above selenium sensitizers can be used in combination. A combination of an unstable selenium compound and a non-unstable selenium compound is preferred.

The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the ripening temperature and time, and the like.
Preferably, it is from 2 × 10 ⁻⁶ mol to 5 × 10 ⁻⁶ per mol of silver halide. The temperature of chemical sensitization when using a selenium sensitizer is preferably 40 ° C. or higher and 80 ° C. or lower. pAg and pH are arbitrary. For example, the effects of the present invention can be obtained in a wide range of pH from 4 to 9. Selenium sensitization is more effectively achieved by performing it in the presence of a silver halide solvent.

Examples of the silver halide solvent usable in the present invention include, for example, US Pat. No. 3,271,157.
No. 3,531,289, No. 3,574,62
No. 8, JP-A-54-1019 and JP-A-54-158917
(A) organic thioethers described, for example, in JP-A-53-82408, JP-A-55-77737, and JP-A-55-77737;
(B) thiourea derivatives described in JP-A-2982; and (c) silver halide solvents having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319. (D) imidazoles, (e) sulfites described in JP-A-54-100717,
(F) thiocyanate.

Particularly preferred silver halide solvents include:
There are thiocyanate and tetramethylthiourea. The amount of the solvent to be used varies depending on the kind. For example, in this case, the preferable amount is 1 × per mol of silver halide.
It is not less than 10 ^-4 mol and not more than 1 × 10 ^-2 mol.

The emulsion used in the present invention is preferably applied in combination with gold sensitization. As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 or +3, and gold compounds usually used as gold sensitizers can be used. Representative examples include, for example, chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, gold selenide No. The amount of the gold sensitizer to be added varies depending on various conditions.
It is preferably at least ^10-7 mol and not more than 5 ^10-5 mol.

The emulsion used in the present invention is desirably used in combination with sulfur sensitization in chemical sensitization. Sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher, for a certain time.

For the above-mentioned sulfur sensitization, known sulfur sensitizers can be used. Examples include thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like. Other, for example, U.S. Pat.
574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313, 3,656,955,
German Patent 1,422,869, JP-B-56-249
No. 37 and JP-A-55-45016 can also be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, silver halide grain size, etc., but is not less than 1 × 10 ⁻⁷ mol per mol of silver halide.
× 10 ^-5 mol or less is preferred.

The silver halide emulsion used in the present invention may be subjected to reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization.

The reduction sensitization is carried out by adding a reduction sensitizer to a silver halide emulsion or by using a pAg 1 called silver ripening.
7, a method of growing or ripening in a low pAg atmosphere;
Either a method of growing or ripening in a high pH atmosphere of pH 8 to 11 called high pH ripening can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Examples of the reduction sensitizer include stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid,
Silane compounds, borane compounds and the like are known. For the reduction sensitization used in the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds as reduction sensitizers. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide.

The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters, and amides and added during grain growth. Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer several times as the grains grow, or to add them continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion used in the present invention. The oxidizing agent for silver is a compound having an action of acting on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ion generated here may form a silver salt that is hardly soluble in water, such as silver halide, silver sulfide, or silver selenide, or a silver salt that is easily soluble in water, such as silver nitrate. May be. The oxidizing agent for silver may be inorganic or organic. As the inorganic oxidizing agent, ozone, hydrogen peroxide and additives thereof (for example, NaBO ₂ .H ₂ O _{2.
3H 2 O, 2NaCO 3 · 3H} 2 O 2, Na 4 P 2 O 7 · 2H 2
_{O 2, 2Na 2 SO 4 ·} H 2 O 2 · 2H 2 O), peroxy acid salts (e.g., _{K 2 S 2 O 8, K} 2 C 2 O 6, K 2 P 2 O 8), peroxy complex compounds (e.g. , K ₂ [Ti (O ₂ ) C ₂ O ₄ ]
_{· 3H 2 O, 4K 2 SO} 4 · Ti (O 2) OH · SO 4 · 2
_{H 2 O, Na 3 [VO} (O 2) (C 2 H 4) 2 · 6H 2 O),
Oxygenates such as permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine, and perhalates (eg, potassium periodate) ), High valent metal salts (eg, potassium hexacyanoferrate), and thiosulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds which release active halogen (for example, N-
Bromsuccinimide, chloramine T, chloramine B) are mentioned by way of example.

In the present invention, preferred oxidizing agents are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents such as thiosulfonates, and organic oxidizing agents such as quinones.

It is a preferred embodiment to use the above-mentioned reduction sensitization and an oxidizing agent for silver in combination. A method of using an oxidizing agent followed by reduction sensitization, a reverse method thereof, or a method of coexisting both can be used. These methods can be applied to both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention exerts the effects of the present invention preferably by being spectrally sensitized by a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and compound merocyanine dyes. These dyes may contain any nucleus commonly used in cyanine dyes as a basic heterocyclic nucleus. Such nuclei include, for example, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus,
A tetrazole nucleus, a pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, Examples include a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, and a quinoline nucleus. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, and a thiazolidine-2,4-nucleus.
It can have a 5-6 membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus.

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
2,0523, 3,527,641, 3,61
7,293, 3,628,964 and 3,66
6,480, 3,672,898, 3,67
9,4283, 3,703,377, 3,76
9,301, 3,814,609, 3,83
Nos. 7,862, 4,026,707, British Patent Nos. 1,344,281, 1,507,803, JP-B-43-4936, JP-B-53-12375, and JP-A-5
Nos. 2-110618 and 52-109925.

In addition to the sensitizing dye, the emulsion may contain a dye having no spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A-8-969 and JP-A-4225666, spectral sensitization may be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in No. 928, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, these sensitizing dyes are added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these sensitizing dyes are added prior to chemical sensitization, and Can be added after chemical sensitization, and may be at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The sensitizing dye was used in an amount of 4 per mole of silver halide.
It can be used in an amount of from × 10 ^-6 to 8 × 10 ^-3 mol, but more preferably a silver halide grain size of 0.2 to 1.2 μm
Is about 5 × 10 ^-5 to 2 × per mol of silver halide.
10 ^-3 mol is more effective.

The silver halide grains used in the present invention preferably have a twin plane spacing of 0.017 μm or less. It is more preferably 0.007 to 0.017 μm, and particularly preferably 0.007 to 0.015 μm.

The silver halide emulsion used in the present invention is prepared by adding a silver iodobromide emulsion prepared in advance during chemical sensitization.
By dissolving, fog during aging can be improved. The timing of addition may be any time during chemical sensitization, but it is preferable to first add and dissolve the silver iodobromide emulsion, and then add the sensitizing dye and the chemical sensitizer in that order. The silver iodobromide emulsion to be used is a silver iodobromide emulsion having an iodine content lower than the surface iodine content of the host grains, and preferably a pure silver bromide emulsion. The size of the silver iodobromide emulsion is not limited as long as it can be completely dissolved, but is preferably 0.1 μm or less, more preferably 0.05 μm or less, as the equivalent sphere diameter. The addition amount of the silver iodobromide emulsion varies depending on the host grains to be used, but is preferably from 0.005 to 5 mol%, more preferably from 0.1 to 1 mol%, per mol of silver. is there.

Next, the bleaching accelerator releasing compound which can be used in the present invention will be described. The bleach accelerator releasing compound can be preferably represented by the following general formula (I).

Formula (I) A- (L) k-Z A represents a group that reacts with an oxidized developing agent to cleave (L) k-Z, and L represents Z after cleavage of the bond with A. , K represents 0 or 1, and Z represents a bleaching accelerator.

Next, the general formula (I) will be described in detail. In the general formula (I), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include a yellow coupler residue (for example, an open-chain ketomethylene type coupler residue such as acylacetanilide and malondianilide) and a magenta coupler residue (for example, 5-pyrazolone type and pyrazolotriazole). Coupler residue such as type),
Examples thereof include a cyan coupler residue (for example, a phenol-type or naphthol-type coupler residue) and a non-color-forming coupler residue (for example, an indanone-type or acetophenone-type coupler residue). U.S. Pat.
And heterocyclic coupler residues described in JP-A Nos. 070 and 4,183,752.

When A represents a redox group, the redox group is a group which can be cross-oxidized by an oxidized form of a developing agent, and examples thereof include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, , 2-naphthohydroquinones, sulfonamidophenols,
Hydrazides or sulfonamido naphthols are exemplified. These groups are specifically described in, for example, JP-A-61-2.
No. 30135, No. 62-251746, No. 61-27
No. 8852, U.S. Pat. Nos. 3,364,022, 3,
379,529, 3,639,417, 4,6
No. 84,604 or J.P. Org. Chem. , 29,
588 (1964).

L in the general formula (I) is preferably the following. (1) Group utilizing cleavage reaction of hemiacetal For example, US Pat. No. 4,146,396;
-249148 and 60-249149, and are groups represented by the following formula. Here, the symbol * represents a position bonding to the left side in the general formula (I), and the symbol ** represents a position bonding to the right side in the general formula (I).

Formula (T-1)

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In the formula, W is an oxygen atom, a sulfur atom or-
Represents an NR ₆₇ — group, R ₆₅ and R ₆₆ represent a hydrogen atom or a substituent, represent an R ₆₇ substituent, and t represents 1 or 2
Represents When t is 2 the two -W-CR ₆₅ R ₆₆ - represents the same or different. When R ₆₅ and R ₆₆ represent a substituent and representative examples of R ₆₇ are each R ₆₉
Group, R ₆₉ CO— group, R ₆₉ SO ₂ — group, R ₆₉ R ₇₀ NCO—
Or an R ₆₉ R ₇₀ NSO ₂ — group. Here, R ₆₉ represents an aliphatic group, an aromatic group or a heterocyclic group,
R ₇₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. Each of R ₆₅ , R ₆₆ and R ₆₇ represents a divalent group, and includes the case where they are linked to form a cyclic structure.

(2) A group that causes a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction. For example, a timing group described in US Pat. No. 4,248,962 may be mentioned. It can be represented by the following equation.

Formula (T-2) * -Nu-Link-E-** In the formula, the symbol * represents the position bonding to the left side in the general formula (I), and the symbol ** represents the right side in the general formula (I). Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic group, E represents an electrophilic group, and is subjected to nucleophilic attack from Nu to the ** mark. Link is a group capable of cleaving a bond, and Link represents a linking group that sterically links Nu and E so that an intramolecular nucleophilic substitution reaction can occur.

(3) A group which causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system. For example, US Pat. No. 4,409,323 or US Pat.
21,845, which is a group represented by the following formula.

Formula (T-3)

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In the formulas, *, **, W, R ₆₅ , R ₆₆ and t have the same meanings as described for (T-1).

(4) Group utilizing cleavage reaction by hydrolysis of ester For example, a linking group described in West German Patent Publication No. 2,626,315, and the following groups may be mentioned. In the formulas, * and ** have the same meaning as described for Formula (T-1).

Formula (T-4)

Embedded image Formula (T-5)

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(5) Group Utilizing Imino Ketal Cleavage Reaction It is a linking group described in, for example, US Pat. No. 4,546,073, and is a group represented by the following formula.

Formula (T-6)

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In the formula, *, ** and W represent the formula (T-
Have the same meanings as described in 1), R ₆₈ is R ₆₇
Has the same meaning as

Examples of the group represented by L being a coupler or a redox group include the following.
As a coupler, for example, in the case of a phenol type coupler, a coupler bonded to A in the general formula (I) at an oxygen atom excluding a hydrogen atom of a hydroxyl group. In the case of a 5-pyrazolone-type coupler, it is bonded to A at an oxygen atom obtained by removing a hydrogen atom from a hydroxy group of a type tautomerized to 5-hydroxypyrazole.

Each of these functions as a coupler only after leaving from A, and reacts with the oxidized form of the developing agent to release Z bonded to the coupling position. Preferred examples when L is a coupler include the following formulas (C-1) to (C-4).

Formula (C-1)

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Formula (C-2)

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Formula (C-3)

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Formula (C-4)

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Where V₁And V_TwoRepresents a substituent;
_Three, V_Four, V_FiveAnd V₆Is a nitrogen atom or substituted or unsubstituted
V represents a substituted methine group;₇Represents a substituent, and x represents
Represents an integer of 0 to 4;₇Is the same
Two different V₇Are linked
An annular structure may be formed. V₈Is a -CO- group, -SO _Two
-Represents a group, an oxygen atom or a substituted imino group;₉Is

Embedded image Represents a group of nonmetallic atoms for constituting a 5- or 8-membered ring together with V ₁₀ represents a hydrogen atom or a substituent.

When the group represented by L in the general formula (I) is a redox group, it is preferably represented by the following formula (R-1).

Formula (R-1) * -P- (Y = Z) _k -QB wherein P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group; And Z
At least one represents a methine group having Z as a substituent, the other Y and Z represent a substituted or unsubstituted methine group or a nitrogen atom, and k represents an integer of 1 to 3 (k Y and Z represents the same or different), and B represents a hydrogen atom or a group which can be removed by an alkali. Here, the case where any two substituents of P, Y, Z, Q and B are linked to form a divalent group to form a cyclic structure is also included. For example, (Y = Z) _k forms a benzene ring, a pyridine ring and the like.

When P and Q represent a substituted or unsubstituted imino group, they are preferably a sulfonyl group or an imino group substituted with an acyl group.

At this time, P and Q are represented as follows. Formula (N-1)

Embedded image Formula (N-2)

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[0145] Here, the * mark indicates the position bonding to B.
** indicates the position where the bond is established with one of-(Y = Z) _k- free bonds. In the formula, the group represented by G ′ represents an aliphatic group, an aromatic group, or a heterocyclic group.

Particularly preferred groups among the groups represented by the formula (R-1) are those represented by the following formulas (R-2) or (R-3).

Formula (R-2)

Embedded image Formula (R-3)

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In the formula, an asterisk (*) represents a position bonding to A in the general formula (I), and a ** represents a position bonding to Z in the formula (I).

R ₆₄ represents a substituent, and q represents an integer of 0, 1 to 3. q is may be two or more R ₆₄ when two or more be the same or different and represent a linked ring structure, respectively a divalent group when two R ₆₄ are substituents on adjacent carbons The case is also included.

In the formula (I), the group represented by Z is, for example, a known bleaching accelerator group. For example, U.S. Pat. No. 3,893,858, British Patent 1,138,842, JP-A-53-1416.
No. 23, various mercapto compounds, compounds having a disulfide bond described in JP-A-53-95630, and JP-B-53-98.
No. 54 thiazolidine derivative,
Isothiourea derivatives as described in JP-A-53-94927, thiourea derivatives as described in JP-B-45-8506 and JP-B-49-26586, JP-A-49-42349 Thioamide compounds as described in JP-A-55-26506, dithiocarbamates as described in JP-A-55-26506, arylenediamine compounds as described in U.S. Pat. No. 4,552,834, and the like. is there. In these compounds, it is a preferable example that the compound is bonded to A- (L) k- in the formula (I) at a substitutable heteroatom contained in the molecule.

The group represented by Z is preferably a group represented by the following formula (V), (VI) or (VII).

[0152]

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In the formula, the * mark indicates the position at which A- (L) p-
And R₃₁Has 1 to 8, preferably 1 to 5 carbon atoms
Represents a divalent aliphatic group,₃₂Is R₃₁A group with the same meaning as
A divalent aromatic group having 6 to 10 carbon atoms, or 3 to 8 members
Membered ring, preferably a 5- or 6-membered divalent heterocyclic group
And X_ThreeIs -O-, -S-, -COO-, -SO_Two
-, -NR₃₃-, -NR₃₃-CO-, -NR₃₃-SO_Two
-, -S-CO-, -CO-, -NR₃₃-COO-,-
N = CR₃₃-, -NR₃₃CO-NR₃₄-Or -NR
₃₃SO_TwoNR₃₄X represents a group_FourIs 2 of 6 to 10 carbon atoms
X represents a divalent aromatic group,_FiveIs at least combined with S
Preferred are 3- to 8-membered rings having one carbon atom in the ring.
And preferably represents a 5- or 6-membered divalent multicyclic group,
Y₁Represents a carboxyl group or a salt thereof, a sulfo group or
Is a salt, hydroxyl group, phosphonic acid group or
Salt, amino group (even when substituted with an aliphatic group having 1 to 4 carbon atoms)
Good), -NHSO_Two-R₃₅Or -SO_TwoNH-R₃₅
Represents a group (here, salt means sodium salt and potassium salt)
Or ammonium salt), Y_{2 is}Y₁Theory
Represents a group or hydrogen atom having the same meaning as
Represents 0 or 1, and i represents an integer of 0 to 4.
And j represents an integer of 1 to 4, and k represents 0 to 4.
Represents an integer. Where j Y₁Is R₃₁− ｛(X_Three)_r−
R₃₂｝_iAnd X _Four− ｛(X_Three)_r-R₃₂｝_iReplaceable
Join at position, and k Y₁Is X_Five− ｛(X_Three)_r-R
₃₂｝_iWhere k and j are
When there are a plurality of k and j Y₁Are the same or different
And when i and j are plural, i and j are
And j (X_Three)_r-R₃₂Are the same or different
Express. Where R₃₃, R₃₄And R₃₅Are hydrogen atoms or
Or an aliphatic group having 1 to 8, preferably 1 to 5 carbon atoms.
You.

When R ₃₁ to R ₃₅ represent an aliphatic group,
It may be linear or cyclic, linear or branched, saturated or unsaturated, substituted or unsubstituted. Unsubstituted is preferable, but examples of the substituent include a halogen atom, an alkoxy group (for example, methoxy and ethoxy), and an alkylthio group (for example, methylthio and ethylthio).

The aromatic group represented by X ₄ and the aromatic group when R ₃₂ represents an aromatic group may have a substituent. Examples of the substituent include those listed as the substituent of the aliphatic group.

When the heterocyclic group represented by X ₅ or R ₃₂ represents a heterocyclic group, the heterocyclic group may be a saturated or unsaturated, substituted or unsubstituted heterocyclic group having an oxygen, sulfur or nitrogen atom as a hetero atom. It is a ring group. For example, pyridine, imidazole, piperidine, oxolane,
Sulfolane, imidazolidine, thiazepine or pyrazole. Examples of the substituent include those exemplified as the substituent for the aliphatic group.

The following are specific examples of the group represented by the formula (V).

[0158]

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Specific examples of the group represented by the formula (VI) include the following.

[0160]

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The following are specific examples of the group represented by the formula (VII).

[0162]

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Next, specific examples of the compound of the formula (I) preferably used in the present invention will be shown, but the present invention is not limited thereto.

[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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Others, Research Disclosure I
tem No. Nos. 24241 and 11449, JP-A-61-201247, JP-A-63-106749, JP-A-63-121843, and JP-A-63-12184.
4, Japanese Patent Application Laid-Open No. 63-214752,
The compounds described in JP-A-93454 are also used in the same manner.

The compound of the general formula (I) used in the present invention can be easily synthesized based on the description in the above-mentioned patent specification. The compound of the formula (I) may be added to any layer, but is preferably added to the photosensitive silver halide emulsion layer or a layer adjacent thereto.

The use of the compound of the general formula (I) improves desilvering by the bleaching accelerating effect and improves color reproducibility. By using the photosensitive silver halide emulsion layer (e.g., blue-sensitive layer) on the side farther from the surface (closer to the exposed surface) or the layer adjacent thereto, stable processing with small fluctuations in photographic properties in the color processing running process give. The addition amount of the compound of the general formula (I) varies depending on the structure of the compound, but is 5 × 10 ^{−4 to} 1.0 g / m ² . Preferably 1
× 10 ^{-3 to} 5 × 10 ^-1 g / m ² , more preferably 2 × 10 ^-3 to 2 × 10 ^-1 g / m ² .

The tabular grains contained in the emulsion used in the light-sensitive material of the present invention preferably have an electron capture zone. The electron capture zone has a concentration of 1 × a compound serving as an electron capture center (hereinafter, also simply referred to as “electron capture center”).
A portion occupying 5% or more and 30% or less of the grain volume, from 10 ⁻⁵ mol / mol local silver to 1 × 10 ⁻³ mol / mol local silver. More preferably, the electron trapping center content is from 5 × 10 ⁻⁵ mol / mol local silver to 5 × 10 ⁻⁴ mol / mol local silver. "Mole / mol local silver" used in the definition of the electron capture center concentration refers to the concentration of the electron capture center with respect to the amount of silver added simultaneously with the compound serving as the electron capture center.

The electron trapping center concentration in the electron trapping zone needs to be uniform. The term "uniform" means that the electron trapping center is introduced into the grains at a constant amount per unit silver, and the electron trapping centers are introduced into the reaction vessel for grain formation at the same time as the silver nitrate used for grain formation. At this time, a halogen solution may be added at the same time. The compound serving as an electron capture center may be added as an aqueous solution, or fine particles doped or adsorbed with the compound serving as an electron capture center may be prepared and added.

[0175] The electron capture zone may be anywhere in the particle. Also, there may be two or more electron capture zones in the particle. An electron capture center required to form an electron capture zone is represented by the following general formula.

General formula I [M (CN) _x1 L _(6-x1) ] ^{n +} General formula II [M (CN) _x2 L _(4-x2) ] ^{n +} General formula III [ML1 _x3 X _(6-2x3) ] ^{n +} General formula IV [ML1 _{(6-3i) × 1/3} L2 _i X _{(6-3i) × 1/3} ] ^{n +} .

Wherein M is any metal or metal ion;
L represents a compound in which a chain or cyclic hydrocarbon is a parent or a part of carbon or hydrogen atoms of the parent structure is replaced by another atom or atomic group. However, all L may be the same compound or different compounds. L1 represents an organic compound that is bidentately coordinated with a metal or a metal ion, and L2 represents an organic compound that is tridentately coordinated with a metal or a metal ion. X represents any chemical species. x1 is an integer from 0 to 6, x2 is an integer from 0 to 4, x3 is 1, 2 or 3, and i is 1 or 2.

When a six-coordinate octahedral complex is incorporated into a silver halide grain as a dopant, J. Phys. :
Condens. Matter 9 (1997) 3227
[AgX ₆ ] ^5- (X ⁻ ) in silver halide grains, as described in many documents and patent publications including -3240.
= Halogen ions) as one unit, and a part of the grains is replaced with the dopant. It is therefore predicted that if the molecular size of the complex to be doped becomes too large, it will not be suitable for dopants, and that the further the charge of the complex to be doped is from -5, the more disadvantageous in this replacement. According to molecular model considerations, when the complex to be doped has a 5- or 6-membered ring compound as a ligand, the size of the replacement unit in the silver halide grain is larger in the silver chloride grain. It is believed that in silver bromide particles, slight distortion of the lattice or complex molecules would allow them to be incorporated into the particles.

Specifically, the ligand is preferably a compound capable of having a negative charge by removing H ⁺ such as pyrrole, pyrazole, imidazole, triazole and tetrazole, and its derivative may be used as the ligand. Is also preferred. Examples of the substituent in the derivative include a hydrogen atom, a substituted or unsubstituted alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, hexyl group, octyl group, -Ethylhexyl group,
Dodecyl, hexadecyl, t-octyl, isodecyl, isostearyl, dodecyloxypropyl, trifluoromethyl, methanesulfonylaminomethyl, etc.), alkenyl, alkynyl, aralkyl, cycloalkyl (cyclohexyl) Group, 4-t-butylcyclohexyl group, etc.), substituted or unsubstituted aryl group (phenyl group, p-tolyl group, p-anisyl group, p-chlorophenyl group, 4-t-butylphenyl group, 2,4-di -t
-Aminophenyl group, etc.), halogen (fluorine, chlorine, bromine, iodine), cyano group, nitro group, mercapto group, hydroxy group, alkoxy group (methoxy group, butoxy group,
Methoxyethoxy group, dodecyloxy group, 2-ethylhexyloxy group, etc.), aryloxy group (phenoxy group,
p-tolyloxy group, p-chlorophenoxy group, 4-t-butylphenoxy group, etc.), alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, substituted or unsubstituted amino group (amino group, methylamino group, dimethylamino group) Group, anilino group, N-methylanilino group, etc.), ammonium group, carbonamide group, sulfonamide group, oxycarbonylamino group, oxysulfonylamino group,
Substituted ureido group (3-methylureido group, 3-phenylureido group, 3,3-dibutylureido group, etc.), thioureido group, acyl group (formyl group, acetyl group, etc.), oxycarbonyl group, substituted or unsubstituted carbamoyl group (Ethylcarbamoyl group, dibutylcarbamoyl group, dodecyloxypropylcarbamoyl group, 3- (2,4-di-t-aminophenoxy) propylcarbamoyl group, piperidinocarbonyl group, morpholinocarbonyl group, etc.), thiocarbonyl group, thio It is preferably a carbamoyl group, a sulfonyl group, a sulfinyl group, an oxysulfonyl group, a sulfamoyl group, a sulfino group, a sulfano group, a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof.

The center metal of the electron-capturing center of the present invention is not particularly limited, but those having a four-coordinate or six-coordinate structure around the metal are preferred.
It is preferable that the metal or metal ion has no unpaired electrons, or that the stabilized orbitals are all filled with electrons when the d orbital of the metal undergoes ligand field splitting. Among them, +2 valent metal ions are preferable. Particularly preferably, alkaline earth metals, iron (II), ruthenium (I
It is preferable to use each metal ion of I), osmium (II), zinc, cadmium and mercury, and among these, it is most preferable to use each metal ion of magnesium, iron (II), ruthenium (II) and zinc.

Specific examples of the compound serving as an electron capture center (hereinafter, also referred to as “complex of the present invention” and “metal complex”) used in the present invention are shown below, but the compounds of the present invention are not limited to these. is not.

[Fe (CN) ₆ ] ^3- [Fe (CN) ₅ F] ^3- [Fe (CN) ₄ F ₂ ] ^3- [Fe (CN) ₅ Cl] ^3- [Fe (CN) ₄ Cl _2] ^3- [Fe (CN) ₅ Br] ^3- [Fe (CN) ₄ Br _2] ^3- [Fe (CN) ₅ (SCN)] ^3- [Fe (CN) ₅ (SCN)] ^3- [ Fe (CN) ₅ (NO)] ^3- _{[Fe (CN) 5 (H 2} O) ] ^2- [Fe (CN) _6] ^4- [Fe (CN) ₅ F] ^4- [Fe (CN) ₄ F _2] ^4- [Fe (CN) ₅ Cl] ^4- [Fe (CN) ₄ Cl _2] ^4- [Fe (CN) ₅ Br] ^4- [Fe (CN) ₄ Br _2] ^4- [Fe ( CN) ₅ (SCN)] ^4- [Fe (CN) ₅ (SCN)] ^4- [Fe (CN) ₅ (NO)] ^4- _{[Fe (CN) 5 (H 2} O) ] ^3- [Fe ( CN) ₅ (PZ)] ^3- _{[Fe (CN) 4 (PZ)} 2 ] ^2- [Fe (CN) ₅ (Im)] ^3- [Fe (CN) ₄ (I ) _2] ^2- [Fe (CN) ₅ (trz)] ^3- _{[Fe (CN) 4 (trz)} 2 ] ^2-.

[Ru (CN) ₆ ] ^4- [Ru (CN) ₅ F] ^4- [Ru (CN) ₄ F ₂ ] ^4- [Ru (CN) ₅ Cl] ^4- [Ru (CN) ₄ Cl ₂ ] ^4- [Ru (CN) ₅ Br] ^4- [Ru (CN) ₄ Br ₂ ] ^4- [Ru (CN) ₅ I] ^4- [Ru (CN) ₄ I ₂ ] ^4- [Ru (CN) ₅ (SCN)] ^4- [Ru (CN) ₅ (SCN)] ^4- [Ru (CN) ₅ (NO)] ^4- _{[Ru (CN) 5 (H 2} O) ] ^3- [Ru (CN) ₄ (PZ) ₂ ] ^2- [Ru (CN) ₅ (PZ)] ^3- [Ru (CN) ₄ (Im) ₂ ] ^2- [Ru (CN) ₅ (Im) ₂ ] ^3- [Ru (CN) ₄ (trz) ₂ ] ^2- [Ru (CN) ₅ (trz)] ^3- .

[0184] [Re (CN) ₅ F] ^4- [Re (CN) _6] ^4- [Re (CN) ₅ Cl] ^4- [Re (CN) ₄ F _2] ^4- [Re (CN) ₅ Br ] ^4- [Re (CN) ₄ Cl _2] ^4- [Re (CN) ₅ I] ^4- [Re (CN) ₄ Br _2] ^4- [Re (CN) ₄ I _2] ^4-.

[Os (CN) ₆ ] ^4- [Os (CN) ₅ F] ^4- [Os (CN) ₄ F ₂ ] ^4- [Os (CN) ₅ Cl] ^4- [Os (CN) ₄ Cl _2] ^4- [Os (CN) ₅ Br] ^4- [Os (CN) ₄ Br _2] ^4- [Os (CN) ₅ I] ^4- [Os (CN) ₄ I ₂ ] ^4- [Os (CN) ₅ (SCN)] ^4- [Os (CN) ₅ (SCN)] ^4- [Os (CN) ₅ (NO)] ^4- _{[Os (CN) 5 (H 2} O) ] ^3- [Os (CN) ₄ (PZ) ₂ ] ^2- [Os (CN) ₅ (PZ)] ^3- [Os (CN) ₄ (Im) ₂ ] ^3- [Os (CN) ₅ (Im) ] ^3- [Os (CN) ₄ (trz)] ^2- [Os (CN) ₅ (trz)] ^3- .

[0186] [Ir (CN) ₅ Cl] ^3- [Ir (CN) _6] ^3- [Ir (CN) ₅ Br] ^3- [Ir (CN) ₄ Cl _2] ^3- [Ir (CN) ₅ I ^3- [Ir (CN) ₄ Br _2] ^3- [Ir (CN) ₅ (NO)] ^3- [Ir (CN) ₄ I _2] ^3- _{[Ir (CN) 5 (H 2} O) ] ^{2 -}

[Pt (CN) ₄ ] ^2- [Pt (CN) ₄ Cl ₂ ] ^2- [Pt (CN) ₄ Br ₂ ] ^2- [Pt (CN) ₄ I ₂ ] ^2- [Au (CN) _4] ^- [Au (CN) ₂ Cl _2] ^2.

In the above metal complex, PZ = pyrazole, Im = imidazole, and trz = triazole.

[0189]

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[0190]

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[0191]

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[0192]

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[0193]

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[0194]

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[0195]

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[0196]

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[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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[0202]

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[0203] In the present invention, each ligand preferably used, even in a state in which the H ⁺ was added, may be in a state in which de-H ⁺ was.

In the present invention, since the complex molecule is completely dissociated from the counter ion in the aqueous solution and exists in the form of an anion or a cation, the counter ion is not important for photographic performance. When the complex molecule becomes an anion and forms a salt with the cation, the counter cation is a sodium ion, potassium ion, rubidium ion, cesium which is easily dissolved in water and is suitable for the precipitation operation of the silver halide emulsion. It is preferable to use an alkali metal ion such as an ion, an ammonium ion, or an alkyl ammonium ion represented by the following general formula V.

General formula V [NR ₁ R ₂ R ₃ R ₄ ] ^{+ wherein} R ₁ , R ₂ , R ₃ and R ₄ are methyl, ethyl, propyl, iso-propyl, n-butyl Represents a substituent arbitrarily selected from the groups. Among _{them, R 1, R 2, R} 3 and R ₄ are all equal substituent tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion and tetra (n- butyl) ammonium ion. It is also preferable to use a pyrazolium cation or an imidazolium cation in which an H ⁺ ion is added to a non-coordinated nitrogen atom in the ligand as a counter cation.

When the complex molecule becomes a cation and forms a salt with the anion, the counter anion is a halide ion, nitrate ion, or permeate which is easily dissolved in water and is suitable for the precipitation operation of a silver halide emulsion. Chlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, tetraphenylborate ion, hexafluorosilicate ion,
It is preferable to use trifluoromethanesulfonic acid or the like. When a strong coordinating anion such as a cyano ion, a thiocyano ion, a nitrite ion, or an oxalate ion is used as a counter anion, ligand exchange with a halogen ion used as a ligand of the complex can be performed. The use of these anions is not preferred because it is highly likely that a reaction will occur and the composition and structure of the complex of the present invention cannot be maintained.

The complex of the present invention can be synthesized by several methods. For example, magnesium, iron and zinc complexes having pyrazole and imidazole as ligands react pyrazole or imidazole as ligands in dehydrated solvent with perchlorate or tetrafluoroborate of each metal. Can be obtained. As a specific synthesis example, the synthesis method of each complex is described in Rec. Tr
av. Chim. , 1969, 88, 1451. Further, the ruthenium-triazole complex is In
org. Chim. It can be synthesized by referring to the reaction of a ruthenium-triazole complex described in Acta 1983, 71, 155.

As the electron trapping center required for forming the electron trapping zone, a compound represented by the following general formula VI is also preferably used.

[0209] In the general formula _{VI [L 'n M (L} (ML' m) j) k] p Formula, M represents any metal or metal ions. M may be all the same metal species or different metal species.
L is a bridging ligand, and represents an organic compound capable of crosslinking two or more metals or metal ions. L 'is H
_{2 O, NH 3, CO,} N 2, NO 2, CO 2, SO 2, SO 3, N 2 H 4, O 2, PH 3
Represents an uncharged small molecule, any organic compound, or any inorganic anion, which may be of the same or different species. n and m are integers of 1 to 5, j is a positive integer, k is an integer of 1 to 5, p is any positive or negative integer or 0.

Bulgarian Chem. Commun., 20 (1993) 350
-368, Radiat. Eff. Defects Solids 135 (1995) 101-10
4, J. Phys .: Condens Matter, 9 (1997) 3227-3240, etc.
As shown in the above, doping the 6 cyano complex is
Shallow electron traps due to Coulomb field in silver halide grains
Will be introduced. In particular, ICPS, 1998, Finalpr
gram and Proceedings, Vol. 1, p. 89, ICPS, 1998,
Final program and Proceedings, Vol. 1, p.92, JP
As shown in JP-A-8-286306, Fe ²⁺, Ru²⁺
Like d⁶Use low-spin bivalent metal ions as the central metal
Ag when I was ⁺Of particles consisting of
Coulomb by introducing +1 excess charge into the environment
Optoelectronic traps with appropriate depth depending on the field are introduced
This causes the photoelectrons generated by the exposure to be deactivated.
Time in the camera, significantly increasing photographic speed
Can be done. At this time, cyanide ion used as a ligand
Has a strong ligand field effect, i.e.,
Π bond is formed by donating (reverse donating) an electron
And this π bond becomes t_2gFurther stabilization of orbit, metal-configuration
Decrease the ligand distance and increase the effective positive charge of metal ions
As a result, the d-orbital splitting of the metal becomes large
Has an increasing effect. Complex doped by this effect
Body e_gThe orbit (the lowest unoccupied orbit of the complex) is
It has higher energy than the bottom of the conduction band and has no effect on electron capture.
It is a relevant level. This is the first time near the dopant
It is possible to create a shallow electron trap by Coulomb field
Wear. Heterocyclic compounds, especially 1,10-phenanthroline and
2,2'-bipyridine is relatively close to the cyano complex during complex formation
It is generally known that it produces a strong ligand field effect.
Doping these complexes, the same as 6-cyano complex
The orbit of metal ions_gOrbit silver halide
Can be placed at higher energy levels than the bottom of the conduction band
Thought to come. In these heterocyclic compounds,
The π * orbit of the ligand is e _gEnergy level lower than orbit
May be the lowest unoccupied orbit, but this level also
Energy levels higher than the bottom of the conduction band of silver halide
Think there is.

With respect to silver nucleation in silver halide grains, it is considered that free movement of photoexcited electrons over a wide range, such as impurity bands in semiconductors, leads to efficient silver nucleation. In fact, J. Phys .: Condens
In the ENDOR experiment described in Matter, 9 (1997) 3227-3240, in the yellow-doped salt-doped emulsion, the yellow-dose salt doping concentration region at which a signal due to electrons thought to have been captured by the impurity band was observed was And clearly coincides with the density region where the sensitivity is increased. The state of such a shallowly captured electron is described by effective mass approximation, and a hydrogen atom can be considered as a model. Therefore, it is expected that increasing the radius of the field where the electrons are bound (the radius of the hydrogen atom model described by the effective mass approximation) will lead to a greater increase in sensitivity. For this purpose, it is preferable that the complex used as the dopant has a larger size. In this regard, it is considered preferable to use a dinuclear complex or a polynuclear complex larger than a mononuclear complex.

When a complex molecule is incorporated into a silver halide grain, the method described in J. Phys .: Condens. Matter 9 (1997) 3227-
As described in the literature and patents, including 3240, some units in silver halide grains, [AgX ₆ ] ^5- (X
(= Halogen ion) and the complex molecule are replaced, so that the central metal occupies the lattice position of the Ag ⁺ ion, and each ligand occupies the lattice position of the halide ion. Expanding this idea, complexes with more than _two nuclei are [Ag ₂
X ₁₁ ] ^9- , [Ag ₃ X ₁₆ ] ^13- ,... Are expected to be replaced with silver halide units, and from the viewpoint of molecular models, US Pat. No. 5,360,712 describes Dinuclear complex of iron described [(NC) ₅ Fe (m-4,4'-bipyridine) Fe
(CN) ₅ ] ^6- represents [X ₅ Ag-X-Ag-X-AgX ₅ ] ^9-
It is presumed to replace the unit. Thus, when a complex molecule is incorporated into silver halide, replacement with some flexibility is expected to occur, but using an oversized complex molecule as a dopant is still advantageous for replacement. And is not expected to be favorable.
From these facts, it is considered that a polynuclear complex or a trinuclear complex is preferable among the polynuclear complexes for use in doping.

In the present invention, the term “organic compound” means a compound in which a chain or cyclic hydrocarbon has a parent structure, or in which some carbon or hydrogen atoms of the parent structure are replaced by other atoms or atomic groups. Point to. Ligands for bridging between metal and metal are organic compounds, especially compounds that coordinate bidentately with metal, or N atoms that form double or triple bonds, or aromatic rings. It is preferable that the compound is capable of accepting a d-electron from a metal in a p * orbital in which an N atom, a P atom, an S atom or the like is a coordinating atom (ie, capable of forming a reverse dative bond). That is, the bridging ligand is preferably one that strongly binds to the metal ion, and more preferably a compound that gives a strong ligand field effect.

The other ligands are also preferably the same organic compounds as the bridging ligands, and particularly, compounds that coordinate bidentately with the metal and form a reverse dative bond with the metal. It is preferable that the compound can be used. It is also preferred that these ligands have a negative charge. This is because when considering that the complex is incorporated into the silver halide grains, the organic compound, which is a ligand, is originally replaced by a halogen ion having a negative charge, so that the charge is closer to a silver halide replacement unit. Think good. However, when considering a wider range of electron capture as described above, on the contrary, it is also preferable to use an uncharged ligand. In order to obtain an appropriate shallow electron trap due to the dopant, it is considered that it is better to have a small charge distribution in the molecule used for the dopant so that localization of electrons does not occur in the electron trap. If there is a heteroatom or other donor site in the ligand other than the donor site for the central metal in the ligand, polarization is highly likely to occur in the ligand, and the electron is uniformly and loosely bound by a loose binding force. May not be suitable for capturing Also, when the molecular size of the ligand increases and the replacement of the ligand portion extends not only to the position of the halogen ion but also to the silver ion adjacent thereto, the ligand of the dopant becomes uncharged. It is considered that the compound of formula (1) is more preferable. At present, both when using a negatively charged organic compound as a ligand and when using an uncharged organic compound, there is a large contribution to the increase in sensitivity, and it is necessary to say which is more preferable. However, as a sensitizing dopant, an organic compound, in particular, a complex having an aromatic compound or a heterocyclic compound as a ligand, and especially considering a ligand field effect, it is coordinated to a metal ion in bidentate or tridentate. Can be said to be more preferable.

In the present invention, specifically as the bridging ligand, those having a saturated or unsaturated hydrocarbon as a basic skeleton are preferably oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, tartaric acid, meso acid, -2,3-dimethylcaptosuccinic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, oxamide, oxamic acid, malonamide, succinamide, adipic amide, dithiooxamide, 1,1,3,3-propanetetra Carbonitrile, tetracyanoethylene,
Diaminomaleonitrile, 1,2,4,5-benzenetetramine, and 1,2,4,5-benzenetetracarboxylic acid, among which small molecules such as oxalic acid, malonic acid, oxamide and oxamic acid are particularly preferable. It is also preferable that H ⁺ of the OH group in the alcohol or phenol is eliminated, and the —O ⁻ site crosslinks two metals or metal ions.

On the other hand, as the heterocyclic compound used as a bridging ligand, pyrazole, imidazole, triazole, tetrazole, oxazole, isoxazole, thiazole, thiadiazole, thiatriazole, tetrathiafulvalene, 4,4′-bipyridine, -Hydroxypyridine, isonicotinic acid, 4-cyanopyridine,
Pyridazine, pyrimidine, pyrazine, 2,3-bis (2-pyridyl) pyrazine, 2,5-bis (2-pyridyl) pyrazine, triazine, 2,2′-bipyrimidine, 2,2′-imidazole, 2,
2'-benzimidazole, and derivatives thereof having a skeleton of these, especially, pyrazole, 4,4'-
Bipyridine, pyrazine, 2,3-bis (2-pyridyl) pyrazine, 2,5-bis (2-pyridyl) pyrazine, 2,2'-bipyrimidine, 2,2'-imidazole, 2,2'-benzimidazole preferable.

The other ligand is preferably an aromatic compound or a heterocyclic compound in view of the magnitude of the ligand field effect as described above. As the aromatic compound, a compound having a substituent serving as a coordination site at each of two adjacent carbon atoms is preferable, and examples thereof include veratrol, catechol, (+/-)-hydrobenzoin, 1,2-
Benzenedithiol, 2-aminophenol, o-anisidine, 1,2-phenylenediamine, 2-nitronaphthol, 2-
Examples include nitroaniline and 1,2-dinitrobenzene.
Further, it is not a compound in which a substituent serving as a coordination site is bonded to two adjacent carbon atoms, but an aromatic compound in which two substituents serving as a coordination site can be coordinated to one metal is also preferable. Benzyl, 1,8-dinitronaphthalene,
Specific examples include 1,8-naphthalenediol and the like.

The monocyclic heterocyclic compound preferably has an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, and a nitrogen atom as a hetero atom in the ligand, and has a phosphorus atom. It is also preferred. Specifically preferred as monodentate ligand, furan, thiophenin, 2H-
Pyrrole, pyran, pyridine, and derivatives thereof. The bidentate or tridentate heterocyclic compound coordinated to a metal or metal ion is preferably a ring-assembled heterocyclic compound in which these monodentate heterocyclic compounds are linked. Compounds in which the above preferred monodentate ligands are linked are preferred. In particular, for bidentate ligands
2,2′-bithiophene, 2,2′-bipyridine and derivatives thereof are preferred, and the tridentate ligand is 2,2 ′: 5 ′, 2 ″ -terthiophene, 2,2 ′: 5 ′, 2 "-terpyridine and derivatives thereof are preferred. Further, 2,2′-biquinoline, 1,10-phenanthroline, and derivatives thereof having a condensed ring in the skeleton of these bidentate ligands are also preferable. Further, as a ligand other than a bridging ligand, a ligand which binds to a metal ion at a coordination site exceeding tridentate is also preferable, such as 1,4,8,11-tetraazacyclotetradecane and 18-crown-6. Also preferred are crown ethers.

Examples of the substituent in these derivatives include a hydrogen atom, a substituted or unsubstituted alkyl group (methyl, ethyl, n-propyl, isopropyl, n-butyl, t-
Butyl group, hexyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, t-octyl group, isodecyl group, isostearyl group, dodecyloxypropyl group, trifluoromethyl group, methanesulfonylaminomethyl group, etc.), Alkenyl, alkynyl, aralkyl, cycloalkyl (cyclohexyl, 4-t-butylcyclohexyl, etc.), substituted or unsubstituted aryl
(Phenyl group, p-tolyl group, p-anisyl group, p-chlorophenyl group, 4-t-butylphenyl group, 2,4-di-t-aminophenyl group, etc.), halogen (fluorine, chlorine, bromine, iodine) ), Cyano group, nitro group, mercapto group, hydroxy group, alkoxy group (methoxy group, butoxy group, methoxyethoxy group, dodecyloxy group, 2-ethylhexyloxy group, etc.), aryloxy group (phenoxy group, p-tolyloxy group , P-chlorophenoxy group, 4-t-butylphenoxy group, etc., alkylthio group, arylthio group, acyloxy group, sulfonyloxy group, substituted or unsubstituted amino group
(Amino group, methylamino group, dimethylamino group, anilino group, N-methylanilino group, etc.), ammonium group, carbonamide group, sulfonamide group, oxycarbonylamino group, oxysulfonylamino group, substituted ureido group (3
-Methylureido, 3-phenylureido, 3,3-dibutylureido, etc., thioureido, acyl (formyl, acetyl, etc.), oxycarbonyl, substituted or unsubstituted carbamoyl (ethylcarbamoyl, dibutyi) Rucarbamoyl group, dodecyloxypropylcarbamoyl group, 3- (2,4-di-t-aminophenoxy) propylcarbamoyl group, piperidinocarbonyl group, morpholinocarbonyl group, etc.), thiocarbonyl group, thiocarbamoyl group, sulfonyl group, Sulfinyl group, oxysulfonyl group, sulfamoyl group, sulfino group, sulfano group,
It is preferably a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof. Here, it is also preferable that R ₂ and R ₃ are closed to form a saturated carbocycle, aromatic carbocycle or heteroaromatic ring.

Although the central metal of the present invention is not particularly limited, as described in many literatures and patents including J. Phys .: Condens. Matter 9 (1997) 3227-3240, a 6-coordinate metal is used. when octahedral complex is incorporated into silver halide grains as dopants, [AgX _6] in the silver halide grains ^{5-(X -}
(Halogen ion) as one unit, it is preferable that the coordination structure around the metal has a plane four-coordinate structure or a six-coordinate structure. More preferably, the metal or metal ion has no unpaired electrons, or the metal
It is preferable that the orbit stabilized when the d orbital undergoes ligand field splitting is completely filled with electrons. Specifically preferred are alkaline earth metals, iron, ruthenium, manganese, cobalt, rhodium, iridium, copper, nickel, palladium, platinum, gold, zinc, titanium, chromium, osmium, cadmium, and mercury. Among them, particularly preferred are iron, ruthenium, manganese, cobalt, rhodium, iridium, titanium, chromium, and osmium, and most preferred are iron, ruthenium and cobalt ions.

Specific examples of the complex of the present invention are shown below, but the compounds of the present invention are not limited thereto.

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The complex of the present invention can be synthesized by several methods. For example, regarding the ruthenium complex, Coord. Chem. Rev. 84 (1988) 85-277 is a well summarized review, and many complexes can be synthesized based on the references cited therein. Coo for other complexes
It can be synthesized based on the synthesis methods listed in the reviews for each metal, which is featured once every few years in rd. Chem. Rev.

The complex of the present invention may be added directly to the reaction solution when forming silver halide grains, or may be added to an aqueous halide solution for forming silver halide grains, or to another solution. It is preferable to add it to the reaction solution so that it is contained in the silver halide grains.
Further, these methods may be combined to dope silver halide grains.

When the complex of the present invention is doped into silver halide grains, they may be uniformly present inside the grains, or may be incorporated in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188847. As disclosed in the gazette,
The particle surface layer may be doped, or a complex may be doped only inside the particle and an undoped layer may be added to the particle surface. In the present invention, it is preferable to dope the particle surface layer. No. 5,252,451 and US Pat.
As disclosed in U.S. Patent No. 256,530, the surface phase of particles may be modified by physical ripening with doped fine particles. Further, a method in which fine particles doped with a complex are prepared, and the fine particles are added and physically ripened to dope the silver halide particles with the complex is also preferable. Further, the above doping methods may be used in combination.

The doping amount of the complex is suitably from 1 × 10 ⁻⁹ mol to 1 × 10 ⁻² mol per mol of silver halide.
Preferably it is 1 × 10 ⁻⁷ or more and 1 × 10 ⁻³ mol or less. The doping amount of the complex preferably does not vary between emulsion grains.

It is preferable to add a hexacyanoiron (II) complex and a hexacyanoruthenium complex (hereinafter, also simply referred to as “metal complex”) to the emulsion used in the present invention.
The addition amount of this metal complex is 1 per mole of silver halide.
It is preferably from 0 ^-7 mol to 10 ^-3 mol, and more preferably from 1.0 × 10 ^-5 mol to 5 × 10 ^-4 mol, per mol of silver halide.

The metal complex used in the present invention may be added and contained at any stage before the preparation of silver halide grains, that is, before and after nucleation, growth, physical ripening, and chemical sensitization. Further, it may be added and contained by dividing it several times. However, it is preferable that 50% or more of the total content of the metal complex contained in the silver halide grains is contained in a layer whose silver content is within １ ／ from the outermost surface of the silver halide grains used. A layer containing no metal complex may be provided further outside the layer containing a metal complex described here.

These metal complexes can be dissolved in water or a suitable solvent and added directly to the reaction solution at the time of forming silver halide grains, or they can be dissolved in an aqueous halide solution for forming silver halide grains. It is preferable to add them in an aqueous solution or another solution to form particles. Further, it is also preferable to add and dissolve silver halide fine particles containing a metal complex in advance and to deposit on a separate silver halide particle to contain these metal complexes.

When these metal complexes are added, the hydrogen ion concentration in the reaction solution is preferably pH 1 or more and 10 or less, more preferably pH 3 or more and 7 or less.

In the light-sensitive material of the present invention, at least one red light-sensitive layer, green light-sensitive layer and blue light-sensitive layer are respectively provided on a support. Each color-sensitive layer has a light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. In the silver halide color photographic light-sensitive material of the present invention, generally, the arrangement of the unit light-sensitive layers is, in order from the support side, a red-sensitive layer, a green-sensitive layer,
They are installed in the order of blue color sensitivity. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These include couplers described below,
It may contain a DIR compound, a color mixing inhibitor and the like. A plurality of silver halide emulsion layers constituting each unit photosensitive layer,
DE 1,121,470 or GB 923,04
As described in 5, the high-sensitivity emulsion layer and the low-sensitivity emulsion layer are preferably arranged so that the sensitivity gradually decreases toward the support. Also, JP-A-57-11275
As described in JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543, a low-speed emulsion layer is provided on the side farther from the support and a high-speed emulsion layer is provided on the side closer to the support. Good.

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL) / High-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
And so on.

As described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the farthest side from the support. JP-A-56-25738 and JP-A-62-63936.
As described in the above, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a higher sensitivity than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such three layers having different sensitivities are used, as described in JP-A-59-202264, a medium-sensitivity emulsion layer / high The layers may be arranged in the order of a light-sensitive emulsion layer / a light-sensitive emulsion layer.

In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. The arrangement may be changed as described above even in the case of four or more layers.

The silver halide photographic light-sensitive material of the present invention comprises at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler, at least one green-sensitive silver halide emulsion layer containing a magenta coupler, In the case of a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer containing a coupler and a non-light-sensitive layer and having an ISO speed of 640 or more, the above-mentioned red-sensitive silver halide emulsion layer at 580 nm It is preferable that the spectral sensitivity S _R (580) has the following relationship with the spectral sensitivity S _{R (max) at} the maximum sensitivity wavelength of the layer. 0.6 ≦ SR _(max) −SR ₍₅₈₀₎ ≦ 0.9.

The red-sensitive silver halide emulsion layer (as a whole two or more emulsion layers) has a thickness of 500 nm to 600 nm.
In the range of nm, the center-of-gravity sensitivity wavelength (λ- _R ) of the spectral sensitivity distribution of the multilayer effect received from another layer is 500 nm <λ- _R ≦ 560 n.
m, the center-of-gravity sensitivity wavelength (λ _G ) of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer (as a whole two or more emulsion layers) is 520 nm ≦ λ _G ≦ 580 nm, and λ _G
It is preferable that -λ- _R ≧ 5 nm.

As the sensitizing dye and solid disperse dye used in this case, those described in JP-A-11-305396 can be used. The center-of-gravity sensitivity wavelength of the spectral sensitivity distribution of the multilayer effect received by the above-described ISO sensitivity and red-sensitive silver halide emulsion layer from other layers can be determined by the method described in JP-A-11-305396.

The silver halide photographic light-sensitive material of the present invention has a red color.
Spectral sensitivity S of photosensitive layer and green photosensitive layer _{R (580)}, S_{G (580)}But
It is preferable to satisfy the following ranges at the same time. Where S
_{G (58 0)}, S_{R (580)}Is magenta at each wavelength
The minimum density of cyan color and cyan color plus a density of 1.0
Defined by the logarithm of the reciprocal of the exposure required to
You. S_{G (max)}And S_{R (max)}Are the red sensitive layer and the green
This refers to the sensitivity at the maximum sensitivity wavelength of the optical layer. Also, the spectral sensitivity
The degree changes from underexposed to overexposed.
Preferably not. 0.6 ≦ S_{R (max)}-S_{R (580)}≦ 0.9 0.6 ≦ S_{G (max)}-S_{G (580)}≦ 1.1.

The wavelength at which the red photosensitive layer has the highest sensitivity is from 610 nm to 640 nm, preferably 620 nm.
nm to 635 nm. Further, it is desirable that the spectral sensitivity S _{R (650)} of the red photosensitive layer at 650 nm has the following relationship. SR ₍₆₅₀₎ ≦ SR _(max) −0.7 Here, the definition of the spectral sensitivity is the same as the above definition.

The wavelength at which the green photosensitive layer has the highest sensitivity is from 520 nm to 580 nm, preferably 540 nm.
nm to 565 nm. Further, it is desirable that the spectral sensitivity S _{G (525)} of the green photosensitive layer at 525 nm has the following relationship. 0.1 ≦ _{SG (max)} −SG ₍₅₂₅₎ ≦ 0.3.

As a means for improving color reproducibility, it is preferable to use an interlayer suppression effect. In particular, the center-of-gravity sensitivity wavelength (λG) of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer
Is 520 nm <λ _G ≦ 580 nm, and the center-of-gravity sensitivity wavelength (λ _−R ) of the spectral sensitivity distribution of the multilayer effect that the red-sensitive silver halide emulsion layer receives from other silver halide emulsion layers in the range of 500 nm to 600 nm. Is 500 nm <λ- _R <5.
It is preferably 60 nm and λ _G -λ- _R is 5 nm or more, preferably 10 nm or more.

In order to provide the above-mentioned layering effect on the red-sensitive layer in a specific wavelength region, it is preferable to provide a layering effect donor layer separately containing predetermined spectrally sensitized silver halide grains. In order to realize the spectral sensitivity of the present invention, the multilayer sensitivity wavelength of the multilayer effect donor layer is 510 nm to 540 n.
m.

Here, the red-sensitive silver halide emulsion layer was 50
The center-of-gravity sensitivity wavelength λ _-R of the spectral sensitivity distribution of the multilayer effect received from another silver halide emulsion layer in the range of 0 nm to 600 nm
Can be determined by the method described in JP-A-11-305396. When λ _-B is determined in the same manner as in the procedure for determining λ _-R , the multilayer effect given by the multilayer effect donor layer must satisfy the condition (formula (2)) described in JP-A-11-305396. .

As a material giving the layering effect, a compound which reacts with an oxidation product of a developing agent obtained by development to release a development inhibitor or a precursor thereof is used. For example, D
An IR (development inhibitor releasing type) coupler, a DIR-hydroquinone, a coupler releasing DIR-hydroquinone or a precursor thereof, and the like are used. In the case of a development inhibitor having a large diffusivity, the development suppression effect can be obtained regardless of where the donor layer is located in the multilayer structure, but the development suppression effect in an unintended direction also occurs, so this is corrected. Color the donor layer (e.g., to the same color as the layer affected by the undesired development inhibitor).
Is preferred. In order to obtain the desired spectral sensitivity of the light-sensitive material of the present invention, it is preferable that the donor layer giving the multilayer effect develops magenta color.

The size and shape of the silver halide grains used in the layer giving the layering effect to the red-sensitive layer are not particularly limited. For example, tabular grains having a high aspect ratio and monodispersed emulsions having a uniform grain size can be used. Silver iodobromide grains having a layered structure of iodine are preferably used.
In order to enlarge the exposure latitude, it is preferable to mix two or more emulsions having different grain sizes.

The donor layer which gives the layer effect to the red-sensitive layer may be provided at any position on the support. However, the donor layer is provided closer to the support than the blue-sensitive layer and farther from the support than the red-sensitive layer. Is preferred. Further, it is more preferable that it is closer to the support than the yellow filter layer.

The donor layer which gives the red-sensitive layer a multilayer effect is preferably closer to the support than the green-sensitive layer, more preferably farther from the support than the red-sensitive layer, and closer to the support of the green-sensitive layer. Most preferably, it is located adjacent to the side. In this case, “adjacent” means that no intermediate layer or the like is interposed. The layer giving the multilayer effect to the red-sensitive layer may be composed of a plurality of layers. In that case, their positions may be adjacent to or separated from each other.

The emulsion used in the light-sensitive material of the present invention may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside a grain, or a type having a latent image on both the surface and the inside. However, it is necessary that the emulsion be a negative emulsion. Of the internal latent image type,
The emulsion may be a core / shell type internal latent image type emulsion described in No. 0, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical sensitization and spectral sensitization are used. The additive used in such a process is RD No. 1764
3, the same No. No. 18716 and the same No. 307105, and the corresponding portions are summarized in the table below.

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more emulsions differing in at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

US Pat. No. 4,082,553, US Pat. No. 4,082,553.
4,626,498, and JP-A-59-214852, in which a silver halide grain or a colloidal silver is coated with a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. It is preferably applied to
The term "silver halide particles having a fogged interior or surface" refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. Its preparation is described in US Pat. No. 4,626,498 and JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01
To 0.75 μm, particularly preferably 0.05 to 0.6 μm. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or number of silver halide grains has a grain size within ± 40% of the average grain size). Is preferable.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide has an average grain size (average value of the circle equivalent diameter of the projected area).
It is preferably from 0.01 to 0.5 μm, more preferably from 0.02 to 0.2 μm.

Fine grain silver halides can be prepared in the same manner as for ordinary light-sensitive silver halides. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, before adding this to the coating solution, a triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound. Colloidal silver can be contained in the layer containing fine silver halide grains.

The above-mentioned various additives are used in the light-sensitive material according to the present technology, but other various additives can be used according to the purpose. These additives are
For more details, Research Disclosure Item 17
643 (December 1978), Item 18716 (1
November 997) and Item 308119 (198).
(December 2009), and the relevant locations are summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23, page 648, right column, page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648, right column-996 right-998 right Super strong Sensitizer page 649 right column 4 Brightener 24 page 998 right 5 Antifoggant page 24-25 page 649 right column 998 right-1000 right and stabilizer 6 light absorber, page 25-26 page 649 right column 1003 Left to 1003 right Filter dye 650 page left column UV absorber 7 Stain inhibitor 25 page right column 650 left to right column 1002 right 8 Dye image stabilizer 25 page 1002 right 9 Hardening agent 26 page 651 left column 1004 right to 1005 left 10 Binder 26 Same as above 1003 right to 1004 right 11 Plasticizer, lubricant page 27 650 right column 1006 left to 1006 right 12 Coating aid, page 26 to 27 Same as above 1005 left to 1006 left Surfactant 13 Static page 27 Same as above 1006 right to 1007 left Inhibitor 14 matting agent 1008 left to 1009 left.

Techniques such as layer arrangement and the like which can be used for the photographic light-sensitive material of the present invention and the emulsion usable in the light-sensitive material, silver halide emulsion, dye-forming coupler, DI
Functional couplers such as R couplers, various additives, and development processing are described in European Patent No. 0565096A1 (published on October 13, 1993) and the patents cited therein. The following is a list of each item and the corresponding locations.

[0263] 1. Layer structure: page 61, lines 23 to 35, page 61, lines 41 to 62
Page 14 line, 2. 2. Intermediate layer: page 61, lines 36 to 40, 3. Multilayer effect imparting layer: page 62, lines 15 to 18, 4. Silver halide composition: page 62, lines 21 to 25; 5. Silver halide grain habit: page 62, lines 26 to 30, 6. Silver halide grain size: page 62, lines 31 to 34, 7. Emulsion production method: page 62, lines 35 to 40, Silver halide grain size distribution: page 62, 41 to 42
Row, 9. Tabular grains: page 62, lines 43 to 46,10. 10. Internal structure of particle: page 62, lines 47 to 53, Emulsion latent image forming type: page 62, line 54 to page 63, 5
Line, 12. 12. Physical ripening and chemical sensitization of emulsion: p. 63, lines 6 to 9, 13. Mixed use of emulsion: page 63, lines 10-13, 14. Fogged emulsion: p. 63, lines 14 to 31, Non-light-sensitive emulsion: page 63, lines 32-43, 16. 16. Silver coating amount: page 63, lines 49 to 50; Formaldehyde scavenger: page 64, 54-5
7 lines, 18 19. mercapto antifoggant: page 65, lines 1-2, Release agent such as fogging agent: page 65, lines 3-7, 20. Dye: page 65, lines 7 to 10, 21. 22. Color coupler in general: p. 65, lines 11 to 13, Yellow, magenta and cyan couplers: page 65, 1
Lines 4 to 25, 23. Polymer coupler: page 65, lines 26 to 28, 24. 25. Diffusible dye-forming coupler: page 65, lines 29 to 31, 25. Colored coupler: page 65, lines 32-38, 26. Functional couplers overall: p. 65, lines 39-44, 27. 25. Bleach accelerator releasing coupler: page 65, lines 45 to 48, Development accelerator releasing coupler: page 65, lines 49 to 53, 29. Other DIR couplers: page 65, line 54 to page 66, 4
Line, 30. Coupler dispersion method: page 66, lines 5-28, 31. Preservatives / fungicides: page 66, lines 29-33, 32. Type of photosensitive material: page 66, lines 34 to 36, 33. Photosensitive layer thickness and swelling speed: page 66, line 40 to page 67, 1
Row, 34. Back layer: page 67, lines 3 to 8, 35. General processing: page 67, lines 9-11, 36. Developer and developer: page 67, lines 12 to 30, 37. 38. Developer additive: page 67, lines 31 to 44, Reverse processing: page 67, lines 45 to 56, 39. Processing liquid opening ratio: page 67, line 57 to page 68, line 12, 40. Developing time: page 68, lines 13 to 15, 41. Bleach-fixing, bleaching, fixing: page 68, 16 lines-page 69, 31
Row, 42. Automatic developing machine: page 69, lines 32 to 40, 43. Rinsing, rinsing, stabilization: page 69, line 41 to page 70, line 18
Row, 44. Processing solution replenishment, reuse: page 70, lines 19-23, 45. 46. Built-in developer sensitive material: page 70, lines 24-33, Developing temperature: 70, lines 34-38, 47. Use for film with lens: page 70, lines 39-41.

A bleaching solution described in EP-A-602600 containing a 2-pyridinecarboxylic acid or 2,6-pyridinedicarboxylic acid, a ferric salt such as ferric nitrate, and a persulfate is also used. It can be used preferably. In the use of this bleaching solution, it is preferable to interpose a stopping step and a washing step between the color developing step and the bleaching step,
It is preferable to use an organic acid such as acetic acid, succinic acid, and maleic acid for the stop solution. In addition, this bleaching solution contains p
Organic acids such as acetic acid, succinic acid, maleic acid, glutaric acid, adipic acid, etc.
It is preferable to contain the compound in a range of 2 mol / liter (hereinafter, liter is also referred to as “L”).

Next, the magnetic recording layer preferably used in the present invention will be described. The magnetic recording layer preferably used in the present invention is a layer in which an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder is provided on a support.

The magnetic particles used in the present invention are γFe ₂ O
Ferromagnetic iron oxide such as ₃ , Co-coated γFe ₂ O ₃ , Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite , Ca ferrite and the like can be used. Co-coated ferromagnetic iron oxide, such as Co-coated γFe ₂ O _3, is preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g.

The saturation magnetization (σs) of the ferromagnetic material is preferably from 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 ⁵ A / m.
10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. JP-A-4-25
No. 9911, the surface described in 5-81652 is inorganic,
Magnetic particles coated with an organic substance can also be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural product described in JP-A-4-219569. Polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin has a Tg of −40 ° C. to 300 ° C. and a weight average molecular weight of 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable.
The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent.
Examples of the isocyanate-based crosslinking agent include isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates with polyalcohol (for example, tolylene diisocyanate). Reaction products of 3 mol of isocyanate and 1 mol of trimethylolpropane), and polyisocyanates formed by condensation of these isocyanates, and the like, which are described in, for example, JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. JP-A-5-08828
The dispersant described in No. 3 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to 3 μm. The weight ratio of the magnetic particles and the binder is preferably 0.5:
100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably
It is 0.01 to ² g / m ² , more preferably 0.02 to 0.5 g / m ² .
The transmission yellow density of the magnetic recording layer is preferably from 0.01 to 0.50, more preferably from 0.03 to 0.20, and particularly preferably from 0.04 to 0.15. The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method for applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in 341436 is preferred.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
5,229,259, 5,215,874 and EP 466,130.

Next, the polyester support preferably used in the present invention will be described. For details including photosensitive materials, treatments, cartridges and examples described later, refer to Published Technical Report, Official Technique No. 94-6023 (Invention Association; 1994.15.). The polyester used in the present invention is formed by using diol and aromatic dicarboxylic acid as essential components. As aromatic dicarboxylic acids, 2,6-, 1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, and terephthalic acid are used. Acids, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexane dimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene-2,
6-naphthalate. The average molecular weight range is about 5,000
Or 200,000. T of the polyester used in the present invention
g is 50 ° C. or higher, preferably 90 ° C. or higher.

Next, the polyester support has a curl.
The heat treatment temperature should be 40 ° C or higher and lower than Tg to reduce
More preferably, the heat treatment is performed at Tg-20 ° C. or higher and lower than Tg.
The heat treatment may be performed at a constant temperature within this temperature range,
The heat treatment may be performed while cooling. This heat treatment time is 0.
1 hour or more and 1500 hours or less, more preferably 0.5 hour or more
Less than 200 hours. The heat treatment of the support is performed in roll form.
Or may be carried out while being transported in web form.
Good. The surface is made uneven (for example, SnO_TwoAnd Sb_TwoO _FiveEtc.
(Apply conductive inorganic fine particles.)
No. Also, knurling is applied to the end and only the end is raised slightly.
To prevent cuts in the core
It is desirable. These heat treatments are performed on the surface after forming the support.
After treatment, after coating the back layer (antistatic agent, slip agent, etc.)
It may be carried out at any stage after the application. Preferred
Is after the application of the antistatic agent.

An ultraviolet absorbent may be kneaded into the polyester. In order to prevent light piping, the purpose can be achieved by kneading a commercially available dye or pigment for polyester, such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to perform a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

Next, the undercoating method will be described. The coating may be a single layer or two or more layers. As a binder for the undercoat layer,
Starting from copolymers starting from monomers selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc., polyethylene imine, epoxy resin, grafting Gelatin, nitrocellulose and gelatin are included.
Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, as a gelatin hardener, chromium salt (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6) are used.
-Hydroxy-S-triazine), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. As those antistatic agents, carboxylic acid and carboxylate, polymers including sulfonate,
Examples include cationic polymers and ionic surfactant compounds.

The most preferred antistatic agent is Zn
O, TiO_Two, SnO_Two, Al_TwoO_Three, In_TwoO_Three, SiO _Two, MgO, BaO, Mo
O_Three, V_TwoO_FiveAt least one type of volume resistivity selected from
Ten⁷Ωcm or less, more preferably 10^FiveGrains that are Ω · cm or less
0.001 to 1.0 μm crystalline metal oxide or
Fine particles of these composite oxides (Sb, P, B, In, S, Si, C, etc.),
Furthermore, sol-like metal oxides or composite oxides thereof
Particles.

The content in the light-sensitive material is from 5 to 500 mg / m^TwoBut
Preferably particularly preferably 10 to 350 mg / m ^TwoIt is. Conductive
Ratio of the amount of the crystalline oxide or its composite oxide to the binder
Is preferably 1/300 to 100/1, more preferably 1/100 to 100
/ 5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25
° C, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level.

The sliding agents usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and the like. Siloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow, and the average particle size is 0.9 to 1.1.
It is preferable that 90% or more of the total number of particles be contained during the doubling. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), Polystyrene particles (0.25 μm) and colloidal silica (0.03 μm).

Next, the film cartridge used in the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone used in the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A-1-312537,
No. 1-312538. Especially 25 ℃, 25
The resistance at% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be the same as the current 135 size.
It is also effective to set the diameter of the m cartridge to 22 mm or less. The volume of the patrone case is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. Weight of plastic used for patrone and patrone case is 5g
~ 15 g is preferred.

Further, a patrone used in the present invention to feed a film by rotating a spool may be used. Further, a structure may be employed in which the leading end of the film is housed in the patrone main body, and the leading end of the film is sent out from the port portion of the patrone by rotating the spool shaft in the film sending direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development or a photographic film that has been subjected to development processing. Also, raw film and developed photographic film may be stored in the same new patrone,
A different patrone may be used.

The color photographic light-sensitive material of the present invention is also suitable as a negative film for an advanced photo system (hereinafter referred to as an AP system), and NEXIA A manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film). NEXIA
Films processed into the AP system format like F, NEXIA H (in order, ISO 200/100/400) and stored in a special cartridge can be mentioned. These AP system cartridge films are used by loading them into an AP system camera such as the EPION series (e.g., EPION 300Z) manufactured by Fujifilm. Further, the color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as a super color slim made by Fujifilm.

The film photographed by the above is printed in the mini-lab system through the following steps.

(1) Receipt (exposed cartridge film received from customer) (2) Detach step (transfer film from cartridge to intermediate cartridge for development step) (3) Film development (4) Rear touch step (development (Return the used negative film to the original cartridge.) (5) Print (C / H / P3 type prints and index prints on color paper (preferably made by FUJIFILM)
(Continuous automatic printing on SUPER FA8]) (6) Collation and shipping (collating cartridges and index prints with ID numbers and shipping with prints).

[0287] These systems include Fujifilm Minilab Champion Super FA-298 / FA-278 / FA-258 / F
A-238 and Fujifilm Digital Lab System Frontier are preferred. FP922AL / FP562B / FP562B, AL / FP362B / FP as a minilab champion film processor
362B, AL, and the recommended treatment chemicals are Fujicolor Justit CN-16L and CN-16Q. PP3008AR / PP3008A / PP1828AR / PP1828A /
PP1258AR / PP1258A / PP728AR / PP728A are the recommended treatment chemicals. Fujicolor Justit CP-47L and CP-4
0FAII. In the frontier system, a scanner & image processor SP-1000 and a laser printer & paper processor LP-1000P or a laser printer LP-1000W are used. The detacher used in the detaching process and the rear toucher used in the rear touching process are Fujifilm's DT200 / DT100 and AT200 / AT1 respectively.
00 is preferred.

The AP system can also be enjoyed by a photo joy system centered on Fujifilm's Aladdin 1000 digital image workstation. For example, Aladdin 1000 can be directly loaded with a developed AP system cartridge film, or negative, positive, and print image information can be transferred to a 35mm film scanner FE.
The digital image data obtained by inputting using the -550 or PE-550 flat head scanner can be easily processed and edited. The data are stored in a digital color printer NC-550AL using a light fixing type thermal color printing system and a pictograph 3000 using a laser exposure thermal development transfer system.
Or as prints by existing laboratory equipment through a film recorder. The Aladdin 1000 can also output digital information directly to a floppy (registered trademark) disk or Zip disk, or to a CD-R via a CD writer.

On the other hand, at home, the developed AP system cartridge film is transferred to a Fuji Film Photo Player AP.
You can enjoy photos on TV just by loading it in -1,
By loading it onto a Fujifilm AS-1 photo scanner, image information can be continuously and rapidly captured on a personal computer. To input a film, print or three-dimensional object to a personal computer, use Fujifilm PhotoVision FV-10 / FV
-5 is available. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R, or hard disk can be variously processed and enjoyed on a personal computer using Fujifilm's application software Photo Factory. In order to output high-quality prints from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fujifilm of a light fixing type thermal color print system is suitable.

In order to store the developed AP system cartridge film, the Fuji Color Pocket Album AP-5 POP L, AP-1 POP L, AP-1 POP KG or the cartridge file 16 is preferable.

[0291]

Example 1 <Preparation of Sample 001 (Invention)> Em-O was prepared from a silver halide emulsion Em-A by the following production method.

(Preparation of Em-A) An aqueous solution containing 1.0 g of low-molecular-weight gelatin having a molecular weight of 15,000, 1.0 g of KBr and 1,200 g of KBr (hereinafter referred to as "m
L ". ) Was kept at 35 ° C. and stirred vigorously. 30 mL of aqueous solution containing 1.9 g of AgNO ₃ , KB
r1.5 g and low molecular weight gelatin having a molecular weight of 15,000.
30 mL of an aqueous solution containing 7 g was added by a double jet method over 30 seconds to form nuclei. At this time, the excess concentration of KBr was kept constant. 6 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After ripening, 35 g of succinated gelatin was added. The pH was adjusted to 5.5. AgNO ₃ , 30
g of an aqueous solution containing 150 g and an aqueous KBr solution were added over 16 minutes by the double jet method. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. further,
An aqueous solution containing 110 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over 15 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time,
An AgI fine grain emulsion having a size of 0.03 µm was simultaneously added at an accelerated flow rate such that the silver iodide content became 3.8 mol%, and the silver potential was kept at -25 mV.

132 m of an aqueous solution containing 35 g of AgNO ₃
L and KBr aqueous solution were added by a double jet method over 7 minutes. K is adjusted so that the potential at the end of the addition becomes -20 mV
The addition of the aqueous Br solution was adjusted. After raising the temperature to 40 ° C,
5.6 g of Compound 1 was added in KI conversion, and 0.8 M
64 cc of an aqueous solution of sodium sulfite was added. Further, an aqueous NaOH solution was added to raise the pH to 9.0 and maintained for 4 minutes to rapidly generate iodide ions. Then, the pH was returned to 5.5. After the temperature was returned to 55 ° C., 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After completion of the addition, an aqueous solution 2 containing 70 g of AgNO ₃
50 mL and an aqueous KBr solution were added over 20 minutes while maintaining the potential at 60 mV. At this time, 1.0 × 10 ⁻⁵ mol of yellow blood salt was added to 1 mol of silver. After washing with water,
80 g of lime-processed gelatin having a calcium concentration of 1 ppm was added, and the mixture was adjusted to pH 5.8 and pAg 8.7 at 40 ° C.

[0294]

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The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy, and found to be 15 ppm, 2 ppm and 1 ppm, respectively.

The above emulsion was heated to 56 ° C. First, 1 g of a pure AgBr fine grain emulsion having a size of 0.05 μm was added thereto in terms of Ag and shelled. Next, sensitizing dyes 1, 2, 3
In the form of a solid fine dispersion,
5.85 × 10 ^-4 mol, 3.06 × 10 ^-4 mol, 9.0
0 × 10 ^-6 mol was added. As shown in the preparation conditions in Table 1, after dissolving the inorganic salt in ion-exchanged water, a sensitizing dye was added, and the solution was treated with a dissolver blade at 60 ° C. using a dissolver blade.
By dispersing at 0 rpm for 20 minutes, sensitizing dye 1,
A few solid fine dispersions were made. When the sensitizing dye is added and the adsorption of the sensitizing dye reaches 90% of the amount adsorbed in the equilibrium state, calcium nitrate is added at a calcium concentration of 250 ppm.
Was added so that The amount of sensitizing dye adsorbed is determined by separating the solid layer and the liquid layer by centrifugal sedimentation, measuring the difference between the amount of sensitizing dye added first and the amount of sensitizing dye in the supernatant, and adsorbing the sensitizing dye. The amount of dye was determined. After addition of calcium nitrate, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N,
N-dimethylselenourea and compound 4 were added for optimal chemical sensitization. N, N-dimethylselenourea was added in an amount of 3.40 × 10 ⁻⁶ mol per mol of silver. At the end of the chemical sensitization, Compound 2 and Compound 3 were added to prepare Em-A.

[0297]

[Table 1]

[0298]

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[0299]

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[0300]

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[0301]

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[0302]

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[0303]

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(Preparation of Em-B) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 5 g, and the succinated gelatin was converted to a trimellitization ratio of 98,000 having a molecular weight of 100,000 containing 35 μmol methionine per gram. %
The compound 1 was replaced with the compound 6, and the added amount of the compound 6 was 8.0 in terms of KI.
g, and the amount of the sensitizing dye added before the chemical sensitization was 6.50 × 10 ^-4 mol, 3.40 × 10 ^-4 mol, and 1.40 × 10 ^-4 mol, respectively, with respect to the sensitizing dyes 1, 2, and 3, respectively. Em-B in the same manner as Em-A, except that the amount was changed to 00 × 10 ⁻⁵ mol and the amount of N, N-dimethylselenourea added during chemical sensitization was changed to 4.00 × 10 ⁻⁶ mol. Was prepared.

[0305]

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(Preparation of Em-C) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 1.5 g.
The succinated gelatin was replaced with phthalated gelatin having a molecular weight of 100,000 and a phthalation rate of 97%, containing 35 μmol / g of methionine, compound 1 was replaced with compound 7, and the added amount of compound 7 was changed to 7.1 g in terms of KI. The amount of sensitizing dye added before chemical sensitization was changed to sensitizing dye 1,
7.80 × 10 ^-4 mol and 4.0 with respect to 2, 3, respectively.
Em except that the amounts were changed to 8 × 10 ⁻⁴ mol and 1.20 × 10 ⁻⁵ mol, and the amount of N, N-dimethylselenourea added during chemical sensitization was changed to 5.00 × 10 ⁻⁶ mol. Em-C was prepared in the same manner as in -A.

[0307]

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(Preparation of Em-E) 1200 mL of an aqueous solution containing 1.0 g of low-molecular-weight gelatin having a molecular weight of 15,000 and 1.0 g of KBr was maintained at 35 ° C. and stirred vigorously. Ag
30 mL of an aqueous solution containing 1.9 g of NO ₃ , KBr 1.5
g and 0.7 g of low molecular weight gelatin having a molecular weight of 15,000 were added over 30 seconds by a double jet method over 30 seconds to form nuclei. At this time, the excess concentration of KBr was kept constant. 6 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After ripening, 15 g of succinated gelatin and 20 g of the above-mentioned trimellitated gelatin were added. p
H was adjusted to 5.5. 150 mL of an aqueous solution containing 30 g of AgNO ₃ and an aqueous KBr solution were added over 16 minutes by a double jet method. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. Furthermore, AgNO ₃ 1
An aqueous solution containing 10 g and an aqueous KBr solution were added by a double jet method over 15 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the size is 0.
An AgI fine grain emulsion of 03 µm was prepared by using a silver iodide content of 3.8.
At the same time, the flow rate was accelerated so as to be mol%, and the silver potential was kept at -25 mV.

132 mL of an aqueous solution containing 35 g of AgNO ₃
And an aqueous KBr solution were added over 7 minutes by the double jet method. K is adjusted so that the potential at the end of the addition becomes -20 mV.
The addition of the aqueous Br solution was adjusted. After KBr was added and the potential was adjusted to −60 mV, 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was added. After the completion of the addition, an aqueous solution of low molecular weight gelatin having a molecular weight of 15,000, an aqueous solution of AgNO _{3 and an} aqueous solution of KI were prepared by premixing immediately before addition in another chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570. While continuously adding 8.0 g of an AgI fine particle emulsion having a particle size (equivalent sphere diameter) of 0.008 μm in terms of KI, 250 mL of an aqueous solution containing 70 g of AgNO ₃ and an aqueous KBr solution were adjusted to a potential of −60 mV.
Over a period of 20 minutes. At this time, 1.0 × 10 ⁻⁵ mol of yellow blood salt was added to 1 mol of silver.
After washing with water, 80 g of lime-processed gelatin having a calcium concentration of 1 ppm was added, and the pH and pAg at 40 ° C. were 5.8 and 8.7, respectively.
Was adjusted.

[0310] The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy.
ppm. In chemical sensitization, sensitizing dyes 1, 2, and 3 were changed to sensitizing dyes 4, 5, and 6, and the added amount was 7.
73 × 10 ^-4 mol, 1.65 × 10 ^-4 mol, 6.20 ×
Em-E was prepared by performing chemical sensitization in the same manner as in Em-A except that the amount was changed to 10 ^-5 mol.

[0311]

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[0312]

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[0313]

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(Preparation of Em-F) Low molecular weight of 15,000
Water containing 1.0 g of molecular weight gelatin and 1.0 g of KBr
The liquid (1200 mL) was kept at 35 ° C. and stirred vigorously. Ag
NO_Three 30 mL of an aqueous solution containing 1.9 g, KBr 1.5
g and 0.7 g of low molecular weight gelatin having a molecular weight of 15,000.
30 mL of aqueous solution for 30 seconds by the double jet method
To form nuclei. At this time, the excess concentration of KBr
Kept constant. Add 5 g of KBr, raise the temperature to 75 ° C, and ripen
Done. After aging, 20g succinated gelatin and phthalate
15 g of gelatinized gelatin was added. Adjust the pH to 5.5
Was. AgNO_Three 150 mL of aqueous solution containing 30 g and KBr
Add the aqueous solution by the double jet method over 16 minutes
Was. At this time, the silver potential is set to −25 with respect to the saturated calomel electrode.
mV. Furthermore, AgNO _Three Water containing 110g
The initial flow rate of the liquid and KBr aqueous solution is initial by the double jet method.
Increase the flow rate to 1.2 times the flow rate and
Or added. At this time, the AgI having a size of 0.03 μm
The fine grain emulsion was adjusted to have a silver iodide content of 3.8 mol%.
At the same time with accelerated flow rate and silver potential of -25 mV
Kept.

132 mL of an aqueous solution containing 35 g of AgNO ₃
And an aqueous KBr solution were added over 7 minutes by the double jet method. After adjusting the potential to −60 mV by adding a KBr aqueous solution, 9.2 g of an AgI fine grain emulsion having a size of 0.03 μm in terms of KI was added. 1 mg of sodium benzenethiosulfonate was added, and the calcium concentration was 1
13 g of lime-treated gelatin at 13 ppm were added. After completion of the addition, 250 mL of an aqueous solution containing 70 g of AgNO ₃ and KB
The aqueous solution was added over 20 minutes while maintaining the potential at 60 mV. At this time, the yellow blood salt was added in an amount of 1. mol per mol of silver.
0 × 10 ^-5 mol was added. After washing with water, 80 g of lime-processed gelatin having a calcium concentration of 1 ppm was added, and the mixture was adjusted to pH 5.8 and pAg 8.7 at 40 ° C.

The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy to find that they were 15 ppm, 2 ppm and 1 ppm, respectively.
ppm. In chemical sensitization, sensitizing dyes 1, 2, and 3 were replaced with sensitizing dyes 4, 5, and 6, and the amount added was 8.5.
0 × 10 ^-4 mol, 1.82 × 10 ^-4 mol, 6.82 × 1
0 except that the ^-5 mol performs chemical sensitization in the same manner as Em-B, was prepared Em-F.

(Preparation of Em-G) A low molecular weight of 15,000
Water containing 1.0 g of molecular weight gelatin and 1.0 g of KBr
The liquid (1200 mL) was kept at 35 ° C. and stirred vigorously. Ag
NO_Three 30 mL of an aqueous solution containing 1.9 g, KBr 1.5
g and 0.7 g of low molecular weight gelatin having a molecular weight of 15,000.
30 mL of aqueous solution for 30 seconds by the double jet method
To form nuclei. At this time, the excess concentration of KBr
Kept constant. Add 1.5 g of KBr and raise the temperature to 75 ° C
And matured. After ripening, the above mentioned trimellitized gelatin
And 15 g of the above-mentioned phthalated gelatin were added.
The pH was adjusted to 5.5. AgNO _ThreeContaining water, 30g
150 mL of the solution and KBr aqueous solution
Added over 6 minutes. At this time, the silver potential is
-25 mV with respect to the metal electrode. Furthermore, AgNO
_Three Double-jet the aqueous solution containing 110 g and the aqueous KBr solution.
Flow rate so that the final flow rate is 1.2 times the initial flow rate by the
Accelerated and added over 15 minutes. At this time, the size
A 0.03 μm AgI fine grain emulsion having a silver iodide content of
At the same time, the flow rate is increased to 3.8 mol%, and
And the silver potential was kept at -25 mV.

AgNO_Three132m aqueous solution containing 35g
L and KBr aqueous solution for 7 minutes by double jet method
Was added. KBr aqueous solution so that the potential becomes -60 mV
Was adjusted. AgI fine particles with a size of 0.03 μm
7.1 g of the emulsion was added in terms of KI. Benzenethios
Add 1 mg of sodium sulfonate and add calcium
13 g of lime-processed gelatin having a concentration of 1 ppm was added.
After the addition is completed, AgNO _Three250 mL of aqueous solution containing 70 g
And the KBr aqueous solution for 20 minutes while maintaining the potential at 60 mV.
Added over time. At this time, yellow blood salt was added to 1 mole of silver.
1.0 × 10^-FiveMole was added. After washing with water,
80 g of lime-processed gelatin having a concentration of 1 ppm
The pH was adjusted to 5.8 and pAg to 8.7 at 40 ° C.

The content of calcium, magnesium and strontium in the above emulsion was measured by ICP emission spectroscopy.
ppm. Sensitizing dyes 1, 2, and 3 are sensitizing dyes 4,
5 and 6, and the added amount of each was 1.00 × 10 ^−3.
Em-G was prepared in the same manner as Em-C, except that the moles were 2.15 × 10 ⁻⁴ mol and 8.06 × 10 ⁻⁵ mol.

(Preparation of Em-J) In the preparation of Em-B, sensitizing dyes added before chemical sensitization were changed to sensitizing dyes 7 and 8, and the added amount of each was 7.65 × 10 ^-4. Mole,
Em-J was prepared in the same manner as Em-B except that the amount was 2.74 × 10 ⁻⁴ mol.

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(Preparation of Em-L) (Preparation of silver bromide seed crystal emulsion) A bromide containing 0.66 μm in average equivalent sphere diameter, an aspect ratio of 9.0, and 1.16 mol of silver per kg of emulsion and 66 g of gelatin. A silver tabular emulsion was prepared.

(Growth step 1) 1.2 g of potassium bromide and 9
Aqueous solution 12 containing succinated gelatin with a succinating rate of 8%
0.3 g of modified silicone oil was added to 50 g. 0.
After adding the above silver bromide tabular emulsion containing 086 mol of silver, 7
The mixture was stirred at 8 ° C. An aqueous solution containing 18.1 g of silver nitrate and the silver iodide fine particles having a particle size of 0.037 μm were added so as to be 5.4 mol with respect to silver to be added. Further, at this time, an aqueous potassium bromide solution was added while adjusting the pAg to be 8.1 with a double jet.

(Growth Process 2) After adding 2 mg of sodium benzenethiosulfonate, 0.45 g of 3,5-disulfocatechol disodium salt and 2.5 g of thiourea dioxide were added.
mg was added.

Further, an aqueous solution containing 95.7 g of silver nitrate and an aqueous solution of potassium bromide were accelerated by a double jet to obtain an aqueous solution.
Added over minutes. At this time, the silver iodide fine particles of 0.037 μm were added so as to be 7.0 mol% with respect to the added silver. At this time, the amount of potassium bromide in the double jet was adjusted so that the pAg became 8.1. After the addition was completed, 2 mg of sodium benzenethiosulfonate was added.

(Growth Process 3) An aqueous solution containing 19.5 g of silver nitrate and an aqueous potassium bromide solution were added by a double jet over 16 minutes. At this time, the amount of the aqueous potassium bromide solution was adjusted so that the pAg became 7.9.

(Addition of sparingly soluble silver halide emulsion 4) After adjusting the pAg of the above host particles to 9.3 with an aqueous potassium bromide solution, the above 0.037 μm silver iodide fine grain emulsion 2 was prepared.
5 g was added rapidly within 20 seconds.

(Formation of outermost shell layer 5) Further, 34.9 g of silver nitrate
Was added over 22 minutes.

This emulsion was tabular grains having an average aspect ratio of 9.8 and an average equivalent sphere diameter of 1.4 μm, and the average silver iodide content was 5.5 mol%.

[Chemical sensitization] After washing with water, the succinization ratio was 98.
% Succinated gelatin and calcium nitrate at 40 ° C
And adjusted to pH 5.8 and pAg 8.7. The temperature was raised to 60 ° C., 5 × 10 ⁻³ mol of a 0.07 μm silver bromide fine grain emulsion was added, and sensitizing dyes 9, 10 and 11 were added 20 minutes later. Thereafter, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea, compound 4
Was added for optimal chemical sensitization. Compound 3 was added 20 minutes before the end of the chemical sensitization, and Compound 5 was added at the end of the chemical sensitization. Here, the optimal chemical sensitization means that the sensitizing dye and each compound are added in an amount of 10 ^-1 to 10 ^-8 per mol of silver halide so that the sensitivity at the time of exposure at 1/100 is maximized.
It means that it was selected from the range of addition amount of mol.

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(Preparation of Em-O) An aqueous gelatin solution (1250 mL of distilled water, 48 g of deionized gelatin, 0.75 g of KBr) was placed in a reaction vessel equipped with a stirrer, and the temperature of the solution was kept at 70 ° C. To this solution was added 276 mL of an aqueous solution of AgNO ₃ (containing 12.0 g of AgNO ₃ ) and an aqueous solution of KBr having an equimolar concentration while maintaining the pAg at 7.26 over 7 minutes by a controlled double jet addition method. Then, the temperature was reduced to 68 ° C, and thiourea dioxide (0.05
wt%) was added to 7.6 mL.

Subsequently, 592.9 mL of an AgNO ₃ aqueous solution
(Including 108.0 g of AgNO ₃ )
A mixed aqueous solution of r and KI (2.0 mol% KI) was added over 18 minutes and 30 seconds by a controlled double jet addition method while maintaining the pAg at 7.30. Five minutes before the end of the addition, 18.0 m of thiosulfonic acid (0.1 wt%) was added.
L was added.

The obtained grains were cubic grains having an equivalent sphere diameter of 0.19 μm and an average silver iodide content of 1.8 mol%. E
m-O was re-dispersed by desalting and washing with a normal flocculation method, and then at 40 ° C., pH 6.2 and pAg.
Adjusted to 7.6. Subsequently, Em-O was subjected to the following spectral and chemical sensitization.

First, sensitizing dye 10, sensitizing dye 11, and sensitizing dye 12 were each added in an amount of 3.37 × 10 ^-4 per mol of silver.
Mol / mol, KBr 8.82 × 10 ^-4 mol / mol, sodium thiosulfate 8.83 × 10 ^-5 mol / mol, aqueous potassium thiocyanate 5.95 × 10 ^-4 mol / mol and potassium chloroaurate 3. Aging was performed at 68 ° C. by adding 07 × 10 ⁻⁵ mol / mol. The aging time is 1/10
The sensitivity was adjusted so that the 0 second exposure sensitivity was the highest.

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For the preparation of (Em-D, H, I, K, M, N) tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. Further, according to the examples of JP-A-3-237450, gold sensitization was carried out in the presence of the spectral sensitizing dyes shown in Table 2 and sodium thiocyanate.
Sulfur sensitization and selenium sensitization are applied. Emulsions D, H,
I and K contain optimum amounts of Ir and Fe. Emulsion M, N
Is subjected to reduction sensitization during grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

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[Table 2]

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[Table 3]

In Table 3, dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.

1) Support The support used in this example was prepared by the following method. 1) First layer and undercoat layer For a polyethylene naphthalate support having a thickness of 90 μm, a treatment atmosphere pressure of 0.2 Torr was applied to both surfaces of each support.
r, partial pressure of H ₂ O in atmosphere gas 75%, discharge frequency 30
A glow discharge treatment was performed at a frequency of 2500 kHz, an output of 2500 W, and a treatment intensity of 0.5 kV · A · min / m ² . A coating solution having the following composition was applied as a first layer on the support at a coating amount of 5 mL / m ² using a bar coating method described in Japanese Patent Publication No. 58-4589.

Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by weight 10% aqueous dispersion. Secondary aggregate having a primary particle diameter of 0.005 μm and an average particle diameter of 0.05 μm) Gelatin 0.5 parts by weight Water 49 parts by weight Polyglycerol polyglycidyl ether 0.16 parts by weight Poly (degree of polymerization 20) oxyethylene 0.1 parts by weight Sorbitan monolaurate.

Further, after the first layer was applied, it was wound around a stainless steel core having a diameter of 20 cm, and was subjected to a heat treatment at 110 ° C. (Tg of the PEN support: 119 ° C.) for 48 hours, subjected to a heat history, and annealed. Thereafter, a coating solution having the following composition was applied to the side opposite to the first layer side as an undercoat layer for the emulsion at a coating amount of 10 mL / m ² using a bar coating method.

Gelatin 1.01 parts by weight Salicylic acid 0.30 parts by weight Resorcin 0.40 parts by weight Poly (degree of polymerization 10) oxyethylene nonylphenyl ether 0.11 parts by weight Water 3.53 parts by weight Methanol 84.57 parts by weight n -Propanol 10.08 parts by weight.

Further, a second layer and a third layer described later are sequentially coated on the first layer, and finally, a color negative photosensitive material having a composition described later is overlaid on the opposite side to form a silver halide emulsion. A transparent magnetic recording medium with a layer was produced.

2) Second layer (transparent magnetic recording layer) Dispersion of magnetic material Co-coated γ-Fe ₂ O ₃ magnetic material (average major axis length: 0.25 μm)
m, S _BET : 39 m ² / g, Hc: 831 Oe, σs
: 77.1 emu / g, σr: 37.4 emu / g)
1100 parts by weight, 220 parts by weight of water, and 165 parts by weight of a silane coupling agent [3- (poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane] were added and kneaded well with an open kneader for 3 hours. The coarsely dispersed viscous liquid was dried at 70 ° C. for 24 hours to remove water, and then heat-treated at 110 ° C. for 1 hour to produce surface-treated magnetic particles.

Further, the mixture was kneaded again in an open kneader for 4 hours according to the following formulation.

The above-mentioned surface-treated magnetic particles 855 g Diacetyl cellulose 25.3 g Methyl ethyl ketone 136.3 g Cyclohexanone 136.3 g Further, the following formulation was finely dispersed in a sand mill (1/4 G sand mill) at 2,000 rpm for 4 hours. did. As the medium, glass beads having a diameter of 1 mm were used.

The kneading liquid 45 g diacetyl cellulose 23.7 g methyl ethyl ketone 127.7 g cyclohexanone 127.7 g Further, a magnetic substance-containing intermediate liquid was prepared according to the following formulation.

Preparation of Magnetic Substance-Containing Intermediate Solution 674 g of the above magnetic substance fine dispersion liquid 24280 g (solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) cyclohexanone 46 g After mixing these, The mixture was stirred with a disper to prepare a "magnetic substance-containing intermediate liquid".

The α-alumina abrasive dispersion used in the present invention was prepared according to the following formulation. (A) Sumicorundum AA-1.5 (average primary particle diameter 1.5 μm, specific surface area 1.3 m ² / g).

Preparation of Particle Dispersion Liquid Sumicorundum AA-1.5 152 g Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone Co., Ltd.) 0.48 g Diacetyl cellulose solution 227.52 g (solid content 4.5%, solvent: methyl ethyl ketone) / Cyclohexanone = 1/1).

According to the above formula, a ceramic-coated sand mill (1/4 G sand mill) was used at 800 rpm.
m for 4 hours. As the media, zirconia beads having a diameter of 1 mm were used.

(B) Colloidal silica particle dispersion (fine particles) "MEK-ST" manufactured by Nissan Chemical Industries, Ltd. was used. This is a dispersion liquid of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium,
The solids content is 30%.

Preparation of Second Layer Coating Solution The above magnetic substance-containing intermediate solution 19053 g Diacetyl cellulose solution 264 g (solid content: 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion “MEK-ST” [Dispersion b] 128 g (solid content 30%) AA-1.5 dispersion [dispersion a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Co., Ltd.) Diluent 203 g (solid content 20%, dilution Solvent: methyl ethyl ketone / cyclohexanone = 1/1) methyl ethyl ketone 170 g cyclohexanone 170 g.

The coating solution obtained by mixing and stirring the above was applied by a wire bar so as to have an application amount of 29.3 mL / m ² . Drying was performed at 110 ° C. The thickness of the dried magnetic layer was 1.0 μm.

3) Third Layer (Higher Fatty Acid Ester Slip Agent-Containing Layer) Preparation of Dispersion Solution of Slip Agent The following solution A was heated and dissolved at 100 ° C., added to Solution A, and dispersed with a high-pressure homogenizer. Was prepared.

Solution A The following compound 399 parts by weight C ₆ H ₁₃ CH (OH) (CH ₂ ) ₁₀ COOC ₅₀ H _{101 The following} compound 171 parts by weight nC ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H cyclohexanone 830 Parts by weight A Liquid Cyclohexanone 8600 parts by weight.

Preparation of Spherical Inorganic Particle Dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation.

Isopropyl alcohol 93.54 parts by weight Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone) Compound 1-1: (CH ₃ O) ₃ Si— (CH ₂ ) ₃ —NH ₂ ) 5.53 parts by weight Compound 2-1 2.93 parts by weight

Embedded image Seahoster KEP50 88.00 parts by weight (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.).

After stirring for 10 minutes with the above formulation, the following is further added.

Diacetone alcohol 252.93 parts by weight.

While the above solution was cooled with ice and stirred, an ultrasonic homogenizer “SONIFIER450 (BRANSON) was used.
(Manufactured by Co., Ltd.) for 3 hours to obtain a spherical inorganic particle dispersion c1.

Preparation of Spherical Organic Polymer Particle Dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation.

XC99-A8808 (manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by weight Methyl ethyl ketone 120 parts by weight Cyclohexanone 120 parts by weight (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone) = 1/1).

While cooling with ice and stirring, an ultrasonic homogenizer “SONIFIER450 (BRANSON CORPORATION)
(2) for 2 hours to obtain a dispersion liquid c2 of spherical organic polymer particles.

Preparation of Third Layer Coating Solution The following was added to 542 g of the above-mentioned slip agent dispersion stock solution to prepare a third layer coating solution.

Diacetone alcohol 5950 g Cyclohexanone 176 g Ethyl acetate 1700 g The above-mentioned Seahosta KEP50 dispersion [c1] 53.1 g The above-mentioned spherical organic polymer particle dispersion [c2] 300 g FC431 2.65 g (3M Corporation) BYK310 5.3 g (manufactured by BYK Chemi Japan KK, solid content 25%).

The above third layer coating solution was coated on the second layer by 10.3
It was applied at a coating amount of 5 mL / m ² , dried at 110 ° C., and further dried at 97 ° C. for 3 minutes.

4) Coating of Photosensitive Layer Next, on the opposite side of the back layer obtained above, layers having the following compositions were applied in a multi-layered manner to prepare a color negative film.

(Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow Coupler H: gelatin hardener (specific compounds are described below with numerical values following symbols and chemical formulas after). The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.122 0.07 μm Silver Iodobromide Emulsion Silver 0.01 Gelatin 0.919 ExC-1 0.002 ExC-3 0.002 Cpd -2 0.001 HBS-1 0.005 HBS-2 0.002.

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.055 Gelatin 0.425 ExF-1 0.002 Solid Disperse Dye ExF-9 0.120 HBS-1 0.074.

Third layer (low-sensitivity red-sensitive emulsion layer) Em-D silver 0.577 Em-C silver 0.347 ExC-1 0.188 ExC-2 0.011 ExC-3 0.075 ExC-40 .121 ExC-5 0.010 ExC-6 0.007 Cpd-2 0.025 Cpd-4 0.025 Cpd-7 0.050 Cpd-8 0.050 HBS-1 0.114 HBS-5 0.038 Gelatin 1.474.

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Em-B Silver 0.431 Em-C Silver 0.432 ExC-1 0.154 ExC-2 0.068 ExC-3 0.018 ExC-40 .103 ExC-5 0.023 ExC-6 0.010 Cpd-2 0.036 Cpd-4 0.028 Cpd-7 0.010 Cpd-8 0.010 HBS-1 0.129 Gelatin 1.086.

Fifth layer (high-sensitivity red-sensitive emulsion layer) Em-A silver 1.108 ExC-1 0.180 ExC-3 0.035 ExC-6 0.029 Cpd-2 0.064 Cpd-4 077 Cpd-7 0.040 Cpd-8 0.040 HBS-1 0.329 HBS-2 0.120 Gelatin 1.245.

Sixth layer (intermediate layer) Cpd-1 0.094 Cpd-9 0.369 Solid disperse dye ExF-4 0.030 HBS-1 0.049 Polyethyl acrylate latex 0.088 Gelatin 0.886.

Seventh Layer (Layer that Gives Layering Effect to Red Sensitive Layer) Em-J Silver 0.293 Em-K Silver 0.293 Cpd-4 0.030 ExM-2 0.120 ExM-3 0.016 ExY -1 0.016 ExY-6 0.036 Cpd-6 0.011 HBS-1 0.090 HBS-3 0.003 HBS-5 0.030 Gelatin 0.610.

Eighth layer (low-sensitivity green-sensitive emulsion layer) Em-H silver 0.329 Em-G silver 0.333 Em-I silver 0.088 ExM-2 0.378 ExM-3 0.047 ExY-1 0.017 HBS-1 0.098 HBS-3 0.010 HBS-4 0.077 HBS-5 0.548 Cpd-5 0.010 Gelatin 1.470.

Ninth Layer (Medium Speed Green Sensitive Emulsion Layer) Em-F Silver 0.457 ExM-2 0.032 ExM-3 0.029 ExM-4 0.029 ExY-1 0.007 ExC-6 010 HBS-1 0.065 HBS-3 0.002 HBS-5 0.020 Cpd-5 0.004 Gelatin 0.446.

Tenth Layer (High Sensitive Green Sensitive Emulsion Layer) Em-E Silver 0.794 ExC-6 0.002 ExM-1 0.013 ExM-2 0.011 ExM-3 0.030 ExM-40 017 ExY-5 0.003 Cpd-3 0.004 Cpd-4 0.007 Cpd-5 0.010 HBS-1 0.148 HBS-5 0.037 Polyethyl acrylate latex 0.099 Gelatin 0.939.

Eleventh layer (yellow filter layer) Cpd-1 0.094 Solid disperse dye ExF-2 0.150 Solid disperse dye ExF-5 0.010 Oil-soluble dye ExF-7 0.010 HBS-1 0.049 Gelatin 0.630.

12th layer (low-sensitivity blue-sensitive emulsion layer) Em-O silver 0.112 Em-M silver 0.320 Em-N silver 0.240 ExC-1 0.027 ExY-1 0.027 ExY-2 0.890 ExY-6 0.120 Cpd-2 0.100 Cpd-3 0.004 HBS-1 0.222 HBS-5 0.074 Gelatin 2.058.

Thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Em-L silver 0.714 ExY-2 0.211 Cpd-2 0.075 Cpd-3 0.001 HBS-1 0.071 gelatin 0.678.

Fourteenth Layer (First Protective Layer) 0.07 μm Silver Iodobromide Emulsion Silver 0.301 UV-1 0.211 UV-2 0.132 UV-3 0.198 UV-4 0.026 F -18 0.009 S-1 0.086 HBS-1 0.175 HBS-4 0.050 gelatin 1.984.

Fifteenth layer (second protective layer) H-1 0.400 B-1 (1.7 μm in diameter) 0.050 B-2 (1.7 μm in diameter) 0.150 B-3 0.050 S- 10.20 Gelatin 0.750.

Further, in order to improve the storability, processability, pressure resistance, fungicidal / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-6, B-4 to B -6, F
-1 to F-17, and lead salts, platinum salts, iridium salts, and rhodium salts.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 in the eleventh layer was dispersed by the following method. ExF-2 wet cake (containing 17.6% by weight of water) 2.800 kg Sodium octylphenyldiethoxymethanesulfonate (31% by weight aqueous solution) 0.376 kg F-15 (7% aqueous solution) 0.011 kg Water 4.020 kg 7.210 kg in total (adjusted to pH = 7.2 with NaOH).

After the slurry having the above composition was coarsely dispersed by stirring with a dissolver, using an agitator mill LMK-4,
Circumferential speed 10m / s, discharge rate 0.6kg / min, 0.3m
The dispersion was dispersed until the absorbance ratio of the dispersion became 0.29 at a filling rate of zirconia beads of m diameter of 80% to obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.29 μm.

Similarly, ExF-4 and ExF-9
Was obtained. The average particle size of the fine dye particles was 0.28 μm and 0.49 μm, respectively. ExF-5
Was dispersed by a microprecipitation dispersion method described in Example 1 of European Patent No. 549,489A. The average particle size was 0.06 μm.

The compounds used for forming each layer are shown below.

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The color negative photosensitive material prepared as described above is designated as Sample 001.

Preparation of Sample 002 (Invention) Sample 002 was prepared from Sample 001 by making the following changes. (Preparation of Em-A ′) In the preparation of Em-A, the addition amounts of AgNO ₃ and KBr at the time of nucleation were 0.7 times, and the addition amounts of spectral sensitizing dyes added before chemical sensitization were all changed. In addition to 0.9 times, the amount of N, N-dimethylselenourea added during chemical sensitization was set to 0, and the amounts of other compounds added were appropriately changed so as to optimize chemical sensitization. Em-A ′ was prepared in the same manner as Em-A, except for the above changes. The aspect ratio was 15.

(Preparation of Em-E ′) In the preparation of Em-E, the addition amounts of AgNO ₃ and KBr during nucleation were 0.7
And the addition amount of the spectral sensitizing dye added before chemical sensitization is all 0.9 times.
-The addition amount of dimethylselenourea was set to 0, and the addition amounts of the other compounds were appropriately changed so that chemical sensitization could be optimally performed.
Em-E ′ was prepared in the same manner as Em-E except for the above changes. The aspect ratio was 15.

(Preparation of Em-L ') In the preparation of Em-L, the addition amount of the silver bromide seed crystal emulsion was 0.7 times, and the addition amount of the spectral sensitizing dye added before chemical sensitization was increased. All 0.
At the same time, the addition amount of N, N-dimethylselenourea during chemical sensitization was set to 0, and the addition amounts of other compounds were appropriately changed so as to optimize chemical sensitization. Em-L ′ was prepared in the same manner as Em-L except for the above changes.

In the preparation of sample 001, Em-A was replaced with E
mA ', Em-E to Em-E', Em-L to Em
-Changed to L '. A sample 002 was prepared in the same manner as the sample 001 except for the above changes.

<Preparation of Sample 101 (Comparative Example)> Sample 00
In the preparation of No. 1, Em-A was disclosed in JP-A-63-22665.
The silver iodobromide emulsion contained in the fifth layer (third red-sensitive emulsion layer) of Sample 001 of Experimental Example 0 described above (average grain size 2.
0 μm, non-tabular grains having an average silver iodide content of 10 mol%), and Em-E was changed to the ninth layer (third green emulsion layer) of Sample 001 of the experimental example described in JP-A-63-226650. Silver iodobromide emulsion (average grain size 2.0μ)
m, non-tabular grains having an average silver iodide content of 10 mol%). Sample 101 was prepared in the same manner as Sample 001 except for the above changes.

<Preparation of Samples 102 (Comparative Example), 103 (Comparative Example), and 104 (Comparative Example)> Sample 102 (Comparative Example) was prepared by changing the silver content of each layer of Sample 001 as shown in Table 4. Then, the silver content of each layer of Sample 002 was changed as shown in Table 4 to prepare Sample 103 (Comparative Example), and the silver content of each layer of Sample 101 was changed as shown in Table 4 to obtain Sample 104 (Comparative Example). Example) was created.

[0416]

[Table 4]

The above samples 001 to 002, 101 to 104
Was maintained at a temperature of 30 ± 1 ° C. and a relative humidity of 60 ± 5% for 2 weeks to react with a gelatin hardener.
Stored under the same storage conditions.

Table 5 Storage conditions A Immediate processing B Post-processing after naturally storing for 1 year in Ashikaga Laboratory, Fuji Photo Film Co., Ltd., Minamiashigara, Kanagawa Prefecture. The storage condition B is a condition in which natural conditions are stored for one year.
The radiation dose in the laboratory is TLD (Thermo Lu)
min. Detector) was about 40 mR / year.

After storing under the conditions shown in Table 5 above, the sample was exposed for 1/100 sec through a gelatin filter SC-39 manufactured by FUJIFILM Corporation and a continuous wedge.

[0420] Development was performed by an automatic developing machine F manufactured by Fuji Photo Film Co., Ltd.
Performed as follows using P-360B. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. This FP-360B is equipped with the evaporation correction means described in Hatsumei Kyokai Disclosure Technique 94-4992.

The processing steps and the composition of the processing solution are shown below. (Processing process) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 mL 11.5L Bleaching 50 seconds 38.0 ° C 5 mL 5L Fixing (1) 50 seconds 38.0 ° C-5L fixing (2) 50 38.0 ℃ 8mL 5L Rinse with water 30sec 38.0 ℃ 17mL 3L stable (1) 20sec 38.0 ℃-3L stable (2) 20sec 38.0 ℃ 15mL 3L Dry 1 min 30sec 60.0 ℃ 35 mm per 1.1 m width (equivalent to 24 Ex. 1 line).

The stabilizing solution and the fixing solution were of the countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm in width of the photosensitive material and 1.1 m wide.
2.5 mL, 2.0 mL, and 2.0 mL, respectively. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step. Open area 100 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

The composition of the processing solution is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate disodium 0.3 0.3 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonatoethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3mg-4-Hydroxy-6 Methyl-1,3,3a, 7-tetrazaindene 0.05-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate Salt 4.5 6.5 Add water 1.0 L 1.0 L pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18.

(Bleaching solution) Tank solution (g) Replenishing solution (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Succinic acid 34 51 Maleic acid 28 42 Water was added and 1.0 L 1.0 L pH [adjusted with ammonia water] 4.6 4.0.

(Fixing (1) tank liquid) A 5/95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid (pH
6.8).

(Fixing (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 240 mL 720 mL (750 g / L) Imidazole 7 21 Ammonium methanethiosulfonate 515 Ammonium methanesulfinate 10 30 Ethylenediaminetetraacetic acid 13 39 Add water 1.0 L 1.0 L pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45.

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 m.
g / L or less, followed by sodium diisocyanurate 20 mg / L and sodium sulfate 150 mg / L
Was added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) 1,2-benzo Isothiazolin-3-one sodium 0.10 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0. 75 Add water to 1.0 L pH 8.5.

For each sample after the above treatment, the sensitivity, fogging,
The graininess was measured. For graininess, use conventional RMS
(Root Mean Square) method.
Table 6 shows the measurement results of sensitivity, fogging, and graininess. Also RM
S indicates a value at an exposure amount of 0.0005 lux seconds.

[0430]

[Table 5]

From Table 6, it can be seen that the silver content of the highest sensitive layer was low and 2
Samples 001 and 002 of the present invention, which use a high aspect ratio emulsion for the two highest sensitivity layers, have a sensitivity after one year of natural aging that is higher than that of Comparative Samples 102 and 103 in which the silver content of the highest sensitivity layer is high. RMS after storage
It is understood that excellent performance is exhibited. Also, it can be seen that the sample of the present invention using the highest aspect ratio flat plate for the highest sensitivity layer has better granularity than the sample 101 of the comparative example using the non-tabular grains for the highest sensitivity layer. Using a non-tabular grain, which was widely used in the prior art, the sample 104 of the comparative example in which the coated silver amount of the highest sensitive layer was large, the fog increase by storage was large,
RMS after storage is large. In contrast, the effects of the samples 001 and 002 of the present invention are very large and useful.

Also, the Macbeth color correction chart was photographed and printed on a commercially available color photographic paper from the developed negative. As a result, the sample of the present invention clearly showed a higher color saturation than any of the comparative samples. Was high and excellent.

Example 2 <Preparation of Sample 221 (Comparative Example)> Sample 221 was prepared by making the following changes from Sample 001. Sample 221 was prepared in the same manner as sample 001, except that Em-A and Em-E used in sample 001 were replaced with Em-A2 and Em-E2, respectively, prepared as follows.

(Preparation of Em-A2) In the preparation of Em-A, the gelatin to be added was changed from "35 g of succinated gelatin" to "35 g of lime-processed gelatin" after completion of ripening at 75 ° C. during grain formation. The addition amount of the spectral sensitizing dye added before chemical sensitization was set to 0.7 times as much as the optimum amount for obtaining the sensitivity, and the addition amounts of the other compounds were appropriately changed so as to optimize the chemical sensitization. Em- except for the above changes
Em-A2 was prepared in the same manner as in A. The particle volume of Em-A2 was equivalent to Em-A, but the aspect ratio was 7.3.

(Preparation of Em-E2) In the preparation of Em-E, after ripening at 75 ° C. during grain formation, the gelatin to be added was changed from “15 g of succinated gelatin and 20 g of trimellitated gelatin” to “35 g of lime-processed gelatin”. "And further increase the amount of spectral sensitizing dye added before chemical sensitization to 0.7 times to be the optimal amount to obtain sensitivity, and to optimize the amount of other compounds to be optimally chemical sensitized. Was changed as appropriate. Except for the above changes, Em-E is the same as Em-E.
2 was prepared. The particle volume of Em-E2 was equivalent to Em-E, but the aspect ratio was 7.3.

<Preparation of Samples 202, 203, 222, and 223> Table 7 shows the coated silver amounts of the sixth layer (high-sensitivity red-sensitive emulsion layer) and the eleventh layer (high-sensitivity green-sensitive emulsion layer) of Samples 001 and 221.
And the sample 202, 203, 222, 22
3 was made, and the same evaluation as in Example 1 was performed. Table 7 shows the results.

[0437]

[Table 6]

Samples 001 and 2 of the present invention using high aspect ratio emulsions Em-A and E and having a silver content within the range of the present invention.
02 is a favorable result in sensitivity, RMS, sensitivity after storage, and Δfog. In comparison, Samples 221 and 222 using emulsions Em-A2 and E2 having a low aspect ratio,
Low sensitivity, low sensitivity after storage, and poor RMS.

The sample 223 in which the amount of silver coated was increased outside the range of the present invention by using an emulsion having a low aspect ratio was close to the sample of the present invention in sensitivity, but the sensitivity after storage was still low, and fogging due to storage was particularly low. The increase Δfog was large, and the granularity after storage was significantly deteriorated.

Even when a high aspect ratio emulsion was used, Sample 203 in which the coated silver amount was increased outside the range of the present invention had low sensitivity after storage, large fog increase Δfog upon storage, and granularity after storage. It is significantly worse and inferior to the sample of the present invention.

Among the samples 001 and 202 of the present invention,
Small change in sensitivity due to storage, small fog increase Δfog due to storage, small deterioration in RMS due to storage,
Sample 001, in which the RMS after storage is small, the coated silver amount of the highest sensitivity layer is 1.2 g / m ² or less, and the total of the coated silver amount of the highest sensitivity layer is 2.61 g / m ^2. This is particularly preferable for the sample 202 in which the total amount of coated silver in the highest sensitivity layer is 3.20 g / m ² .

Example 3 <Preparation of Sample 441 (Invention)> A sample 441 was prepared by making the following changes from Sample 001. Sample 0 was prepared except that Em-A and Em-E used in sample 001 were replaced with Em-A5 and Em-E5, respectively, prepared as follows.
Sample 441 was prepared in the same manner as in Sample No. 01.

(Preparation of Em-A5) In the preparation of Em-A, the amount of N, N-dimethylselenourea added was 0.800 × 10 ^-6 mol per mol of silver, and the other compounds were added. Em-A5 was prepared in the same manner as Em-A5, except that the amount was changed appropriately so as to optimize chemical sensitization. The addition amount of N, N-dimethylselenourea was 6.0 × 10 ⁻⁶ mol per mol of silver, and the addition amounts of other compounds were appropriately changed. Only one result was obtained.

(Preparation of Em-E5) In the preparation of Em-E, the amount of N, N-dimethylselenourea added was 0.80 × 10 ^-6 mol per mol of silver, and the amount of other compounds was added. Em-E5 was prepared in the same manner as Em-E, except that was appropriately changed so as to allow optimal chemical sensitization. In addition,
N, N-dimethylselenourea was added in an amount of 6.0 × 10 ⁻⁶ mol per mol of silver, and the addition amounts of other compounds were appropriately changed. Only the result of was obtained.

<Preparation of Samples 202, 203, 442, and 443> Table 8 shows the coated silver amounts of the sixth layer (high-sensitivity red-sensitive emulsion layer) and the eleventh layer (high-sensitivity green-sensitive emulsion layer) of Samples 001 and 441.
And the sample 202, 203, 442, 44
3 was made, and the same evaluation as in Example 1 was performed. Table 8 shows the results.

[0446]

[Table 7]

Samples 001 and 202 of the present invention using emulsions Em-A and E sensitized with selenium to give a concentration of 3.4 × 10 ^-6 mol / mol silver and having an amount of silver within the range of the present invention were used. , R
MS, sensitivity after storage, and Δfog are also favorable results.

Emulsions Em-A5, E sensitized with selenium to give 0.80 × 10 ⁻⁶ mol / mol silver
Samples 441 and 442 using Sample No. 5 have low sensitivity, but do not show a large decrease in sensitivity due to storage, and a small increase in fog due to storage, Δfog, and both RMS and RMS after storage are small, exhibiting the effects of the present invention. I have. From the viewpoint of high sensitivity, a sample using an emulsion sensitized with selenium at 3.4 × 10 ⁻⁶ mol / mol silver is more preferable.

Sample 443 in which the amount of silver coated was increased outside the range of the present invention using an emulsion selenium sensitized to 0.80 × 10 ⁻⁶ mol / mol silver, the sensitivity of the sample of the present invention was In particular, the sensitivity after storage was low, the fog increase Δfog due to storage was large, and the granularity after storage was significantly deteriorated.

Example 4 <Preparation of Sample 551 (Invention)> A sample 551 was prepared by making the following changes from Sample 001.

Cpd-7,8 added to the third, fourth, and fifth layers of Sample 001 reacts with an oxidized aromatic primary amine color developing agent to cause a bleaching accelerator. Is a compound that releases Sample 551 was prepared in the same manner as Sample 001, except that all of them exhibited the same color-forming properties, but were replaced by ExC-3, which did not release the bleaching accelerator, in the same weight.

<Preparation of Samples 202, 203, 552, and 553> The coating amounts of the sixth layer (high-sensitivity red-sensitive emulsion layer) and the eleventh layer (high-sensitivity green-sensitive emulsion layer) of Samples 001 and 551 are shown in Table 9.
And the sample 202, 203, 552, 55
3 was made, and the same evaluations as in Example 2 were performed. Table 9 shows the results.

[0453]

[Table 8]

Samples 001 and 202 of the present invention containing a compound capable of releasing a bleaching accelerator and having a silver content within the range of the present invention have favorable results in sensitivity, RMS, sensitivity after storage, and Δfog.

In comparison, Samples 551 and 552, which did not contain a compound that releases a bleaching accelerator, showed the R in the red-sensitive emulsion layer.
Although the MS is large, the decrease in sensitivity due to storage is not large, and the fog increase Δfog due to storage is preferably small, and both the RMS and the RMS after storage are small, thus exhibiting the effects of the present invention. In the point that the RMS of the red-sensitive layer is small, a sample using a compound that releases a bleaching accelerator is a more preferable result.

A compound that releases a bleaching accelerator,
Sample 203 in which the coated silver amount was increased outside the range of the present invention
As compared with Sample 553 in which the amount of coated silver was increased outside the range of the present invention without containing a compound that releases a bleaching accelerator, fog increase Δfog due to storage was large, and the granularity after storage deteriorated. That is, in a system containing a compound that releases a bleaching accelerator, the effect of reducing the amount of coated silver in the highest sensitivity layer is particularly large.

Example 5 <Preparation of Samples 331 and 332 (the present invention)> Samples 331 and 332 were prepared by making the following changes from Sample 001.

Em-A and Em used in sample 001
-E were Em-A3, A4, respectively created by
Samples 331 and 332 were prepared in the same manner as Sample 001 except that Em-E3 and E4 were used.

(Preparation of Em-A3 and A4) In the preparation of Em-A, the addition of yellow blood salt was not performed, and the addition amounts of other compounds were appropriately changed so that chemical sensitization could be optimally performed. Em-A3 in the same manner as Em-A except for the above changes
Was prepared.

In the preparation of Em-A, [Ru (bpy) ₃ ] Cl ₂ was used in place of yellow blood salt, the silver potential during the addition was adjusted, and the amount of other compounds added was optimized. It was changed appropriately so that chemical sensitization could be performed. Em- except for the above changes
In the same manner as in A, emulsion Em-A4 was prepared. The volume and aspect ratio of each particle were equivalent to Em-A.

(Preparation of Em-E3 and E4) In the preparation of Em-E, the addition of yellow blood salt was not performed, and the addition amounts of other compounds were appropriately changed so as to optimize chemical sensitization. Em-E3 in the same manner as Em-E except for the above changes
Was prepared.

In the preparation of Em-E, [Ru (bpy) ₃ ] Cl ₂ was used in place of yellow blood salt, the silver potential during the addition was adjusted, and the amount of other compounds added was optimized. It was changed appropriately so that chemical sensitization could be performed. Em- except for the above changes
Emulsion Em-E4 was prepared in the same manner as E. The volume and aspect ratio of each particle were equivalent to Em-E.

<Samples 202, 203, 333, 334,
Preparation of 335, 336> The silver coating amounts of the sixth layer (high-sensitivity red-sensitive emulsion layer) and the eleventh layer (high-sensitivity green-sensitive emulsion layer) of Samples 001, 331, and 332 were changed as shown in Table 10. Sample 20
2, 203, 333, 334, 335, 336 were prepared and evaluated in the same manner as in Example 2. Table 10 shows the results.

[0464]

[Table 9]

Samples 001 and 001 of the present invention using high aspect ratio emulsions Em-A and E provided with an electron capture zone using yellow blood salt as an electron capture center and having a silver content within the range of the present invention.
202 has high sensitivity, high sensitivity after storage, small fog increase Δfog due to storage, RMS, RMS after storage
These are small and favorable results.

Sample 33 prepared using emulsions Em-A3 and E3 having no electron capture zone with yellow blood salt
In Nos. 1 and 333, although the sensitivity is low, the decrease in sensitivity due to storage is not large, and the fog increase Δfog due to storage is preferably small, and both the RMS and the RMS after storage are small, thus exhibiting the effects of the present invention. A sample using an emulsion having an electron capture zone by yellow blood salt is more preferable in terms of high sensitivity.

In Sample 335, which has no electron capture zone due to yellow blood salt and has a coated silver amount increased outside the range of the present invention, the sensitivity approaches that of Sample 001 of the present invention.
The sensitivity after storage is clearly low, and the fog increase due to storage Δ
The fog was large, and the RMS after storage was significantly deteriorated.

Samples 332 and 334 prepared using an emulsion having an electron capture zone using [Ru (bpy) ₃ ] Cl ₂ as an electron capture center in place of yellow blood salt are the same as Sample 001 of the present invention. , 202, which is preferable and falls within the scope of the present invention. In the case of sample 336 in which the amount of coated silver was increased outside the range of the present invention, similar to sample 203, the sensitivity after storage was particularly low, and the fog due to storage was low. The increase Δfog is large, and the RMS after storage is significantly deteriorated, which is inferior to the sample of the present invention.

Example 6 The above-mentioned effects of the sample of the present invention show excellent results in the form of a photographic product incorporating a photosensitive material provided with an exposure function. Samples of the present invention were taken in 35 mm 24 sheets to make a patrone processed product. Fuji Photo Film Co., Ltd. "Sharun is Super80
0 27 shots ”and the sample of the present invention
Created a 25-PS cartridge processed product, and made a photo slim super slim star made by Fuji Photo Film Co., Ltd.
25 shots ".

As a result of the preservation test in the above embodiment, as in the above-described embodiment, excellent effects were exhibited for the sample of the comparative example. In addition, the result of comparing the sample loaded with the sample of the present invention and the sample of the comparative example in the form of "Photo Run Super 800 27 shots" through baggage inspection using X-rays at Narita Airport, particularly excellent results showed that.

[0471] This is because, in contrast to the normal form stored in a metal patrone, the above-mentioned form is light-shielded by a synthetic resin, and thus is more strongly affected by X-rays in baggage inspection. . As described above, it was shown that the photosensitive material of the present invention exhibited particularly excellent results only in the form of a photographic product incorporating a photosensitive material provided with an exposure function.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 7/00 510 G03C 7/00 510 7/20 7/20 7/392 7/392 Z

Claims (9)

[Claims] 1. A support having at least one red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer each having an ISO sensitivity of 64.
In a silver halide color negative photographic light-sensitive material of 0 or more, the content of all silver contained in the photographic light-sensitive material is 3.0 g / m ² or more and 9.0 g / m ² or less, and the same sensitivity described above. Each silver halide emulsion layer of chromaticity is composed of two or more silver halide emulsion layers having different sensitivities, and the silver content of the highest-sensitive emulsion layer among the two or more emulsion layers of the same color sensitivity is reduced. All are 0.3 g / m ² or more and 1.3 g / m ² or less,
Among the two or more emulsion layers having the same color sensitivity, at least 50% or more of the total projected area of the silver halide grains contained in at least two of the most sensitive layers are composed of tabular silver halide grains. Tabular silver halide grains having an average aspect ratio of 8
A silver halide color negative photographic material characterized by the above. 2. The silver content of the highest sensitive layer among two or more emulsion layers having the same color sensitivity is 0.3 g / m ² or more.
^{2. The} silver halide color negative photographic material according to claim 1, wherein the photographic material is not more than g / m < ² >. 3. A silver halide emulsion layer comprising an emulsion in which the tabular silver halide grains occupy 50% or more of the total projected area, wherein at least one of the silver halide emulsion layers contains silver 1
The selenium sensitizer is contained in an amount of 2 × 10 ⁻⁶ mol or more and 5 × 10 ⁻⁶ mol or less per mol.
2. The silver halide color negative photographic light-sensitive material described in 1. above. 4. A support having at least one red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer each having an ISO sensitivity of 64.
In a silver halide color negative photographic light-sensitive material of 0 or more, the content of all silver contained in the photographic light-sensitive material is 3.0 g / m ² or more and 9.0 g / m ² or less, and the same sensitivity described above. Each of the silver halide emulsion layers having the same color sensitivity is composed of two or more silver halide emulsion layers having different sensitivities, and the silver content of the highest emulsion layer among the two or more emulsion layers having the same color sensitivity is determined. Silver halide grains having a total sum of 1.5 g / m ² or more and 3.5 g / m ² or less and contained in at least two of the highest sensitive layers among two or more emulsion layers having the same color sensitivity. A silver halide color negative photographic light-sensitive material, characterized in that tabular silver halide grains account for 50% or more of the total projected area, and the tabular silver halide grains have an average aspect ratio of 8 or more. 5. The total silver content of the highest-sensitivity emulsion layer of two or more emulsion layers having the same color sensitivity is 1.5 g / m ² or more and 3.0 g / m ² or less. Claim 4
2. The silver halide color negative photographic light-sensitive material described in 1. above. 6. At least one of the silver halide emulsion layers containing an emulsion in which the tabular silver halide grains occupy 50% or more of the total projected area is at least one layer of silver 1 contained in the emulsion layer.
The selenium sensitizer is contained in an amount of 2 x 10 ^-6 mol or more and 5 x 10 ^-6 mol or less per mol.
2. The silver halide color negative photographic light-sensitive material described in 1. above. 7. A color negative photographic light-sensitive material wherein at least one layer contains a compound which reacts with an oxidized aromatic primary amine color developing agent to release a bleaching accelerator. 7. The silver halide color negative photographic material as described in any one of 1 to 6 above. 8. An emulsion containing tabular silver halide grains having an average aspect ratio of 8 or more contained in at least two of the highest sensitivity layers among two or more emulsion layers having the same color sensitivity. 2. The method according to claim 1, wherein one of the silver halide grains contains tabular silver halide grains having an electron capture zone.
8. The silver halide color negative photographic light-sensitive material according to any one of items 1 to 7, 9. A silver halide color negative photographic light-sensitive material according to claim 1, wherein the color photographic light-sensitive material is a photographic material having a built-in color photographic light-sensitive material and provided with an exposure function. A photographic product with a built-in photosensitive material, provided with an exposure function.