JP2000275771A - Silver halide photographic emulsion and photosensitive material containing the same, and image forming method by using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic emulsion high in sensitivity and yet, small in the change of gradation and capable of obtaining superior photographic characteristics, and to provide a color photographic sensitive material using it and an easy and rapid color image forming method small in environmental load by using this material. SOLUTION: All the flat silver halide grains contained in the silver halide grains of the silver halide emulsion have an average corresponding circle diameter of 2.0-4.0 μm, and contain at least one kind of metal complex having heterocyclic compounds in a number of over the half of the coordination number of the metal atom (in the case of a chelating compound, a number of chelated heterocyclic compounds), and this invention includes the color photographic sensitive material and the color image forming method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion having a high sensitivity, a small change in gradation upon exposure to high illuminance, and excellent characteristics, a silver halide color photographic light-sensitive material using the same, The present invention relates to a simple and rapid color image forming method using the photosensitive material.

[0002]

2. Description of the Related Art In recent years, photographic light-sensitive materials utilizing silver halide have been increasingly developed, and it is now possible to easily obtain high-quality color images. For example, in a method generally called a color photograph, a photograph is taken using a color negative film, and image information recorded on the developed color negative film is optically printed on color photographic paper to obtain a color print. In recent years, this process has been highly developed, and anyone can use the color lab, which is a large-scale centralized base that produces large amounts of color prints with high efficiency, or the so-called minilab, which is a small, simple printer processor installed in stores. But you can easily enjoy color photos. More recently, a new concept APS system using a color negative film capable of recording various information as magnetic recording using a support coated with a magnetic material has been introduced to the market. This system proposes the enjoyment of photography, such as the simplicity of film handling and the ability to change the print size by recording information during shooting. In addition, a tool for editing and processing an image by reading image information from a processed negative film with a simple scanner has been proposed. In this way,
It has become possible to easily digitize high-quality image information of silver halide photographs, and a wide range of applications is becoming more familiar beyond the conventional way of enjoying photographs.

[0003] The principle of color photography that is currently widespread employs color reproduction by a subtractive color method. In a general color negative, a photosensitive layer using a silver halide emulsion, which is a photosensitive element having photosensitivity in the blue, green, and red regions, is provided on a transparent support. So-called color couplers forming dyes of yellow, magenta and cyan which are complementary hues are contained in combination.
The color negative film that has been imagewise exposed by photography is developed in a color developer containing an aromatic primary amine developing agent. At this time, the exposed silver halide grains are developed or reduced by the developing agent, and respective dyes are formed by a coupling reaction between the oxidized product of the developing agent and the color coupler described above. Metallic silver (developed silver) generated by development and unreacted silver halide are removed by bleaching and fixing, respectively, to obtain a dye image. A color photographic paper, which is a color photographic material in which a photosensitive layer having a similar combination of a photosensitive wavelength region and a color hue is coated on a reflective support, is subjected to optical exposure through a color negative film after development processing, and By performing the color development, bleaching, and fixing processes described above, it is possible to obtain a color print composed of a dye image reproducing the original scene.

With respect to such a classic image forming method,
Recently, it has become possible to convert image information recorded on a color negative into digital information by a scanner and to perform various image processing on the information to improve the image quality of a print obtained. In fact, a minilab system equipped with this technology has been announced. Under these circumstances, there has been an increasing demand in recent years to enhance the simplicity of color negative image forming methods. First, the processing bath for performing the color development, bleaching, and fixing described above requires precise control of the composition and temperature, and requires specialized knowledge and skilled operations. Second, these processing solutions contain substances that must be environmentally controlled, such as color developing agents and iron chelates, which are bleaching agents. Is often required. Third, although the development process has been shortened in recent years, these development processes require time and are still inadequate for the demand for quickly reproducing a recorded image.

[0005] From the above background, it has been proposed to reduce the environmental burden and improve the simplicity by constructing a system that does not use a color developing agent or a bleaching agent used in current color image forming systems. Demands are growing. In view of these viewpoints, many improved techniques have been proposed. For example, IS &T's 48th Annual Confe
rence Proceedings page 180 shows that the dye generated in the development reaction is transferred to the mordant layer and then removed to remove developed silver and unreacted silver halide. A system is disclosed that eliminates the need for a bath. However, the technology proposed here still requires development processing in a processing bath containing a color developing agent, and it cannot be said that the environmental problem has been solved.

As a system that does not require a processing solution containing a color developing agent, Fuji Photo Film Co., Ltd. provides a pictography system. In this system, a small amount of water is supplied to a photosensitive material containing a base precursor, and the photosensitive material is overlapped with an image receiving member and heated to cause a development reaction. This method is environmentally advantageous in that the above-mentioned treatment bath is not used. However, since this method is used for fixing the formed dye to a dye fixing layer and viewing the dye as a dye image, it has been desired to develop a system that can be used as a recording material for photographing. In particular, a digital lab system which has been rapidly developed in recent years has increased a need for a system and a recording medium for simply and quickly digitizing photographed image information. For example, Fuji Photo Film Co., Ltd. Digital Lab System Frontier (input machine "High-speed scanner / Image processing workstation" Scannrer & Image Processor SP-1000)
If the negatives of input information, such as the output machine “Laser Printer / Paper Processor” and the Laser Processor LP-1000P, can be processed more simply and promptly, the performance of the system will increase.

In response to such demands, there is an imaging negative with a built-in developing agent as an imaging negative capable of performing processing that is simple, quick and has a low environmental load. Since this system is a photographic material, the emulsion used is required to have higher sensitivity. Further, high levels of demands have been made for improvement of the relationship between sensitivity / granularity ratio, improvement of sharpness, and good gradation. One of the techniques for sensitizing silver halide emulsions is to use tabular grains, which include an increase in sensitivity including an improvement in color sensitization efficiency by a sensitizing dye, an improvement in the relationship between sensitivity / granularity, and a specific tabular grain. Advantages such as improvement of sharpness and covering power due to optical characteristics are known. A technique for using a tabular grain emulsion in a heating development system incorporating a developing agent is disclosed in, for example, JP-A-9-2742.
No. 95 and JP-A-10-62932. However, there is no description in these patents relating to the use of a silver halide tabular grain emulsion containing a metal complex having more than half of the coordination number of a metal atom as a ligand of the present invention as a ligand. . On the other hand, in view of the above points,
The use of an emulsion containing tabular grains in a heat-developing silver halide color photographic light-sensitive material incorporating a color developing agent, which is a photographic material capable of simple and rapid image recording with a low environmental load, makes it possible to perform ordinary liquid development. In comparison, when exposure with high illuminance is performed during heat development, gradation changes (softening) tend to occur,
In particular, when tabular grains having a large average equivalent circle equivalent diameter were used, the deterioration was remarkable, and it became clear that this became a practical problem.

[0008]

As apparent from what has been described above, a first object of the present invention is to provide an excellent, low-gradation, high-illuminance exposure with a small change in gradation. A silver halide photographic emulsion that provides photographic characteristics, a color photographic light-sensitive material using it, and a simple and
An object of the present invention is to provide a color image forming method which is quick and has a low environmental load.

[0009]

Means for Solving the Problems As a result of diligent research, the present inventors have found that a metal having a large average equivalent circle equivalent diameter and having as a ligand a heterocyclic compound having a number exceeding half of the coordination number of metal atoms is used as a ligand. The use of silver halide tabular grain emulsions containing a complex in a color photographic light-sensitive material for photothermography using a built-in heat treatment system has an unexpected effect on sensitivity enhancement and softening during high-illumination exposure. discovered.

The above object of the present invention has been effectively achieved by the following present invention. That is, of the silver halide grains contained in (1), the average equivalent circle diameter of all tabular grains is 2.0 to 4.0 μm, and the number of the grains exceeds half the coordination number of metal atoms. It is characterized in that it contains one or more metal complexes having a heterocyclic compound (when the heterocyclic compound is a chelate compound, the number of coordinating atoms is the number of heterocyclic compounds) as a ligand. (2) The average equivalent circle diameter of all tabular grains is 2.5 to 4.0 μm.
(3) The silver halide color photographic emulsion as described in (1) above, wherein (3) the average equivalent circle diameter of all tabular grains is 3.0 to 4.0 μm or less. , (4) is a complex having, as a central metal, magnesium, calcium, strontium, barium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, zinc, cadmium or mercury. (1) The silver halide photographic emulsion according to any one of (1) to (3), wherein (5) the average aspect ratio of all tabular grains is from 8 to 40. Or the silver halide photographic emulsion according to any one of (4) to (4),
(6) The silver halide emulsion is characterized in that tabular grains containing 10 or more dislocation lines per grain substantially only in the fringe portion of the grains occupy 100 to 50% (number) of all grains. The silver halide photographic emulsion according to any one of (1) to (5) and (7) the silver halide photographic emulsion according to any one of (1) to (6) above on a support. (8) The silver halide photographic light-sensitive material according to (7), further comprising (8) a developing agent and a compound which forms a dye by a coupling reaction with an oxidized form of the developing agent. Silver halide color photographic light-sensitive material, (9) the developing agent is represented by the following general formula (1)
The silver halide color photographic material according to the item (8), which is at least one of the compounds represented by the item (4).

[0011]

Embedded image

[0012]

Embedded image

[0013]

Embedded image

[0014]

Embedded image

In the formula, R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group. Group, alkylthio, arylthio, alkylcarbamoyl, arylcarbamoyl, carbamoyl, alkylsulfamoyl, arylsulfamoyl, sulfamoyl, cyano, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl, aryl It represents an oxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group or an acyloxy group, and R ₅ represents an alkyl group, an aryl group or a heterocyclic group. Z represents an atomic group forming an aromatic ring (including a heteroaromatic ring). When Z is an element necessary for forming a benzene ring, the total value of the Hammett constant (σ) of the substituent is 1 or more. It is. R ₆ represents an alkyl group. X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom. R ₇ and R ₈ are
Represents a hydrogen atom or a substituent, and R ₇ and R ₈ may combine with each other to form a double bond or a ring. Further, each of the general formulas (1) to (4) contains at least one ballast group having 8 or more carbon atoms in order to impart oil solubility to the molecule.
(10) After exposing the photosensitive material, a processing material comprising a support and a constituent layer including a processing layer containing a base and / or a base precursor coated thereon, and the entirety of the photosensitive material and the processing material except for the back layer, After supplying water equivalent to 1/10 to 1 times the total amount of water required for the maximum swelling of the coating film to the photosensitive layer surface of the photosensitive material or the processing layer surface of the processing material, the photosensitive layer surface of the photosensitive material and the processing of the processing material are processed. The layers are brought into close contact with each other and superimposed at a temperature of 60 ° C. or more and 100 ° C. or less for 5 seconds or more.
An image can be formed by heating within seconds.
0) The photosensitive material described in item 0) is imagewise exposed, and a processing material comprising a support and a constituent layer including a processing layer containing a base and / or a base precursor coated thereon, and a backing of both the photosensitive material and the processing material After supplying water equivalent to 1/10 to 1 times the total amount of water required for the maximum swelling of all the coating films except the layers to the photosensitive layer surface of the photosensitive material or the processing layer surface of the processing material, The processing layer surfaces of the processing materials are brought into close contact with each other and superimposed at a temperature of 60 ° C. or more and 100 ° C. or less, and
It is an object of the present invention to provide a color image forming method in which an image is formed in a photosensitive material by heating for at least 60 seconds to within 60 seconds. In the present invention, a change in gradation hardly occurs even by high-illuminance exposure. Here, “high illuminance” in “high illuminance scanning exposure” preferably refers to illuminance that is 100 times or more the illuminance in surface exposure. In the metal complex, the heterocyclic compound can be coordinated through a hetero atom.

[0016]

DETAILED DESCRIPTION OF THE INVENTION In one preferred embodiment of the present invention, at least three silver halide emulsions containing a blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion, a color developing agent, and a coupler are provided on a support.
A photographic material comprising a photographic light-sensitive silver halide emulsion layer and a non-photosensitive layer, and a processing material having a processing layer containing at least a base and / or a base precursor on a support. 1/10 to 1 of the amount required to swell all coating films except the back layer of both processing materials
The photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material are overlapped and heated at a temperature of 60 ° C. or more and 100 ° C. or less and for 5 seconds or more and 60 seconds or less on the photosensitive material in the presence of twice as much water. An image based on at least three non-diffusible dyes is formed, and a color image is obtained on another recording material based on the image information.

First, the silver halide emulsion of the present invention will be described below. The silver halide emulsion of the present invention preferably contains a large amount of tabular grains. In the present invention, tabular grains are 2
It is a tabular silver halide grain having an aspect ratio of 2 or more having two opposing parallel (111) planes as main planes. In the present invention, the tabular grains have one twin plane or two or more parallel twin planes, but preferably have two twin planes.

When viewed from above, the tabular grains of the present invention have a triangular shape, a hexagonal shape or a shape in which these corners are rounded. In the case of a hexagonal shape, the opposite sides are parallel to each other. It has a good outer surface.

The twin plane spacing of the tabular grains of the present invention can be 0.012 μm or less as described in US Pat. No. 5,219,720, or (11) as described in
1) The distance between main planes / the distance between twin planes may be 15 or more, and may be selected according to the purpose.

In the emulsion of the present invention, the projected area of tabular grains preferably accounts for 100 to 80% of the total projected area of all grains, more preferably 100 to 90%, even more preferably 100 to 95%. If the projected area of the tabular grains is less than 80% of the total projected area of all the grains, the merits of the tabular grains (improvement in sensitivity / granularity ratio and sharpness) cannot be fully utilized, which is not preferable.

In the emulsion of the present invention, hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.5 to 1 occupy 100 to 50% of the projected area of all grains in the emulsion. Is preferred. More preferably 100 to 70%,
More preferably, it accounts for 100 to 80%. In the emulsion of the present invention, more preferably, hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.2 to 1 occupy 100 to 50% of the projected area of all grains in the emulsion. .
More preferably, it occupies 100 to 70%, particularly preferably 100 to 80%. Mixing of tabular grains other than the above hexagons is not preferable in terms of homogeneity between grains.

The average grain thickness of the tabular grains of the present invention is preferably from 0.05 to 0.3 μm, more preferably from 0.10 to 0.25 μm, even more preferably from 0.10 to 0.20 μm. . The average grain thickness is the arithmetic average of the grain thicknesses of all tabular grains in the emulsion. Emulsions having an average grain thickness of less than 0.05 μm are difficult to prepare. If it exceeds 0.3 μm, it is difficult to obtain the advantages of tabular grains, which is not preferred.

The average equivalent circle diameter of the tabular grains of the present invention is preferably 2.0 to 4.0 μm.
It is more preferably from 2.5 to 4.0 μm, particularly preferably from 3.0 to 4.0 μm. The average equivalent circle diameter is the arithmetic mean of the equivalent circle equivalent diameters of all tabular grains in the emulsion. If the average equivalent circle diameter is less than 2.0 μm, the effects of the present invention are hardly obtained, which is not preferable. If the thickness exceeds 4.0 μm, the pressure property deteriorates, which is not preferable.

The ratio of the equivalent circle equivalent diameter to the thickness of the silver halide grains is called the aspect ratio. That is, it is a value obtained by dividing the equivalent circle diameter of the projected area of each silver halide grain by the grain thickness. As an example of measuring the aspect ratio,
There is a method in which a transmission electron micrograph is taken by a replica method to determine the diameter (equivalent circle equivalent diameter) and thickness of a circle having an area equal to the projected area of each particle. In this case, the thickness is calculated from the length of the shadow of the replica.

The emulsion of the present invention has an aspect ratio of 4 to 5.
0 tabular grains preferably occupy 100 to 80% of the projected area of all silver halide grains in the emulsion, and more preferably, tabular grains having an aspect ratio of 6 to 50 are projected from all silver halide grains in the emulsion. 100 to 80 of area
%, More preferably 8 to 50 tabular grains having an aspect ratio of 1 to 5 of the projected area of all silver halide grains in the emulsion.
It accounts for 00 to 80%.

In the emulsion of the present invention, the average aspect ratio of all tabular grains in the emulsion is preferably from 8 to 40, more preferably from 12 to 40, and still more preferably from 15 to 30. The average aspect ratio is the arithmetic average of the aspect ratios of all tabular grains in the emulsion. Outside these ranges, the effects of the present invention are hardly obtained, which is not preferable.

The emulsion of the present invention preferably comprises monodisperse grains. The variation coefficient of the grain size (equivalent sphere equivalent diameter) distribution of all silver halide grains of the present invention is preferably 30% to 3%, more preferably 25% to 3%, and even more preferably 20% to 3%. is there. The variation coefficient of the equivalent sphere equivalent diameter distribution is a value obtained by dividing the variation (standard deviation) of the equivalent sphere equivalent diameter of each tabular grain by the average equivalent sphere equivalent diameter. If the variation coefficient of the equivalent sphere equivalent diameter distribution of all tabular grains exceeds 30%, it is not preferable in terms of homogeneity between grains. Emulsions of less than 3% are difficult to prepare.

The variation coefficient of the equivalent circle equivalent diameter distribution of all tabular grains of the emulsion of the present invention is preferably 30% to 3%, more preferably 25% to 3%, and further preferably 20% to 3%. . The variation coefficient of the equivalent circle equivalent diameter distribution is a value obtained by dividing the variation (standard deviation) of the equivalent circle equivalent diameter of each tabular grain by the average equivalent circle equivalent diameter. The coefficient of variation of the equivalent circle equivalent diameter distribution of all tabular grains is 30%
If it exceeds 300, it is not preferable in terms of homogeneity between particles. Also,
Emulsions below 3% are difficult to prepare.

The coefficient of variation of the grain thickness distribution of all tabular grains of the emulsion of the present invention is preferably 30 to 3%, more preferably 25 to 3%, and further preferably 20 to 3%. The variation coefficient of the grain thickness distribution is a value obtained by dividing the variation (standard deviation) of the grain thickness of each tabular grain by the average grain thickness. If the variation coefficient of the grain thickness distribution of all tabular grains exceeds 30%, it is not preferable in terms of homogeneity between grains. Emulsions of less than 3% are difficult to prepare.

In the present invention, the particle thickness, aspect ratio and monodispersity in the above ranges may be selected according to the purpose, but it is preferable to use monodisperse tabular grains having a small particle thickness and a high aspect ratio. In the present invention, various methods can be used for forming tabular grains having a high aspect ratio, for example, US Pat. Nos. 5,496,694 and 5,498,595.
The particle forming method described in No. 16 can be used. Further, as a method for forming tabular grains having an ultra-high aspect ratio, the grain forming methods described in U.S. Patent Nos. 5,494,789 and 5,503,970 can also be used. In order to form monodisperse tabular grains having a high aspect ratio, it is important to generate small-sized twin nuclei in a short time. Therefore, it is preferable to form nuclei in a short time under low temperature, high pBr, low pH and low gelatin amount, and gelatin having a low molecular weight or a low methionine content as a kind of gelatin,
Those in which the amino group is modified with phthalic acid, trimellitic acid or pyromellitic acid are preferred. After nucleation, the normal crystallization, single twin and non-parallel multiple twin nuclei are eliminated by physical ripening, and parallel double twin nuclei are selectively left. It is preferable to further ripen the remaining parallel double twin nuclei to increase the monodispersity. In addition, physical aging is performed, for example, in US Pat.
0, 220 and 5, 147, 771.
Performing in the presence of (polyalkylene oxide) is also preferred because it increases monodispersity. Thereafter, gelatin is added, and then a soluble silver salt and a soluble halogen salt are added to perform grain growth. As the additional gelatin, a gelatin obtained by modifying an amino group with phthalic acid, trimellitic acid, pyromellitic acid, or the like is preferable. It is also preferred to add silver halide fine particles prepared separately in advance or simultaneously prepared in another reaction vessel to supply silver and halide to grow the grains. It is important to control and optimize the reaction solution temperature, pH, binder amount, pBr, supply rate of silver and halogen ions, etc. even during grain growth.

To form silver halide emulsion grains used in the present invention, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride,
Silver chloride, silver chloroiodobromide and the like can be used, but silver iodobromide or silver chloroiodobromide is preferably used. Iodide,
Alternatively, when there is a phase containing chloride, these phases may be uniformly distributed in the particles or may be localized.
Other silver salts, such as silver rhodanate, silver sulfide, silver selenide,
Silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains.

The preferred range of the silver bromide content of the emulsion grains in the present invention is at least 80 mol%, more preferably at least 90 mol%. The preferred range of the silver iodide content of the emulsion grains in the present invention is 1 to 20 mol%.
More preferably, it is 2 to 15 mol%, and still more preferably 3 to 10 mol%. If it is less than 1 mol%, it is difficult to obtain effects such as enhancement of dye adsorption and increase of intrinsic sensitivity, which is not preferable. If it exceeds 20 mol%, the developing speed is generally slow, which is not preferable.

In the present invention, the variation coefficient of the silver iodide content distribution among the emulsion grains is preferably 30% or less, more preferably 25 to 3%, and further preferably 20 to 3%. If it exceeds 30%, it is not preferable in terms of homogeneity between particles. The variation coefficient of the silver iodide content distribution between grains is a value obtained by dividing the standard deviation of the silver iodide content of each emulsion grain by the average silver iodide content. The silver iodide content of each emulsion grain can be measured by analyzing the composition of each grain using an X-ray microanalyzer. The measuring method is described, for example, in EP 147,868. When obtaining the distribution of the silver iodide content of each grain of the emulsion of the present invention, it is preferable to measure the silver iodide content of at least 100 grains or more, more preferably 200 grains or more, particularly preferably It is determined by measuring 300 or more particles.

The emulsion grains of the present invention mainly comprise {111} faces and {100} faces. The proportion occupied by {111} planes with respect to the total surface of the emulsion grains of the present invention is at least 70%. On the other hand, in the emulsion grains of the present invention, the site where the {100} plane appears is the side face of the tabular grain, and the {100} plane ratio is at least 2% of the area where the {111} plane occupies the emulsion grain surface. It is preferably at least 4%.
It is preferable to increase the {100} plane ratio, and it may be selected according to the purpose. The {100} plane ratio can be controlled by referring to JP-A-2-298935.
The {100} plane ratio is {11} in the sensitizing dye adsorption.
It can be determined using a method utilizing the difference in the adsorption dependence between the {1} plane and the {100} plane, for example, the method described in T. Tani, J. Imaging Sci., 29, 165 (1985). # 10 at the edge of tabular grains in the emulsion grains of the present invention
The area ratio of the 0 ° plane is preferably 15% or more, more preferably 25% or more, and still more preferably 3% or more.
5% or more. # 10 at edge of tabular grain
The area ratio of the 0 ° plane can be determined, for example, by the method described in JP-A-8-334850.

The tabular grains in the present invention preferably have dislocation lines inside the grains. Hereinafter, introduction of dislocation lines into tabular grains will be described. A dislocation line is a linear lattice defect on a slip surface of a crystal at a boundary between a region that has already slipped and a region that has not slipped. Regarding dislocation lines of silver halide crystals, 1) C.I. R. Berry, J.M. App
l. Phys. , 27, 636 (1956), 2) C.I.
R. Berry, D.M. C. Skilman, J .; App
l. Phys. , 35, 2165 (1964), 3).
J. F. Hamilton, Photo. Sci. En
g. , 11, 57 (1967), 4) T.I. Shioza
wa, J .; Soc. Photo. Sci. Jap. , 3
4, 16 (1971), 5) T.I. Shiozawa,
J. Soc. Photo. Sci. Jap. , 35,21
3 (1972), which can be analyzed by an X-ray diffraction method or a direct observation method using a low-temperature transmission electron microscope. When directly observing dislocation lines using a transmission electron microscope, place the silver halide grains taken out of the emulsion on a mesh for electron microscope observation, taking care not to apply enough pressure to generate dislocation lines on the grains, Observation is performed by a transmission method in a state where the sample is cooled so as to prevent damage (for example, printout) by an electron beam. In this case, the thicker the particle, the more difficult it is for the electron beam to pass therethrough.
The use of an electron microscope (200 kV or more for a thickness of 5 μm) enables more clear observation.

On the other hand, the effect of dislocation lines on photographic performance is described in C. Farnell, R .; B. Flint,
J. B. Chanter, J.A. Photo. Sci. , 1
3, 25 (1965) discloses that in a large size high aspect ratio tabular silver halide grain, a place where a latent image nucleus is formed is closely related to a defect in the grain. I have. For example, U.S. Pat.
No. 61, 498, 516, 5, 496, 694,
JP-A-5,476,760, JP-A-5,567,580, JP-A-4-149541 and JP-A-4-149737 describe a technique for introducing dislocation lines into silver halide grains while controlling the dislocation lines. In these patents, it is shown that tabular grains into which dislocation lines are introduced are superior in photographic properties such as sensitivity and pressure properties as compared with tabular grains without dislocation lines. In the present invention, it is preferable to use the emulsions described in these patents.

In the present invention, it is preferable to introduce dislocation lines into tabular grains as follows. That is, epitaxial growth of a silver halide phase containing silver iodide on tabular grains (also referred to as host grains) serving as a base, and introduction of dislocation lines by forming a silver halide shell thereafter.

The silver iodide content of the host grains is preferably from 0 to 15 mol%, more preferably from 0 to 12 mol%, and particularly preferably from 0 to 10 mol%. good. If it exceeds 15 mol%, the developing speed is generally slow, which is not preferable. The composition of the silver halide phase to be epitaxially grown on the host grains preferably has a higher silver iodide content. The silver halide phase to be epitaxially grown may be any of silver iodide, silver iodobromide, silver chloroiodobromide, and silver chloroiodide, but is preferably silver iodide or silver iodobromide. Is more preferable. The preferred silver iodide (iodide ion) content in the case of silver iodobromide is 1 to 45 mol%, more preferably 5 to 45 mol%, and particularly preferably 10 to 45 mol%. The silver iodide content is preferably as high as possible in terms of forming a misfit necessary for introducing dislocation lines, but 45 mol% is the solid solubility limit of silver iodobromide. The amount of halogen added to form the high silver iodide content phase to be epitaxially grown on the host grains is preferably 2 to 15 mol%, more preferably 2 to 10 mol% of the silver amount of the host grains. And particularly preferably 2 to 5 mol%. If it is less than 2 mol%, dislocation lines are hardly introduced, which is not preferable. If it exceeds 15 mol%, the developing speed is undesirably slow. At this time, the high silver iodide content phase is 5 to 60% of the total grain silver amount as viewed after grain formation.
It is preferably present in the range of mol%, more preferably in the range of 10 to 50 mol%, particularly preferably in the range of 20 to 40 mol%. If the amount is less than 5 mol% or more than 60 mol%, it is difficult to obtain high sensitivity by introducing dislocation lines, which is not preferable.

The location where the high silver iodide content phase is formed on the host grains is arbitrary. The phase may be formed so as to cover the host grains or to be formed only in a specific portion. Controlling the position of dislocation lines within the grain by doing so is preferred. In the present invention, it is particularly preferable to form the high silver iodide content phase at the edge or the top of the host tabular grain. At this time, the composition of the halide to be added, the method of addition, the temperature of the reaction solution, p
Ag, solvent concentration, gelatin concentration, ionic strength and the like may be freely selected and used. The silver iodide content phase in the grains can be measured, for example, by an analytical electron microscope described in JP-A-7-219102.

In forming the high silver iodide content phase on the host grains in the present invention, a water-soluble iodide solution such as potassium iodide is added alone or simultaneously with a water-soluble silver salt solution such as silver nitrate. Method, a method of adding silver halide containing silver iodide in the form of fine grains, or, for example, US Pat.
No. 8,516, 5, 527, 664, a method of releasing iodide ions from an iodide ion releasing agent by reaction with an alkali or a nucleophile can be preferably used.

After the high silver iodide content phase is epitaxially grown on the host grains, when a silver halide shell is formed outside the host tabular grains, dislocation lines are introduced. The composition of the silver halide shell may be any of silver bromide, silver iodobromide and silver chloroiodobromide, but is preferably silver bromide or silver iodobromide. In the case of silver iodobromide, the preferred silver iodide content is 0.1 to 12 mol%, more preferably 0.1 to 10 mol%, and most preferably 0.1 to 3 mol%.
It is. If the amount is less than 0.1 mol%, it is not preferable because effects such as enhancement of dye adsorption and development acceleration are not easily obtained. If it exceeds 12 mol%, the developing speed is undesirably slow. The amount of silver used for this silver halide shell growth is 10% of the total grain silver amount.
It is preferably from 50 to 50 mol%, more preferably from 20 to 40 mol%.

The preferred temperature in the above-described dislocation line introduction step is 30 to 80 ° C., more preferably 35 to 75 ° C.
° C, particularly preferably 35 to 60 ° C. To perform temperature control at a low temperature of less than 30 ° C. or at a high temperature of more than 80 ° C., a high-performance manufacturing apparatus is required, which is not preferable in manufacturing. In addition, a preferable pA in the above-described dislocation line introduction process.
g is 6.4 to 10.5.

In the case of tabular grains, as described above, the position and number of dislocation lines for each grain as viewed from the direction perpendicular to the main plane can be determined from the photograph of the grain taken using an electron microscope. it can. When the tabular grain in the present invention has a dislocation line, its position can be selected from, for example, a vertex portion of the grain, limited to the fringe portion, or introduced over the entire main plane portion. Preferably, it is limited. The fringe portion referred to in the present invention refers to the outer periphery of a tabular grain. Specifically, in the distribution of silver iodide from the side to the center of the tabular grain, the silver iodide content at a certain point for the first time when viewed from the side is the grain. Outside the point where the average silver iodide content exceeds or falls below the average.

In the present invention, it is preferable to introduce high-density dislocation lines into the fringe portions of the tabular grains.
Tabular grains having zero or more dislocation lines are preferred. More preferably, 30 or more, more preferably 50 or more dislocation lines are provided in the particle fringe portion. When dislocation lines exist in a dense manner 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, the number can be counted to about 10, 20, or 30.

It is desirable that the tabular grains of the present invention have a uniform dislocation dose distribution between the grains. In the present invention, silver halide tabular grains containing 10 or more dislocation lines per grain preferably occupy 100 to 50% (number) of all grains, more preferably 100 to 80%. If it is less than 50%, it is difficult to obtain high sensitivity, which is not preferable. In the present invention, silver halide tabular grains containing 30 or more dislocation lines per grain are 100 to 50% of all grains.
(Number) is also preferable, and 100 to 8
It is even more preferred that it occupies 0%.

Further, the tabular silver grains of the present invention desirably have a uniform dislocation line introduction position in the grains. In the present invention, the higher the proportion of silver halide tabular grains in which dislocation lines are localized only in the fringe portions of the grains, the more preferable in terms of grain homogeneity.
The emulsion is preferably an emulsion in which tabular grains containing 0 or more dislocation lines account for 100 to 50% (number) of all grains.
More preferably, it accounts for 100 to 70%, even more preferably 100 to 80%. In the present invention, it is also preferred that the tabular grains containing 30 or more dislocation lines per grain in only the fringe portion of the grains occupy 100 to 50% (number) of all grains, more preferably 100%.
Occupies from 70 to 70%, more preferably from 100 to 80%.

In the present invention, the area of the fringe portion of the tabular grains is preferably 0.05 to 0.25 μm, more preferably 0.10 to 0.20 μm. Outside this range, an increase in the intrinsic sensitivity is difficult to obtain, which is not preferable. In the present invention, when determining the ratio of particles containing dislocation lines and the number of dislocation lines, it is preferable to directly obtain dislocation lines for at least 100 particles, more preferably 200 particles or more, and particularly preferably 3 or more.
Observe and determine about 00 particles or more.

In the present invention, when the silver iodide content at the fringe portion or the apex portion of the grain is measured using an analytical electron microscope by the method described in JP-A-7-219102, a silver iodide content of 2 mol% or more is measured. The formation of tabular grains having a specific iodide content is preferred from the viewpoint of an increase in intrinsic sensitivity, and more preferably has a silver iodide content of 4 mol% or more, further preferably 5 mol% or more. In the present invention, when the silver iodide content distribution in the tabular grains is measured by a method using the same analytical electron microscope as described above, in the present invention, the fringe portion or the vertex of the grain is compared with the average silver iodide content in the central region of the grain. Either a grain having a high silver iodide content or a grain having a low silver iodide content may be selected, but the former is preferred.

Next, the metal complex dopant used in the present invention will be described. The silver halide grains of the present invention contain at least one metal complex having as a ligand a heterocyclic compound having a number of more than half of the coordination numbers of metal atoms.

The metal complex used in the present invention preferably has a heterocyclic compound as a ligand in a number exceeding half of the coordination number of a metal atom, and in particular, a 5- or 6-membered nitrogen-containing heterocyclic compound. A metal complex having a ligand is preferable. When a hexacoordinate octahedral complex is incorporated into a silver halide grain as a dopant, J. Phys .: Condens.
(1997) 3227-3240 As described in many documents and patents, including, [AgX _6] in the silver halide grains ^5- (X ^- = halide ions) some of the particles as a unit And the dopant are said to be replaced. Therefore, it is considered that the farther the charge of the complex to be doped is from -5, the more disadvantageous the substitution becomes. From such a viewpoint, it is preferable that the ligand of the complex dopant of the present invention is an anion and the complex as a whole has a negative charge. At this time, it is preferable that the solubility of the complex ion silver salt is small in order to increase the doping ratio. Specifically, the ligand is preferably pyrrole, pyrazole, imidazole, triazole, or tetrazole, and it is also preferable to use a derivative thereof as the ligand. As the substituent in the derivative, 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, 2-ethylhexyl group , Dodecyl group, hexadecyl group, t-octyl group, isodecyl group, isostearyl group, dodecyloxypropyl group, trifluoromethyl group, methanesulfonylaminomethyl group, etc.),
Alkenyl group, alkynyl group, aralkyl group, cycloalkyl group (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, 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-dibutyl Reid group, thioureido group, an acyl group (formyl group, such as an acetyl group), an oxycarbonyl group, a substituted or unsubstituted carbamoyl group (ethylcarbamoyl group, dibutylcarbamoyl group, dodecyloxy propylcarbamoyl 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 It is preferably a 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 central metal of the present invention is not particularly limited, but it is preferable that the coordination structure around the metal has a four-coordinate structure or one having a six-coordinate structure. preferable. Furthermore, it is preferable to use metal ions having a closed nucleus structure, and it is preferable to use alkaline earth metal, iron (II), ruthenium (II), osmium (II), zinc, cadmium, and mercury ions. . Among these, it is particularly preferable to use ions of magnesium, iron (II), ruthenium (II), and zinc.

These compounds function as transient or permanent traps for electrons or holes in the silver halide crystal, and can provide effects such as high sensitivity, high contrast, improvement of reciprocity law and improvement of pressure property. Presumed.

The metal complex used in the present invention is added directly to the reaction solution when forming silver halide grains, or in an aqueous halide solution for forming silver halide grains, or in other solutions. It is preferable to add the silver halide grains to the silver halide grains by adding them to the grain forming reaction solution. Further, these methods may be combined to dope silver halide grains.

When the metal complex of the present invention is doped into silver halide grains, it may be uniformly present inside the grains,
JP-A-4-208936, JP-A-2-125245
As disclosed in Japanese Patent Application Laid-Open Nos. Hei 3-18837 and Hei 3-18837, a high concentration doping may be carried out on 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 metal complex (dopant) of the present invention is from 1 × 10 ^-8 mol to 1 mol per mol of silver halide.
X 10 ^-3 mol is preferable, and more preferably 1 X 10 ^-7 to 1 X 10 ^-4 mol. The dopant means an impurity added to the silver halide crystal.

Next, the dopant used in combination with the metal complex dopant used in the present invention will be described. The silver halide grains of the present invention are preferably doped with polyvalent metal ions such as various transition metal elements in combination with the metal complex dopant of the present invention. These polyvalent metal ions can be introduced in the form of halides or nitrates during grain formation, but metal complexes having a polyvalent metal ion as a central metal (halogeno complexes, ammine complexes, cyano complexes,
Nitrosyl complex). The metal complex preferably used in the present invention is a metal complex belonging to the first, second or third transition series, which is a ligand capable of largely splitting the d orbital in the spectrochemical series such as cyanide ion. Complex. The coordination form of these complexes is such that the six ligands are coordinated in an octahedral form.
In the coordination complex, it is preferable that the number of cyan ligands is four or more. Preferred central transition metals include
Examples include iron, cobalt, ruthenium, rhenium, osmium, and iridium. When all of the six ligands of these metal ions are not cyan ligands, the remaining ligands are halide ions such as fluoride, chloride or bromide ions, and inorganic ligands such as SCN, NCS and H ₂ O. Ligand and further, two or less organic ligands such as pyridine, phenanthroline, imidazole and pyrazole can be used. In the emulsion of the present invention, in addition to the above-mentioned metal complex, a complex composed of ruthenium, rhodium, palladium or iridium having a halide ion or a thiocyanate ion as a ligand, and a nitrosyl ligand of 1
Complexes composed of at least one ruthenium and complexes composed of chromium having a cyanide ion ligand can be preferably used in combination. It is preferable that the complex used in combination is also used within the range of the addition method and the addition amount described above. When the metal ions of the cyano complex are doped into the emulsion grains, the reaction between gelatin and the cyano complex may generate cyan, which may inhibit gold sensitization. In such a case, for example, JP-A-6-30
It is preferable to use a compound having a function of inhibiting the reaction between gelatin and a cyano complex in combination, as described in 8653. Specifically, it is preferable to perform the steps after doping with the metal ion of the cyano complex in the presence of a metal ion such as a zinc ion that coordinates with gelatin. The silver halide grains of the present invention are preferably doped with a so-called divalent anion of a so-called chalcogen element such as sulfur, selenium or tellurium, in addition to the above-mentioned metal complexes.
These dopants are also effective for obtaining high sensitivity and improving the dependence on exposure conditions.

In the present invention, the silver halide emulsion of the present invention and other silver halide emulsions used together therewith will be described below. The method for preparing the silver halide grains of the present invention is a known method, that is, "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Gla).
fkides, Chimie et Physique
Photographique, Paul Mont
el, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photo).
graphic Emulsion Chemistr
y, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., published by Focal Press (VL Zelikman et al., Maki).
ng and Coating of Photogr
aphic Emulsion, Focal Pres
s, 1964). That is, it can be prepared in various pH ranges such as an acidic method, a neutral method, and an ammonia method. In addition, as a method for supplying a water-soluble silver salt and a water-soluble halogen salt solution as a reaction solution, a one-side mixing method, a simultaneous mixing method, or the like can be used alone or in combination. Further, it is also preferable to use a controlled double jet method for controlling the addition of the reaction solution so as to keep the pAg during the reaction at a target value. Further, a method of maintaining a constant pH value during the reaction is also used. In forming the grains, a method of controlling the solubility of silver halide by changing the temperature, pH or pAg value of the system may be used, but thioether, thioureas, rhodan salts and the like may be used as the solvent. These examples are shown in
-11386 and JP-A-53-144319.

The silver halide grains of the present invention are usually prepared by controlling a solution of a water-soluble silver salt such as silver nitrate and a solution of a water-soluble halide salt such as an alkali halide in an aqueous solution of a binder such as gelatin. It is performed by supplying under the conditions described above. After the formation of silver halide grains, it is preferable to remove excess water-soluble salts. This is, for example, gelling a gelatin solution containing silver halide grains, cutting it into a string,
A Nudel washing method in which water-soluble salts are washed away with cold water, an inorganic salt comprising a polyvalent anion (eg, sodium sulfate), an anionic surfactant, an anionic polymer (eg, sodium polystyrene sulfonate), or a gelatin derivative (eg, an aliphatic acyl) , Acetylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may be added to agglomerate the gelatin to remove excess salts. When the sedimentation method is used, excess salts are rapidly removed, which is preferable.

In the present invention, it is usually preferable to use a silver halide emulsion which has been subjected to chemical sensitization by a commonly known sensitization method alone or in various combinations. Chemical sensitization imparts high sensitivity to the prepared silver halide grains,
It contributes to imparting exposure condition stability and storage stability.
As a chemical sensitization method, a chalcogen sensitization method using a sulfur, selenium or tellurium compound is preferably used. As these sensitizers, compounds that release the above-described chalcogen elements to form silver chalcogenides when added to a silver halide emulsion are used. Furthermore, it is also preferable to use these in combination in order to obtain high sensitivity and to suppress fog to a low level. Also, a noble metal sensitization method using gold, platinum, iridium or the like is preferable. In particular, a gold sensitization method using chloroauric acid alone or in combination with a thiocyanate ion serving as a gold ligand can provide high sensitivity. When gold sensitization and chalcogen sensitization are used together, higher sensitivity can be obtained. Further, by using a compound having an appropriate reducing property during grain formation, a high sensitivity is obtained by introducing a reducing silver nucleus.
A so-called reduction sensitization method is also preferably used. A reduction sensitization method in which an alkynylamine compound having an aromatic ring is added during chemical sensitization is also preferable. When performing chemical sensitization, it is also preferable to control the reactivity of the compound by using various compounds having adsorptivity to silver halide grains. Prior to chalcogen sensitization or gold sensitization, nitrogen-containing heterocyclic compounds and mercapto compounds,
A method of adding a sensitizing dye such as a cyanine or a merocyanine is particularly preferable. The reaction conditions for performing the chemical sensitization differ depending on the purpose, but the temperature is 30 ° C to 95 ° C, preferably 4 ° C.
0 ° C to 75 ° C, pH is 5.0 to 11.0, preferably 5.5 to 8.5, and pAg is 6.0 to 10.5, preferably 6.5 to 9.8. Regarding the chemical sensitization technology, JP-A-3-110555, JP-A-4-75798, JP-A-62-253159, JP-A-5-45833,
It is described in JP-A-62-40446 and the like.
It is also preferable to form an epitaxial projection in the chemical sensitization step.

In the present invention, the photosensitive silver halide emulsion
The so-called spectral sensitization that gives sensitivity to the desired light wavelength range
Is preferred. In particular, in color photographic materials,
Sensitivity to blue, green, and red for color reproduction faithful to null
Having a photosensitive layer. These photosensitive
Sensitizes silver halide with so-called spectral sensitizing dyes
It is given by Examples of these dyes include shea
Nin pigment, merocyanine pigment, composite cyanine pigment, composite
Merocyanine dye, holopolar dye, hemicyanine color
, Styryl dyes or hemioxonol dyes, etc.
I can do it. Examples of these are described in US Pat.
257, JP-A-59-180550, JP-A-64-13
No. 546, JP-A-5-45828 and 5-45834.
It is described in the specification and the like. Spectral sensitizing dyes alone
In addition to being used, a plurality of types of dyes are used in combination.
This is for the purpose of adjusting the spectral distribution of spectral sensitivity and for supersensitization.
Done in In the combination of dyes exhibiting supersensitization,
It is possible to obtain a sensitivity that greatly exceeds the sum of the sensitivities that can be achieved alone.
Can be. Also, it does not have a spectral sensitizing effect by itself.
Dyes or compounds that do not substantially absorb visible light
Therefore, a compound exhibiting supersensitization may be used in combination.
preferable. Supersensitization of diaminostilbene compounds, etc.
Examples of the agent can be given. As an example of these
Are described in U.S. Pat. No. 3,615,641 and JP-A-63-231.
No. 45, etc. These spectral sensitized colors
The addition of elemental and supersensitizers to silver halide emulsions
At any time of manufacture. For emulsion after chemical sensitization
Added at the time of coating solution preparation, added at the end of chemical sensitization,
Add during chemical sensitization, add before chemical sensitization
To be added after the end of grain formation and before desalting.
Seeds to be added or added prior to particle formation
Each method can be used alone or in combination
You. High sensitivity is added in the step before chemical sensitization.
Preferred to obtain. Addition amount of spectral sensitizing dye or supersensitizer
Is the particle shape and particle size
Although it varies depending on the nature, it is generally 1 mole equivalent of silver halide.
10^{-8 ~}10 ^-1Mole, preferably 10^-Five-10^-2Mo
Range. These compounds can be
As a solution of organic solvent such as hydrogen alcohol
It can be added as a dispersion in water with an active agent or gelatin.

Fogging was prevented in the silver halide emulsion.
Various stabilizers to increase the stability during storage
Is preferred. Preferred stabilizers include Azai
Indene, triazole, tetrazole, purine
And other nitrogen-containing heterocyclic compounds such as mercaptotetrazole
, Mercaptotriazoles, mercaptoimidazo
Compounds such as mercaptothiadiazoles
And the like. Details of these compounds
Is the theory of the photographic process by James, published by Macmillan
(TH James, The Theory of
the Photographic Process,
Macmillan, 1977) pp. 396-399.
And its cited references. In the present invention,
Among these antifoggants, those having 4 or more carbon atoms
Merka having a kill group or a plurality of aromatic groups as substituents
Putazoles can be particularly preferably used. This
Silver halide emulsions of these antifoggants or stabilizers
Can be added at any time during the preparation of the emulsion. Chemical increase
After completion of sensitization, when preparing a coating solution, at the end of chemical sensitization, during chemical sensitization
Medium, before chemical sensitization, after completion of grain formation, before desalination, during grain formation,
Or various methods such as adding prior to particle formation
Can be used alone or in combination. this
The amount of antifoggant or stabilizer added is halogenated
It varies widely depending on the halogen composition and purpose of the silver emulsion,
Generally 10 per mole of silver halide^-6-10 ^-1Mole, good
Preferably 10^-Five-10^-2Range of moles.

The photographic additives used in the light-sensitive material of the present invention as described above are described in Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17643 (December 1978) and No. 18716 (November 1979). And No. 307105 (November 1989), and the relevant portions are summarized below. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23 648 right column 866 Sensitivity enhancer 648 right column Spectral sensitizer 23-24 page 648 right column 866-868 Super sensitizer page 649 Right column Brightener 24 page 648 page 868 right column Antifoggant 24 to 26 page 649 right column 868 to 870 Stabilizer light absorber 25 to 26 page 649 right column 873 filter dye 650 page left column UV absorber Dye image stabilizer page 25 650 page left column 872 Hardener page 26 651 page left column 874-875 Binder page 26 651 page left column 873-874 plasticizer, lubricant page 27 650 page right column Page 876 Coating aid page 26-27 page 650 right column 875-876 Surfactant Antistatic agent page 27 page 650 right column 876-877 Matting agent, pp. 878-879

In the present invention, an organic metal salt can be used in combination with the photosensitive silver halide as an oxidizing agent. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above described organic silver salt oxidizing agents include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 0,626, columns 52 to 53 and the like. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above organic silver salt is used in an amount of 0.01 to 1 mol per mole of the photosensitive silver halide.
10 mol, preferably 0.01 to 1 mol, can be used in combination.

Hydrophilic for photosensitive materials and binders for constituent layers
Is preferably used. For example,
Search Disclosure and JP-A-64-13
No. 546, pages (71) to (75)
No. Specifically, a transparent or translucent hydrophilic vine
And gelatin, gelatin derivatives, etc.
Protein or cellulose derivatives, starch, gum arabic,
Natural compounds such as polysaccharides such as dextran and pullulan
And polyvinyl alcohol, modified polyvinyl alcohol
(For example, Povar with terminal alkyl modification manufactured by Kuraray Co., Ltd.
MP103, MP203, etc.), polyvinylpyrrolidone,
Synthetic polymer compounds such as acrylamide polymers
You. Also, U.S. Pat. No. 4,960,681,
Superabsorbent polymer described in No. 2-245260;
-COOM or -SO_ThreeM (M is a hydrogen atom or
Homopolymers of vinyl monomers containing alkali metals)
Or this vinyl monomer or another vinyl monomer
(E.g., sodium methacrylate,
Ammonium acrylate, Sumika gel manufactured by Sumitomo Chemical Co., Ltd.
L-5H) are also used. These binders are two or more kinds.
They can be used in combination. Especially with gelatin
A combination of the above binders is preferred. Also gelatin
Can be used for various purposes, such as lime-treated gelatin and acid-treated gelatin.
So-called demineralization with reduced content of tin, calcium, etc.
It can be selected from gelatin and can be used in combination
preferable. In the present invention, the coating amount of the binder is 1 to
20g / m ^Two, Preferably 2 to 15 g / m^Two, Even more preferred
3 to 12 g / m^TwoIs appropriate. Gelatin in this
Is 50% to 100%, preferably 70% to 100%
Used in combination.

It is preferable to incorporate a developing agent into the light-sensitive material of the present invention. As the developing agent to be incorporated, it is preferable to use at least one selected from the compounds represented by the aforementioned general formulas (1) to (4).

The compound represented by the general formula (1) is a compound generally called sulfonamidophenol. Where R
_{1 to} R ₄ are each a hydrogen atom, a halogen atom (for example, a chloro group or a bromo group), an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group),
Aryl group (for example, phenyl group, tolyl group, xylyl group), alkylcarbonamide group (for example, acetylamino group, propionylamino group, butyroylamino group),
Arylcarbonamide group (eg, benzoylamino group), alkylsulfonamide group (eg, methanesulfonylamino group, ethanesulfonylamino group), arylsulfonamide group (eg, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy group (eg, methoxy Group, ethoxy group, butoxy group), aryloxy group (eg, phenoxy group), alkylthio group (eg, methylthio group, ethylthio group, butylthio group), arylthio group (eg, phenylthio group, tolylthio group), alkylcarbamoyl group (eg, methylcarbamoyl) Group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoy Groups (eg, phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl), carbamoyl, alkylsulfamoyl (eg, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl) , Diethylsulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, morpholylsulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group) Famoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group, alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (eg, phenylsulfonyl group) 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, Represents a propionyl group, a butyroyl group), an arylcarbonyl group (eg, a benzoyl group, an alkylbenzoyl group), or an acyloxy group (eg, an acetyloxy group, a propionyloxy group, a butyroyloxy group). Among R _{1 to} R ₄ , R ₂ and R ₄ are preferably a hydrogen atom. Further, it is preferable that the sum of the Hammett constant σp values of R _{1 to} R ₄ is 0 or more. R ₅ represents an alkyl group (eg, methyl group, ethyl group, butyl group, octyl group, lauryl group, cetyl group, stearyl group), an aryl group (eg, phenyl group, tolyl group, xylyl group, 4-methoxyphenyl group, dodecylphenyl) A chlorophenyl group, a trichlorophenyl group, a nitrochlorophenyl group, a triisopropylphenyl group, a 4-dodecyloxyphenyl group, a 3,5-di- (methoxycarbonyl) group, or a heterocyclic group (eg, a pyridyl group).

The compound represented by the general formula (2) is a compound generally called carbamoylhydrazine. The compound represented by the general formula (4) is a compound generally referred to as sulfonylhydrazine. In the formula, Z represents an atom group forming an aromatic ring. The aromatic ring formed by Z needs to be sufficiently electron-attracting in order to impart silver developing activity to the present compound. For this reason, an aromatic ring which forms a nitrogen-containing aromatic ring or has an electron-withdrawing group introduced into a benzene ring is preferably used. As such an aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinoxaline ring and the like are preferable. In the case of a benzene ring,
Examples of the substituent include an alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), a halogen atom (eg, chloro group, bromo group), an alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group) Group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (for example, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group ( For example, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl, piperidyls Famoyl group, morpholylsulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano Group,
Alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxy) A carbonyl group), an aryloxycarbonyl group (for example, a phenoxycarbonyl group), an alkylcarbonyl group (for example, an acetyl group, a propionyl group, a butyroyl group), or an arylcarbonyl group (for example, a benzoyl group or an alkylbenzoyl group).
The sum of Hammett constant σ values of the above substituents is 1 or more.

The compound represented by the general formula (3) is a compound generally called carbamoylhydrazone. Where R ₆
Represents a substituted or unsubstituted alkyl group (for example, a methyl group or an ethyl group). X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl- or aryl-substituted tertiary nitrogen atom, preferably an alkyl-substituted tertiary nitrogen atom.
R ₇ and R ₈ represent a hydrogen atom or a substituent, and R ₇ and R ₈ may combine with each other to form a double bond or a ring.

Hereinafter, specific examples of the compounds represented by formulas (1) to (4) are shown, but the compounds of the present invention are not limited thereto.

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

[0078]

Embedded image

As the color developing agent, the above compounds are used alone or in combination of two or more. Separate developing agents may be used for each layer. The total amount of these developing agents used is 0.05 to 20 mmol / m ² , preferably 0.1 to 1 mmol / m ² .
0 mmol / m ² .

Next, the coupler will be described. The coupler in the present invention is a compound that forms a dye by a coupling reaction with an oxidized form of a color developing agent. In the present invention, couplers preferably used are compounds generally referred to as active methylene, 5-pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole. These couplers are described in Research Disclosure (hereinafter abbreviated as RD) No. 38957 (September 1996), 616-624.
The compounds cited on page "x. Dye image former sand modifiers" can be preferably used. These couplers can be divided into so-called 2-equivalent couplers and 4-equivalent couplers. Examples of the group acting as an anionic leaving group of the 2-equivalent coupler include a halogen atom (eg, chloro group, bromo group), an alkoxy group (eg, methoxy group, ethoxy group), an aryloxy group (eg, phenoxy group, 4-cyanophenoxy group) , 4-alkoxycarbonylphenyl), alkylthio (eg, methylthio, ethylthio, butylthio), arylthio (eg, phenylthio, tolylthio), alkylcarbamoyl (eg, methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl) , Diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (for example, phenylcarbamoyl group,
Methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, Dibutylsulfamoyl group, piperidylsulfamoyl group, morpholylsulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfoyl group) Famoyl group), sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (for example, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p Toluenesulfonyl group), alkylcarbonyloxy group (eg, acetyloxy group, propionyloxy group, butyroyloxy group), arylcarbonyloxy group (eg, benzoyloxy group, toluyloxy group, anisyloxy group), nitrogen-containing heterocyclic group (eg, imidazolyl group) Benzotriazolyl group). Examples of the group acting as a cationic leaving group of the 4-equivalent coupler include a hydrogen atom, a formyl group, a carbamoyl group, and a methylene group having a substituent (for the substituent, an aryl group, a sulfamoyl group, a carbamoyl group,
An alkoxy group, an amino group, a hydroxyl group, etc.), an acyl group, a sulfonyl group and the like.

In addition to the compounds described in RD No. 38957, the following couplers can be preferably used. As an active methylene coupler, the formula of EP502,424A is used.
Couplers represented by (I) and (II); Formulas (1) and (2) of EP513,496A
A coupler of the formula (I) in claim 1 of EP568,037A
A coupler represented by the formula: US Pat. No. 5,066,576, column 1 45 to 55
A coupler represented by the general formula (I) in the line; a coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425; EP498, 381A
A coupler described in claim 1 on page 40 of claim 1; a coupler represented by formula (Y) on page 4 of EP447,969A1; a coupler represented by formulas (II) to (IV) in columns 7 to 36 of US Pat. Couplers can be used. Examples of 5-pyrazolone-based magenta couplers include JP-A-57-35858 and JP-A-5-58858.
Compounds described in No. 1-20826 are preferred. Pyrazoloazole-based couplers include US Pat. No. 4,500,
No. 630, imidazo [1,2-b] pyrazoles, U.S. Pat. No. 4,540,654, pyrazolo [1,5-b] [1,2,4] triazoles, U.S. Pat. Pyrazolo [5,1-
c] [1,2,4] triazoles are preferable, and among these, pyrazolo [1,5-b] [1,
[2,4] triazoles are preferred. Preferred examples of the phenolic coupler include US Pat. No. 2,369,9.
No. 29, No. 2,801,171, No. 2,772
No. 162, No. 2,895,826, No. 3,77
2,002 and the like, 2-alkylamino-5-alkylphenols, U.S. Pat. No. 2,772,162,
No. 3,758,308, No. 4,126,396
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729,
9,166,956 and the like, U.S. Patent Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427. , 767, etc., and the like. Preferred examples of the naphthol coupler include U.S. Pat. Nos. 2,474,293 and 4,052,212.
No. 4,146,396, No. 4,228,23
No. 3,296,200 and the like, and 2-carbamoyl-1-naphthols and U.S. Pat.
No. 889, 2-carbamoyl-5-amide-1
-Naphthol type and the like. Preferred examples of the pyrrolotriazole coupler are described in European Patent No. 4
And the couplers described in JP-A-88,248A1, JP-A-491,197A1, and JP-A-545,300.

In addition, fused ring phenol, imidazole,
Pyrrole, 3-hydroxypyridine, active methine, 5,
Couplers having a structure such as a 5-fused heterocycle and a 5,6-fused heterocycle can be used. U.S. Pat. Nos. 4,327,173;
Couplers described in 564,586 and 4,904,575 can be used. U.S. Pat. Nos. 4,818,672 and 5,052 are imidazole couplers.
The couplers described in JP-A No. 1,347 and the like can be used. As pyrrole couplers, JP-A-4-188137,
The couplers described in -190347 and the like can be used. 3
-Hydroxypyridine couplers are disclosed in JP-A No. 1-3
The couplers described in No. 15736 can be used. Activated methine couplers are described in US Pat. No. 5,104,783.
No. 5,162,196 and the like can be used. As the 5,5-condensed heterocyclic coupler, a pyrrolopyrazole coupler described in U.S. Pat. No. 5,164,289, a pyrroleimidazole coupler described in JP-A-4-174429, and the like can be used. 5,6-Fused heterocyclic couplers include U.S. Pat.
For example, pyrazolopyrimidine couplers described in JP-A No. 585, pyrrolotriazine couplers described in JP-A-4-204730, and couplers described in EP 556,700 can be used. In the present invention, in addition to the couplers described above, West German Patent Nos. 3,819,051A and 3,823,04
9, U.S. Patent Nos. 4,840,883 and 5,02
No. 4,930, No. 5,051,347, No. 4,4
No. 81,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, 63-141055
Nos. 64-32260 and 32261, JP-A No. 2
No. -297475, No. 2-44340, No. 2-110
555, 3-7938, 3-160440,
Nos. 3-172839, 4-172247, 4-
No. 179949, No. 4-182645, No. 4-184
Nos. 437, 4-188138, 4-188139
And couplers described in JP-A Nos. 4-194847, 4-204532, 4-204731, and 4-204732. These couplers are used in each color in an amount of 0.05 to 10 mmol / m ² , preferably 0.1 to 5 mmol / m ² .
l / m ^{2 is} used.

Further, the following functional couplers may be contained. US 4,366,237, GB 2,125,570, EP 96,873B, DE
Those described in 3,234,533 are preferred. EP 456,2 as couplers for correcting unnecessary absorption of coloring dyes
57A1 yellow colored cyan coupler,
The yellow colored magenta coupler described in the EP, U
Magenta colored cyan coupler described in S4,833,069, (2) of WO4,837,136, WO9
2/11575, a colorless masking coupler of formula (A) of claim 1 (especially the exemplified compounds on pages 36-45).

Compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound:
Formulas (I) to (I) described on page 11 of EP 378,236A1.
A compound represented by the formula (I) described on page 7 of EP 436,938 A2;
A compound represented by the formula (1) of 7A, a compound represented by the formula (I), (II) or (III) described on pages 5 to 6 of EP440,195A2. Bleaching accelerator releasing compounds: compounds represented by formulas (I) and (I ') on page 5 of EP310, 125A2 and compounds represented by formula (I) of claim 1 of JP-A-6-59411. Ligand releasing compound: a compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478. Leuco dye releasing compound: Compound 1 in columns 3 to 8 of US 4,749,641
~ 6; Fluorescent dye releasing compound: Claim 4, C of US 4,774,181
Compound represented by OUP-DYE. Development accelerator or fogging agent releasing compound: Formulas (1), (2) in column 3 of US 4,656,123,
A compound represented by (3) and ExZK-2 on page 75, lines 36 to 38 of EP450,637A2. Compounds which release a group which becomes a dye only after leaving: a compound represented by the formula (I) of claim 1 of US Pat. No. 4,857,447, a compound represented by the formula (1) of Japanese Patent Application No. 4-134523, Compounds represented by formulas (I), (II) and (III) described on pages 5 and 6;
A compound-ligand releasing compound represented by formula (I) of claim 1 of 325564, a compound represented by LIG-X according to claim 1 of US Pat. No. 4,555,478. Such a functional coupler may be used in an amount of 0.05 to 10 times, preferably 0.1 to 10 times, the amount of the coupler that contributes to color development described above.
It is preferable to use a 5-fold molar amount.

A hydrophobic additive such as a coupler or a color developing agent can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat. No. 4,555,470,
No. 4,536,466, No. 4,536,467, No. 4,587,206, No. 4,555,476, No. 4,599,296, No. 3-62,256, etc. A high boiling organic solvent such as
It can be used in combination with a low boiling point organic solvent of 0 ° C to 160 ° C. Two or more of these dye-donating couplers and high-boiling organic solvents can be used in combination. The amount of the high boiling organic solvent is 10 to 1 g of the hydrophobic additive used.
g or less, preferably 5 g or less, more preferably 1 g or more.
0.1 g. Further, 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable for 1 g of the binder. JP-B-51-39,853, JP-A-51-59,
A dispersion method using a polymer described in No. 943 or a method of adding a fine particle dispersion described in JP-A-62-30242 can be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-15763
No. 6, pp. (37)-(38), and the surfactants described in Research Disclosure described above can be used. Japanese Patent Application Nos. 5-204325 and 6-19
No. 247 and West German Patent Publication No. 1,932,299A can also be used.

In the light-sensitive material of the present invention, it is necessary to provide at least three kinds of light-sensitive layers provided with different light-sensitive areas on a support. A typical example is a silver halide photographic light-sensitive material having, on a support, at least three kinds of light-sensitive layers comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. 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 the aforementioned couplers, developing agents, and DI
An R compound, a color mixture inhibitor, a dye, and the like may be contained.
As described in DE 1,121,470 or GB 923,045, a plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by coating a high-speed emulsion layer and a low-speed emulsion layer toward a support. It is preferable to arrange them so that the sensitivities become lower sequentially. Also, JP-A-57-112751, 62-200350, 62-20654
As described in JP-A-62-206543, a low-speed emulsion layer may be provided on the side remote from the support, and a high-speed emulsion layer may be provided on the side near the support. As a specific example, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) /
High sensitivity red photosensitive layer (RH) / low sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL
/ GH / GL / RL / RH. Also, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738, 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 the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low light sensitivity and sequentially decreasing the light sensitivity toward the support.
An arrangement composed of layers is mentioned. Even in the case of three layers having different sensitivities, Japanese Patent Application Laid-Open No. 59-20246
As described in 4, in the same color-sensitive layer, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in this order from the side away from the support. 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.

In a color negative film which has been conventionally used for photography, not only the silver halide emulsion is improved to achieve the desired granularity, but also the development is suppressed during the coupling reaction with the oxidized developing agent. Techniques such as the use of a so-called DIR coupler that releases a compound having an acidic property have been incorporated. In the photosensitive material of the present invention, D
Excellent granularity is obtained even when no IR coupler is used. In addition, the granularity becomes increasingly better if a DIR compound is combined. In order to improve color reproducibility, U.S. Patent Nos. 4,663,271, 4,705,744,
No. 707,436, JP-A-62-160448 and JP-A-63-89850, the main photosensitive layer of BL, GL, RL, etc., and the donor layer (CL) having a multilayer effect having a different spectral sensitivity distribution from the main photosensitive layer. It is preferred to place it adjacent or close to the layer. In the present invention, the silver halide, the dye-donor coupler and the color developing agent may be contained in the same layer, but may be added separately in separate layers as long as they can react. For example, when the layer containing the color developing agent and the layer containing silver halide are formed as separate layers, the raw storability of the light-sensitive material can be improved.

In the present invention, a light-sensitive material used for recording an original scene and reproducing it as a color image can basically use color reproduction by a subtractive color method. That is, at least three types of photosensitive layers having photosensitivity are provided in the blue, green, and red regions, and yellow, magenta, and cyan dyes are formed in each photosensitive layer, which are complementary colors to the photosensitive wavelength region. The color information of the original scene can be recorded by including a color coupler which can be used. The original scene can be reproduced by exposing the color image having the same relationship between the photosensitive wavelength and the color hue through the dye image thus obtained. Further, information of a dye image obtained by photographing an original scene can be read by a scanner or the like, and an ornamental image can be reproduced based on this information. As the light-sensitive material of the present invention, a light-sensitive layer having photosensitivity in three or more wavelength regions can be provided. It is also possible to provide a relationship other than the above-described complementary colors between the photosensitive wavelength region and the color hue. In such a case, the original color information can be reproduced by performing image processing such as hue conversion after capturing the image information as described above. The relationship between the spectral sensitivity of each layer and the hue of the coupler is arbitrary, but if a cyan coupler is used for the red photosensitive layer, a magenta coupler is used for the green photosensitive layer, and a yellow coupler is used for the blue photosensitive layer, it can be directly applied to conventional color paper. Projection exposure is possible. In the light-sensitive material, various non-light-sensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer are provided between and above the silver halide emulsion layer and the lowermost layer. Various auxiliary layers such as a back layer can be provided on the opposite side of the support. Specifically, the layer constitution as described in the above patent, US Pat.
Undercoat layer as described in JP-A-051,335, JP-A-1-1-1
No. 67,838, JP-A-61-20,943, an intermediate layer having a solid pigment, and JP-A-1-120,55.
No. 3, No. 5-34,884 and No. 2-64,634, an intermediate layer having a reducing agent or a DIR compound, U.S. Pat. Nos. 5,017,454 and 5,139,919.
, An intermediate layer having an electron transfer agent as described in JP-A-2-235,044, a protective layer having a reducing agent as described in JP-A-4-249,245, or a layer obtained by combining them. Can be.

In the present invention, a yellow filter layer,
Dyes that can be used in the magenta filter layer or the antihalation layer include 1 / 3
The concentration is preferably 1/10 or less, and preferably does not contribute to the concentration after the treatment. Specifically, dyes described in European Patent Application EP 549,489A and JP-A No.
And dyes ExF2 to Ex.
Dyes dispersed in a solid as described in Japanese Patent Application No. 6-259805 can also be used. In addition, a mordant and a binder may be dyed with a dye. In this case, as the mordant and the dye, those known in the photographic field can be used, and US Pat. No. 4,500,626, columns 58 to 59,
JP-A-61-88256, pages 32 to 41;
Mordants described in JP-A-244043 and JP-A-62-244036 can be used. In addition, a compound capable of reacting with a reducing agent to release a diffusible dye and a reducing agent may be used to release a movable dye with an alkali at the time of development and to transfer and remove the dye to a processing material. Specifically, U.S. Pat.
59,290, 4,783,396, European Patent No. 220,746A2, and JP-A-87-6119, and paragraphs 0080 to 0081 of Japanese Patent Application No. 6-259805. Have been. A decolorizable leuco dye or the like can also be used.
No. 50,132 discloses a silver halide photosensitive material containing a leuco dye which has been colored in advance with a developer of a metal salt of an organic acid.

In the present invention, as the support of the light-sensitive material, a support which is transparent and can withstand the processing temperature is used. In general, the Photographic Society of Japan, "Basics of Photographic Engineering-Silver halide photography-", Corona Co., Ltd. (1979) (2)
Photographic supports such as papers and synthetic polymers (films) described on pages 23) to (240). Specific examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, and celluloses (for example, triacetyl cellulose). Among these, a polyester containing polyethylene naphthalate as a main component is particularly preferable, but the polyester referred to herein as “polyethylene naphthalate as a main component” refers to a content of naphthalenedicarboxylic acid contained in all dicarboxylic acid residues. Is preferably 50 mol% or more. More preferably, 60 mol%
Above, more preferably 70 mol% or more. It may be a copolymer or a polymer blend. In the case of copolymerization, those obtained by copolymerizing units such as terephthalic acid, bisphenol A, and cyclohexanedimethanol in addition to the naphthalenedicarboxylic acid unit and the ethylene glycol unit are also preferable. Among these, the most preferred is a copolymer of a terephthalic acid unit from the viewpoint of mechanical strength and cost. Preferred partners for the polymer blend are polyethylene terephthalate (PET) and polyarylate (PA) from the viewpoint of compatibility.
r), polyesters such as polycarbonate (PC) and polycyclohexane dimethanol terephthalate (PCT). Among them, a polymer blend with PET is preferable from the viewpoint of mechanical strength and cost. Particularly when heat resistance and curl characteristics are strictly required, JP-A-6-41281 and JP-A-6-41281 are used as a support for a photosensitive material.
No. 3581, No. 6-51426, No. 6-51437
No. 6-51442, Japanese Patent Application No. 4-251845,
4-231825, 4-253545, 4-
258828, 4-240122, 4-221
No. 538, No. 5-21625, No. 5-15926,
4-331919, 5-199704, 6-
The supports described in JP-A Nos. 13455 and 6-14666 can be preferably used. Further, a support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used. The thickness of the support is
Preferably 5-200μ, more preferably 40-120
μ. In order to bond the support and the light-sensitive material constituting layer, surface treatment is preferably performed. Surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and the like. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.
Next, the undercoating method will be described. It may be a single layer or two or more layers. As a binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including a copolymer starting from a monomer selected from maleic anhydride, as a starting material, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, gelatin, polyvinyl alcohol, and modified polymers thereof. Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, chromium salts (such as chrome alum), aldehydes (formaldehyde,
Glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-
s-triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. Si
O ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

Regarding the dye used for film dyeing, the color tone is preferably gray dyeing due to the general properties of the light-sensitive material, and it has excellent heat resistance in the film forming temperature range and excellent compatibility with polyester. Are preferred. From that point of view, as dyes, Mitsubishi Chemical's Diaresin,
The purpose can be achieved by mixing a dye commercially available for polyesters such as Nippon Kayaku Kayset. In particular, from the viewpoint of heat stability, anthraquinone dyes can be used. For example, those described in JP-A-8-122970 can be preferably used.

As a support, for example, JP-A-4-14-1
No. 24645, No. 5-40321, No. 6-35092
It is preferable to record photographic information and the like using a support having a magnetic recording layer described in JP-A-6-317875.
The magnetic recording layer is obtained by coating an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder on a support. Magnetic particles include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal crystal systems Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co deposited γFe ₂ O ₃
Co-coated ferromagnetic iron oxide such as The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like.
The specific surface area is preferably not less than 20 m ² / g by SBET.
0 m ² / g or more is particularly preferred. Saturation magnetization (σ
s) is preferably 3.0 × 104 to 3.0 × 105 A /
m, particularly preferably 4.0 × 104 to 2.5 × 1
005 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-6-16032. Japanese Patent Laid-Open No. 4
Magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-259911 and 5-81652 can also be used.

Next, the polyester support will be described. The polyester support has a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg-2, in order to make it difficult to form a curl.
Heat treatment is performed at 0 ° C. or higher and lower than Tg. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 hours or more and 150 hours.
0 hours or less, more preferably 0.5 hours or more and 200 hours or less. The heat treatment of the support may be performed in a roll form or may be performed while transporting the support in a web form.
Irregularities may be imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ ) may be applied to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and raising the ends only slightly to prevent cut-out of the core. These heat treatments may be carried out at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), or after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this 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, a film cartridge in which a photosensitive material can be loaded will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Further, a patrone that sends out a film by rotating a spool may be used. Alternatively, 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 US4,8
Nos. 34,306 and 5,226,613.

The above photosensitive material is disclosed in Japanese Patent Publication No. 2-3615.
And Japanese Patent Publication No. 3-39784 can be preferably used. The lens-fitted film unit is a unit in which an unexposed color or monochrome photographic photosensitive material is preliminarily light-tightly loaded in a manufacturing process of a unit main body including a photographic lens and a shutter in, for example, an injection-molded plastic housing. After the user takes a picture of this unit, the unit is sent to a photo lab for development. In the photo lab, the photographic film is taken out of the unit and developed and a photographic print is created.

In the present invention, a processing material containing at least a base and / or a base precursor in a processing material layer can be used. As the base, an inorganic or organic base can be used. As the inorganic base, JP-A-62
Hydroxide, phosphate, carbonate, borate, organic acid salt of alkali metal or alkaline earth metal described in JP-A-209448, acetylide of alkali metal or alkaline earth metal described in JP-A-63-25208 And the like.
Examples of the organic base include ammonia, aliphatic or aromatic amines (eg, primary amines, secondary amines, tertiary amines, polyamines, hydroxylamines, heterocyclic amines), amidines, Bis or Tris or tetraamidine, guanidines, water-insoluble mono or bis or Tris or tetraguanidines, quaternary ammonium hydroxides, and the like are included. As the base precursor, decarboxylation type, decomposition type,
A reaction type and a complex salt forming type can be used. In the present invention, as described in European Patent Publication No. 210,660 and US Patent No. 4,740,445,
Adopts a method of generating a base using a combination of a basic metal compound which is hardly soluble in water and a compound capable of forming a complex with water using a metal ion constituting the basic metal compound and water as a base precursor (a complex forming compound). It is effective to do. In this case, it is desirable that the basic metal compound which is hardly soluble in water is added to the light-sensitive material and the complex-forming compound is added to the processing material, and vice versa. The amount of the base or base precursor used is 0.1 to 20 g / m ^2, preferably 1 to 10 g / m ² .

As the binder for the processing layer, a hydrophilic polymer similar to the photosensitive material can be used. The processing material is preferably hardened with the same hardener as the photosensitive material. The processing material may contain a mordant for the purpose of transferring and removing the dye used in the yellow filter layer and antihalation layer of the photosensitive material as described above. As the mordant, a polymer mordant is preferable. For example, 2
Polymers having a quaternary and tertiary amino group, polymers having a nitrogen-containing heterocyclic moiety, polymers having a quaternary cation group, etc., having a molecular weight of 5,000 to 200,000, particularly 100
00 to 50,000. The amount of mordant added is 0.
^{1g / m 2 ~10g / m 2} , and preferably from ^{0.5g / m 2 ~5g / m 2} .

In the present invention, the processing material may contain a development terminator or a precursor of the development terminator, and the development terminator may be activated simultaneously with or at a later timing than the development. As used herein, the term "development terminator" refers to a compound that neutralizes a base or reacts with a base to reduce the base concentration in a film and stop development immediately after appropriate development, or to interact with silver or a silver salt to effect development. It is a compound that suppresses. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that undergoes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For details, see JP-A-62-190.
No. 529, pages (31) to (32). Similarly, a silver halide printout inhibitor may be included in the processing material so that its function can be exhibited simultaneously with the development. Examples of the printout inhibitor include Japanese Patent Publication No. 54-1979.
No. 164, JP-A-53-46020 and JP-A-48-452.
No. 28, JP-B-57-8454, etc .; 1-phenyl-5-mercaptotetrazole compounds described in British Patent No. 1,005,144;
Viologen compounds described in JP-A-184936. The amount of the printout inhibitor used is 10 ^-4 to 1 mol / Ag mol, preferably 10 ^-3 to 10 ^-2 / Ag mol.

Further, physical development nuclei and halogen
A silver halide solvent and develop the photosensitive material
Silver genide may be solubilized and fixed to the treated layer. object
The reducing agent required for development is known in the field of photosensitive materials.
Can be used. It is itself reducing
But not reduced by the action of nucleophiles or heat during processing
It is also possible to use a reducing agent precursor that exhibits
You. As a reducing agent, photosensitive material diffused from photosensitive material
Developing agents that were not used for development
And the reducing agent is contained in the processing material in advance.
You may leave. In the latter case, include it in the processed material
The reducing agent may be the same as the reducing agent contained in the photosensitive material.
And may be different. Use a diffusion-resistant developing agent
If necessary, the electron transfer agent and / or
It may be used in combination with a precursor of an electron transfer agent.
No. The electron transfer agent or its precursor is
You can choose between the base agent or its precursor
You. When the reducing agent is added to the processing material, the amount added is 0.
01 to 10 g / m^TwoAnd preferably silver of the photosensitive material.
Is 1/10 to 5 times the number of moles. As a physical development nucleus
Means zinc, mercury, lead, cadmium, iron, chromium, nickel
Heavy metals such as tin, cobalt, copper, ruthenium, or
Is a precious metal such as palladium, platinum, gold, silver, or
Heavy metals, noble metals such as sulfur, selenium, tellurium, etc.
Uses all known compounds such as colloid particles
it can. The size of these physical development nuclei is 2 to 200 n.
Those having a particle size of m are preferably used. These physical manifestations
The image nucleus has 10^-3mg to 10 g / m ^TwoLet it be included
You.

Known silver halide solvents can be used. For example, thiosulfates, sulfites, thiocyanates, thioether compounds described in JP-B-47-11386, compounds having a 5- or 6-membered imide group such as uracil and hydantoin described in JP-A-8-179458, Compounds having a carbon-sulfur double bond described in Analytical Chem.
Mesoionic thiolate compounds such as trimethyltriazolium thiolate described in Nalytica Chinica Acta, 248, pp. 604-614 (1991) are preferably used. Further, compounds capable of fixing and stabilizing silver halide described in JP-A-8-69097 can also be used as a silver halide solvent.
It is also preferable to use a plurality of silver halide solvents in combination. In the processing layer, the content of the total silver halide solvent is 0.01 to 100 m
mol / m ² , preferably 0.1 to 50 mmol / m ² . The molar ratio is 1/20 to 20 times, preferably 1/10 to 10 times, more preferably 1/20 times the silver amount of the light-sensitive material.
4 to 4 times.

The processing material includes a protective layer as in the case of the photosensitive material,
There may be an undercoat layer, a back layer, and other various auxiliary layers. The processing material is preferably provided with a processing layer on a continuous web. The continuous web as used herein means that the length of the processing material is sufficiently longer than the corresponding long side of the photosensitive material at the time of processing. Having a length capable of processing the photosensitive material. Generally, it means that the length of the processing material is not less than 5 times and not more than 10000 times the width. The width of the processing material is arbitrary, but is preferably equal to or greater than the width of the corresponding photosensitive material. Further, a mode in which a plurality of photosensitive materials are processed in parallel, that is, a plurality of photosensitive materials are arranged and processed is also preferable. In this case, the width of the photosensitive material is preferably equal to or more than the width of the photosensitive material × the number of simultaneous processing. Such continuous web processing is preferably supplied from a delivery roll, wound up on a take-up roll and discarded. Particularly, in the case of a photosensitive material having a large size, disposal is easy. As mentioned above,
The handling material of the continuous web has significantly improved handling properties compared to conventional sheet materials.

The thickness of the support used in the processing material of the present invention is optional, but is preferably thin, particularly preferably 4 μm or more and 120 μm or less. It is preferred to use a processing material having a support thickness of 100 microns or less, more preferably 60 microns or less, especially 40 microns or less. In this case, the amount of the processing material per unit volume increases, so that the processing material roll can be made compact. The material of the support is not particularly limited, and a material that can withstand the processing temperature is used.
In general, the Photographic Society of Japan, "Basics of Photographic Engineering-Silver halide photography-", published by Corona Co., Ltd. (1979) (223-
240 pages) and photographic supports such as synthetic polymers (films). The material for the support can be used alone, or can be used as a support coated or laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, JP-A-62-2
53, 159 (29) to (31), JP-A-1-16
No. 1,236, pages (14) to (17), JP-A-63-31
No. 6,848, JP-A Nos. 2-22,651, 3-5
Supports described in US Pat. No. 6,955, US Pat. No. 5,001,033 and the like can be used. In addition, a support mainly composed of a styrene polymer having a syndiotactic structure can also be preferably used. A hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide, carbon black or other antistatic agents may be applied to the surface of these supports. A support on which aluminum is deposited can also be preferably used.

In the present invention, as a method for developing a photosensitive material photographed by a camera or the like, the amount required for maximally swelling the entire coating film excluding the back layer of both the photosensitive material and the processing material is 0.1 to 1 time. A method is preferred in which the photosensitive material and the processing material are overlapped with each other in the presence of the corresponding water so that the photosensitive layer and the processing layer face each other, and heated at a temperature of 60 ° C to 100 ° C for 5 seconds to 60 seconds. Any water may be used as long as it is generally used. Specifically, distilled water, ion exchange water, tap water, well water, mineral water, and the like can be used. A method in which a small amount of a preservative is added to these waters for the purpose of preventing generation of scale and decay, and circulating and filtering the water with an activated carbon filter, an ion exchange resin filter or the like is also preferably used. In the present invention, the photosensitive material and / or the processing material are stuck together in a state of being swollen with water and heated. The state of the film at the time of swelling is unstable, and it is important to limit the amount of water to the above range in order to prevent local uneven coloring. The amount of water required for maximum swelling is determined by immersing a photosensitive material or processing material with a coating film to be measured in the water used, measuring the film thickness when it swells sufficiently, and calculating the maximum swelling amount before applying. It can be determined by reducing the weight of the membrane. An example of a method for measuring the degree of swelling is also described in Photographic Science Engineering, Vol. 16, p. 449 (1972). Water can be applied to the photosensitive material, the processing material, or both. The amount used is an amount corresponding to 1/10 to 1 times the amount required for maximally swelling the entire coating film (excluding the back layer) of the photosensitive material and the processing material. The timing of applying water may be any point after exposing the photosensitive material to performing heat development.
Preferably, immediately before heat development is selected. The amount of water as defined in the present invention defines an amount required at the time when the photosensitive material and the processing material are bonded and heated and developed. Therefore, for example, a method of once supplying a larger amount of water than specified in the present invention to a photosensitive material or a processing material and then removing excess water by means of squeezing or the like until bonding, and performing heat development is also described in the present invention. It can be included in the scope of the invention. Usually, after the necessary amount of water is supplied to the photosensitive material or the processing material, or both, or after being adjusted to the required amount by the above-described means, the photosensitive material and the processing material are bonded and heated. Development is performed. After the photosensitive material and the processing material are bonded to each other, a necessary amount of water can be made to exist by supplying water to a gap between the two. Various methods can be used for the method of applying moisture. As a method of applying water,
There is a method in which a photosensitive material or a processing material is immersed in water and excess water is removed with a squeeze roller. However, it is preferable to apply a predetermined amount of water to the photosensitive material or the processing material in a completely coated manner. In addition, a plurality of nozzle holes for injecting water are arranged at regular intervals in a straight line or in a plurality of rows along a direction intersecting with the conveying direction of the photosensitive material or the processing material. A method of jetting water by a water application device similar to an ink jet recording head having an actuator for displacing the photosensitive material or the processing material toward the processing material is particularly preferable. In addition, a method of applying water with a sponge or the like is also preferable because the apparatus is simple. The temperature of the applied water is preferably 30C to 60C. Examples of a method of superposing a photosensitive material and a processing material are described in JP-A-62-253,159 and JP-A-61-253,159.
No. 147,244.

As a heating method in the developing step, a heating block or a plate is brought into contact, or a heating plate, a hot presser, a heating roller, a heating drum, a halogen lamp heater, an infrared and far-infrared lamp heater, or the like is contacted. Or passing through a high-temperature atmosphere.
Any of various heat developing apparatuses can be used in the processing of the present invention. For example, Japanese Unexamined Patent Publication Nos.
177,547, 59-181,353, 60
-18,951, Japanese Utility Model Application Laid-Open No. 62-25,944, Japanese Patent Application Nos. 4-277,517, 4-243,072, 4-244,693, and 6-164,421. 6
An apparatus described in JP-A-164,422 or the like is preferably used. As a commercially available device, a Pictrostat 100, a Pictrostat 200, a Pictrostat 300, a Pictrostat 330, a Pictrostat 50, a Pictography 3000, a Pictography 2000, and the like manufactured by Fuji Photo Film Co., Ltd. can be used. . The photosensitive material and / or processing material used in the present invention may have a form having a conductive heating element layer as a heating means for heat development. As the heat generating element of the present invention, those described in JP-A-61-145544 can be used.

In the present invention, image information can be taken in without removing developed silver and undeveloped silver halide generated by development, or an image can be taken after removal. In the latter case, a means for removing these at the same time as or after the development can be applied. At the same time as development, the developed silver in the photosensitive material is removed,
In order to complex or solubilize silver halide, the processing material should contain a silver oxidizing or rehalogenating agent that acts as a bleaching agent, or a silver halide solvent that acts as a fixing agent. These reactions can take place. After the development of the image is completed, a second material containing a silver oxidizing agent, a rehalogenating agent, or a silver halide solvent is attached to the photosensitive material to remove the developed silver or to complex the silver halide. Solubilization can also occur. In the present invention, it is preferable to perform these processes to such an extent that the image information is not obstructed after the photographing and the subsequent image formation and development. In particular, undeveloped silver halide causes a high haze in the gelatin film and raises the background density of the image. Therefore, the haze is reduced or solubilized by using a complexing agent as described above. It is preferable to remove the whole amount or a part of the total amount.

[0106]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In addition,
The structures of the metal complexes used in the examples are shown below.

[0107]

Embedded image

[0108] In the coordination number of the compound metal atom, ligands number of heterocyclic compounds ^{_{[Ru (trz) 6] 4-}} 6/6 [Fe (Im) 6] 2+ 6/6 [Zn (pz) 6 ] ²⁺ 6/6 [Fe (bpy) ₃ ] ²⁺ 6/6 (bidentate) [Ru (phen) ₃ ] ²⁺ 6/6 (bidentate) Example 1 (1) Emulsion Preparation Tabular silver iodobromide emulsion 1-A (comparative emulsion) (Preparation of seed crystal) Low molecular weight gelatin (molecular weight 15,000)
1600 cc of an aqueous solution containing 8.3 g and 4.3 g of KBr
Was stirred at 40 ° C., and 41 cc of a 1.2 M AgNO ₃ aqueous solution and 1.26 M K containing 4.3 mol% of KI were added.
41 cc of an aqueous Br solution was simultaneously added by a double jet for 40 seconds. 36 g of gelatin (lime-processed gelatin)
Was added, the temperature was raised to 58 ° C. in 20 minutes, the pAg was adjusted to 8.44, ammonia was added, the mixture was aged for 15 minutes, and then neutralized. Next, 647 cc of a 1.9 M AgNO ₃ aqueous solution and a 1.9 M KBr aqueous solution were added simultaneously for 55 minutes while accelerating the flow rate while maintaining the pAg at 8.10 (the flow rate at the end was 5 times that at the start). Thereafter, the emulsion was cooled to 35 ° C., washed with water by a conventional flocculation method, and dispersed by adding 49 g of gelatin to pH = 6.2.
It adjusted to pAg = 8.9 and stored. (Grain growth) 1145 cc of water and 36 g of gelatin (lime-processed gelatin) were added to 48 g of the seed crystal containing silver iodobromide equivalent to 9.3 g of AgNO ₃ , and the mixture was stirred at 75 ° C. and stirred at pH = 5. 5. Adjusted to pAg = 8.44. Thereafter, 479 cc of a 1.9 M AgNO ₃ aqueous solution and a 1.7 M KBr aqueous solution containing 2.7 mol% of KI were added to p.
Ag was maintained at 8.29 and the flow rate was accelerated (the flow rate at the end was 2.4 times that at the start), and was simultaneously added for 48 minutes. Further, 50 cc of a 1.9 M aqueous solution of AgNO ₃ and a 1.9 M aqueous solution of KBr were simultaneously added for 5 minutes while maintaining the pAg at 8.44. Thereafter, the temperature was lowered to 40 ° C. in 25 minutes, and 10.5 g of sodium P-iodoacetamidobenzenesulfonate (monohydrate) as an iodide ion releasing agent was added.
Then, 40 cc of a 0.8M aqueous sodium sulfite solution was added in a fixed amount for 1 minute to generate iodide ions while controlling the pH to 9.0.
The temperature was raised to C ゜ over 15 minutes, and then the pH was returned to 5.5. After this, sodium benzenethiosulfonate and K
₂ IrCl ₆ was 3.8 × 1 with respect to the total silver content of the grains.
Only 0 ^-6 mol / mol silver and 1 × 10 ^-8 mol / mol silver were added as a solution, and 269 cc of a 1.9 M AgNO ₃ aqueous solution was added.
And a 1.9 M aqueous KBr solution containing no dopant, p
Ag was kept at 8.59 and added simultaneously for 30 minutes in a fixed amount.

(Washing, dispersion) Thereafter, the emulsion was cooled to 35 ° C.
The mixture was cooled and washed with water by a conventional flocculation method, the pH was increased, and 75 g of gelatin (lime-treated gelatin) was added and dispersed, adjusted to pH = 5.8 and pAg = 8.8, and stored. The shape of the grains in the emulsion was determined by taking a transmission electron micrograph by a replica method and measuring 1000 grains (the same applies to the following emulsions 1-B to 1-H). As for the grains in the obtained emulsion, tabular grains accounted for 98% (number) of all grains.
The ratio of the projected area of tabular grains to the projected area of all grains exceeded 99% (the following emulsions 1-B to 1-B).
The same was true for 1-H). The average equivalent sphere equivalent diameter of all grains is 1.20 μm (emulsions 1-B to 1-
-H), the average equivalent circle diameter of all tabular grains is 1.
90 μm, average grain thickness of all tabular grains is 0.317 μm
m, and the average aspect ratio of all tabular grains was 6.0.
Further, dislocation lines were observed (introduction position, density, distribution) by a high-pressure type (acceleration voltage: 400 kV) electron microscope according to the method described in the text for 200 grains in the emulsion (sample tilt angle −10 for each grain).゜, -5 ゜, 0 ゜, +5
゜, + 10 ° were observed in five ways. Emulsion 1-B below
The same applies to 1-H). In the obtained emulsion, the ratio (number%) of tabular grains having 10 or more dislocation lines per grain substantially only in the fringe portion of the grains to all grains was 80% or more.

Tabular silver iodobromide emulsion 1-B (comparative emulsion) The emulsion was prepared in the same manner as the above emulsion 1-A, except for the following changes. In (grain growth) of emulsion 1-A, [Ru (trz) ₆ ] was used instead of the 1.9 M aqueous KBr solution containing no dopant.
^4- (trz = 1,2,4-triazole) is 1 to the total silver content of the grains.
1.9 cc of a 1.9 M AgNO ₃ aqueous solution was added simultaneously using a 1.9 M aqueous KBr solution containing only × 10 ⁻⁵ mol / mol silver. The grain shape, grain structure, halogen composition, dislocation lines and the like of the obtained grains were the same as those of Emulsion 1-A. Tabular silver iodobromide emulsion 1-C (comparative emulsion) Prepared similarly to Emulsion 1-A above, except for the following changes. 1.9 M Ag in Emulsion 1-A (Preparation of seed crystal)
647 cc of NO ₃ aqueous solution and 1.9 M KBr aqueous solution
Instead of keeping the pAg at 8.10, it was added at 8.58 while accelerating the flow. In the emulsion 1-A (grain growth), 479 cc of a 1.9 M AgNO ₃ aqueous solution was used.
And a 1.7 M KBr aqueous solution containing 2.7 mol% of KI,
Instead of keeping the pAg at 8.29, it was added at an accelerated flow rate of 8.58. The shape of the obtained grains was such that the average equivalent circle diameter of all tabular grains was 2.10 μm, the average grain thickness of all tabular grains was 0.260 μm, and the average aspect ratio of all tabular grains was 8.0. In the obtained emulsion, the ratio (number%) of tabular grains having 10 or more dislocation lines per grain substantially only in the fringe portion of the grains to all grains was 80% or more.

Tabular silver iodobromide emulsion 1-D (Emulsion of the present invention) The emulsion was prepared in the same manner as the above emulsion 1-A, except for the following changes. 1.9 M Ag in Emulsion 1-A (Preparation of seed crystal)
647 cc of NO ₃ aqueous solution and 1.9 M KBr aqueous solution
Instead of keeping the pAg at 8.10, it was added at 8.58 while accelerating the flow. In the emulsion 1-A (grain growth), 479 cc of a 1.9 M AgNO ₃ aqueous solution was used.
And a 1.7 M KBr aqueous solution containing 2.7 mol% of KI,
Instead of keeping the pAg at 8.29, it was added at an accelerated flow rate of 8.58. Further, in (grain growth) of emulsion 1-A, 1.9 M KB containing no dopant was used.
[Ru (trz) ₆ ] ^4- (trz = 1,2,4-triaz
ole) at 1.9 M in aqueous 1.9 M KBr solution containing only 1 × 10 ⁻⁵ mol / mol silver with respect to the total silver content of the grains.
269 cc of the gNO ₃ aqueous solution was added at the same time. The grain shape, grain structure, halogen composition, dislocation lines and the like of the obtained grains were the same as those of Emulsion 1-C.

Tabular silver iodobromide emulsion 1-E (comparative emulsion) (nucleation, grain growth) Low molecular weight gelatin (molecular weight: 10,000)
1,000) An aqueous solution 1200 containing 6.2 g and 6.4 g of KBr.
The mixture was stirred while keeping the cc at 35 ° C., and 0.1M AgNO
43cc of ₃ aqueous solution and 43cc of 0.1M KBr aqueous solution were simultaneously added by a double jet for 5 seconds. Thereafter, 38 g of gelatin (lime-processed gelatin) was added, the temperature was raised to 75 ° C. in 35 minutes, and aging was performed for 15 minutes. Next, 608 cc of a 1.9 M AgNO ₃ aqueous solution and a 1.9 M KBr aqueous solution containing 1 mol% of KI, and pAg of 8.07
While the flow rate was accelerated (the flow rate at the end was 11 times that at the start), and the mixture was added at the same time for 100 minutes. Thereafter, the temperature was lowered to 40 ° C. for 25 minutes, and an aqueous solution containing 12.7 g of sodium P-iodoacetamidobenzenesulfonate (monohydrate) as an iodide ion releasing agent was added. Was added in a fixed amount for 1 minute to generate iodide ions while controlling the pH to 9.0. After 2 minutes, the temperature was raised to 55 ° C. over 15 minutes, and then the pH was returned to 5.5. Thereafter, sodium benzenethiosulfonate and K ₂ IrCl ₆ were added in a solution of 3.8 × 10 ⁻⁶ mol / mol silver and 1 × 10 ⁻⁸ mol / mol silver, respectively, based on the total silver content of the grains, Further, 100 cc of an aqueous solution containing 12 g of gelatin (lime-processed gelatin) was added, and then 269 cc of a 1.9 M aqueous solution of AgNO ₃ and a 1.9 M aqueous solution of KBr containing no dopant were added at a pAg of 8.8.
It was added at the same time for 30 minutes in a fixed amount while keeping the value at 59.

(Washing and Dispersion) Water washing and dispersion were carried out in the same manner as in Emulsion 1-A. The obtained particles will be described in detail.
The grains in the obtained emulsion were tabular grains having an aspect ratio of 8 or more at 98% or more of the projected area of all the grains. The proportion of hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.2 to 1 accounted for 80% or more of the projected area of all grains in the emulsion. The average equivalent circle equivalent diameter of all tabular grains is 2.52 μm, and the average grain thickness of all tabular grains is 0.1
The average aspect ratio of all tabular grains was 14.0 μm. The coefficient of variation of the equivalent sphere equivalent diameter distribution of all particles is 11
%, The coefficient of variation of the equivalent circle equivalent diameter distribution of all tabular grains is 12
%, And the coefficient of variation of the grain thickness distribution of all tabular grains was 12%. EPMA described in European Patent No. 147,868 and the like
The coefficient of variation of the silver iodide content distribution among grains measured for 200 grains by the method using was 11%. In the obtained emulsion, the ratio (number%) of tabular grains having 30 or more dislocation lines per grain in only the grain fringe portion to all grains was 80% or more.
The silver iodide content distribution in the grains of 20 grains was measured at an electron beam spot interval of 50 nm by the method using an analytical electron microscope described in JP-A-7-219102. .15 μm, the average silver iodide content at the center of the grains was 1.0 mol%, and the average silver iodide content at the fringe portions of the grains was 5.5 mol%. T.Tani,
When the area ratio of the emulsion grain surface obtained by the method described in J. Imaging Sci., 29, 165 (1985) was measured, the ratio of the {100} plane to the {111} plane was 4.4%. . In addition, determined by the method described in JP-A-8-334850,
The ratio to the {100} plane at the edge of the tabular grain is 36.
%Met. Tabular silver iodobromide emulsion 1-F (emulsion of the present invention) Prepared similarly to emulsion 1-E described above, except for the following changes. In the emulsion 1-E (nucleation, grain growth), instead of the 1.9 M aqueous KBr solution containing no dopant, [Ru (tr
z) ₆ ] ^4- (trz = 1,2,4-triazole) at a concentration of 1.9 M using a 1.9 M aqueous KBr solution containing only 1 × 10 ⁻⁵ mol / mol silver with respect to the total silver content of the grains. 269 cc of the AgNO ₃ aqueous solution was added at the same time. The grain shape, grain structure, halogen composition, dislocation lines and the like of the obtained grains were the same as those of Emulsion 1-E. FIG. 1 shows a transmission electron micrograph of tabular silver iodobromide grains of Emulsion 1-F of the present invention.

Tabular silver iodobromide emulsion 1-G (comparative emulsion) Prepared similarly to Emulsion 1-E above, except for the following changes. In emulsion 1-E (nucleation, grain growth), gelatin 3
Instead of adding 8 g (lime-processed gelatin), 45 g of gelatin treated with trimellitic acid was added. Also, 1.
608 cc of a 9M AgNO ₃ aqueous solution and a 1.9 M KBr aqueous solution containing 1 mol% of KI were simultaneously maintained at 8.50 while maintaining the pAg at 8.07 while simultaneously accelerating the flow rate to 10%.
Added for 0 minutes. In the shape of the obtained grains, the average equivalent circle diameter of all tabular grains was 3.02 μm, the average grain thickness of all tabular grains was 0.126 μm, and the average aspect ratio of all tabular grains was 24.0. In the obtained emulsion, the ratio (number%) of tabular grains having at least 10 dislocation lines per grain substantially only in the fringe portion of the grains occupied 60% or more of all grains.

Tabular silver iodobromide emulsion 1-H (inventive emulsion) The emulsion was prepared in the same manner as the above emulsion 1-E, except for the following changes. milk
In agent 1-E (nucleation, grain growth), gelatin 3
Instead of adding 8 g (lime-processed gelatin),
45 g of gelatin treated with citrate was added. Also, 1.
9M AgNO_ThreeContains 608 cc of an aqueous solution and 1 mol% of KI
The 1.9 M KBr aqueous solution is maintained at a pAg of 8.07.
Instead, keep the rate at 8.50 and accelerate the flow rate at the same time
Added for 0 minutes. In addition, 1.9 without dopants
Instead of the aqueous KBr solution of M, [Ru (trz) ₆]^Four-(Trz = 1,
2,4-triazole) is 1 × 10^-FiveMole
Using a 1.9 M aqueous KBr solution containing only silver / mole silver.
9M AgNO_Three269 cc of the aqueous solution was added at the same time.
The particle shape, particle structure and halogen composition of the obtained particles
Emulsion 1-G. In addition, the resulting emulsion
10 particles per particle substantially only in the particle fringe portion
Tabular grains having the above dislocation lines account for all grains
The ratio (number%) was 75% or more.

(2) Chemical sensitization For emulsions 1-A to 1-H, 56 ° C., pH = 5.8, p
Under the condition of Ag = 8.4, the following red-sensitive spectral sensitizing dyes I, II and III are used as the spectral sensitizing dyes in the red-sensitive emulsion, and the green-sensitive spectral sensitizing dyes IV, V and VI are used in the green-sensitive emulsion. After adding the blue-sensitive sensitizing dye VII to the blue-sensitive emulsion, a mixed solution of potassium thiocyanate and chloroauric acid is added, and then sodium thiosulfate, the following selenium sensitizer and the following compound I are added, and spectral sensitization is performed. And chemical sensitization. The termination of chemical sensitization was performed using the following mercapto compounds. At this time, the amounts of the spectral sensitizing dye and the chemical sensitizer were adjusted so that the sensitivity of the emulsion at 1/100 second exposure was maximized. The sensitivity mentioned here is a logarithmic value of a reciprocal of an exposure amount giving a density of fog + 0.15 on a characteristic curve obtained when the photosensitive material is exposed and developed as described later. These emulsions were represented by subscripts r, g, and b according to the spectral sensitizing dyes used, as shown in the following table.

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

(3) Preparation of dispersion and coated sample and evaluation thereof <Method of preparing zinc hydroxide dispersion (for fifth and twelfth layers)>
A dispersion of zinc hydroxide used as a base precursor was prepared. 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm, 1.6 g of carboxymethylcellulose and 0.4 g of sodium polyacrylate as a dispersant, 8.5 g of lime-treated ossein gelatin, and 158.5 ml of water were mixed. This mixture was dispersed in a mill using glass beads for 1 hour. After the dispersion, the glass beads were separated by filtration to obtain 188 g of a dispersion of zinc hydroxide.

<Method for Preparing Emulsified Dispersion of Developing Agent and Coupler> (1) Emulsified Dispersion of Developing Agent and Yellow Coupler 10 g of yellow coupler YC-1, developing agent (1)
8.2 g, 1.6 g of the developing agent (2), 21 g of the high boiling point organic solvent (1) and 50.0 ml of ethyl acetate were dissolved at 60 ° C. (Solution II). In 170 g of an aqueous solution (solution I) in which 12 g of lime-processed gelatin and 1 g of surfactant (1) are dissolved
Solution II was mixed, and 10,000
The mixture was emulsified and dispersed for 20 minutes by rotation. After dispersion, the total amount is 3
Then, add distilled water to make the amount of water to 100 g
Mix for minutes.

[0122]

Embedded image

(2) Emulsified dispersion of developing agent and magenta coupler 7.5 g of each of magenta couplers MC-1 and MC-2,
8.2 g of developing agent (3), 1.05 g of developing agent (2),
11 g of high-boiling organic solvent (1) and ethyl acetate 24.0
ml was dissolved at 60 ° C. (Solution II). Lime-treated gelatin 12
(g) and an aqueous solution (I) in which 1 g of the surfactant (1) is dissolved.
Solution II) was mixed in 170 g, and emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver stirrer.
After dispersion, distilled water was added so that the total amount became 300 g, and 2
Mixing at 000 rpm for 10 minutes.

[0124]

Embedded image

(3) Emulsified dispersion of developing agent and cyan coupler 10.7 g of cyan coupler CC-1, developing agent (3)
8.2 g, developing agent (2) 1.05 g, high boiling point organic solvent (1) 11 g and ethyl acetate 24.0 ml were dissolved at 60 ° C. (solution II). In 170 g of an aqueous solution (solution I) in which 12 g of lime-processed gelatin and 1 g of surfactant (1) are dissolved
Solution II was mixed, and 10,000
The mixture was emulsified and dispersed for 20 minutes by rotation. After dispersion, the total amount is 3
Then, add distilled water to make the amount of water to 100 g
Mix for minutes.

[0126]

Embedded image

<Method for Preparing Dye Dispersion for Yellow Filter, Magenta Filter and Antihalation Layer> (1) 14 g of dye dispersion YF-1 for yellow filter layer and 13 g of high boiling organic solvent (2) were weighed, and acetic acid was added. Ethyl was added, and the mixture was heated and dissolved at about 60 ° C. to form a uniform solution. Surfactant (1) was added in an amount of 1.0 g to 100 cc of this solution, and lime-treated gelatin heated to about 60 ° C.
190 cc of a 6% aqueous solution was added, and the mixture was dispersed with a homogenizer at 10,000 rpm for 10 minutes. (2) Dye dispersion for magenta filter layer 13 g of MF-1 and 13 g of high-boiling organic solvent (2) were weighed, ethyl acetate was added, and the mixture was dissolved by heating at about 60 ° C. to form a uniform solution. , Surfactant (1)
Was added to a 6.6% aqueous solution of lime-treated gelatin heated to about 60 ° C.
Dispersed at 10,000 rpm for 1 minute. (3) Dye Dispersion for Antihalation Layer 20 g of CF-1 and 15 g of the high boiling organic solvent (1) were weighed, ethyl acetate was added, and the mixture was dissolved by heating at about 60 ° C. to form a uniform solution. , Surfactant (1)
Was added to a 6.6% aqueous solution of lime-treated gelatin heated to about 60 ° C.
Dispersed at 10,000 rpm for 1 minute.

[0128]

Embedded image

These dispersions and the previously prepared silver halide emulsion were combined, and the coating solutions of the respective layers were coated on a support in the composition shown in Tables 1, 2 and 3 to obtain samples 101 to 108.
A photographic light-sensitive material having a color multilayer structure was prepared. Table 4 shows emulsions A to D of other color forming layers. These emulsions
It was prepared by the tabular grain formation method described in the text of the present specification, and the grain size and aspect ratio were adjusted. Spectral sensitization and chemical sensitization were performed in the same manner as in the examples of the present invention. The sample thus prepared was stored at 25 ° C. and a relative humidity of 65% for 7 days and then cut.

[0130]

[Table 1]

[0131]

[Table 2]

[0132]

[Table 3]

[0133]

[Table 4]

[0134]

Embedded image

Next, the processing materials P-
1, P-2 were prepared.

[0136]

[Table 5]

[0137]

[Table 6]

[0138]

Embedded image

<Evaluation> The photosensitive materials of Samples 101 to 108 were exposed to 500 lux at 1/100 second via an optical wedge. The exposed surface of the photosensitive material is exposed to hot water of 40 ° C. for 15 minutes.
After applying ml / m ² , the processing material P-1 and the respective film surfaces were overlapped with each other, and then heat-developed at 83 ° C. for 17 seconds using a heat drum. When the photosensitive material was peeled off after the processing, a gray wedge-shaped image was obtained. The sample exposed using the blue filter has a wedge-shaped image of yellow color, and the sample exposed using the green filter has a wedge-shaped image of magenta color.
In the sample exposed using the red filter, a wedge-shaped image of cyan color was obtained. For these gray color samples,
The processing of the second step (fixing processing) was performed using the processing material P-2. The processing of the second step is to apply 10cc
/ M ² of water and adhered to the processing material P-2, 6
Heated at 0 ° C. for 30 seconds. The transmission densities of the color samples thus obtained were measured with blue, green and red filters to obtain a so-called characteristic curve. For each characteristic curve, the reciprocal value of the exposure corresponding to the density 0.15 higher than the fog density was used to determine the value as the relative sensitivity, and the average value of the relative sensitivities of the three colors was calculated. Sensitivity. The sensitivity was expressed as a relative value with the value of sample 101 taken as 100. Regarding the change in gradation (gamma) at the time of high illuminance exposure, exposure was performed for 1/100 seconds and 1 / 10,000 seconds (the exposure amount was the same) in the same manner as described above.
For the color characteristic curve, the fog density is 0.1 and 0.1.
The values were determined as relative gamma using the slope of a straight line connecting two points indicating 8 higher densities, and the average value of the relative gamma of the three colors was determined. Furthermore, 1 /
The gamma value at the time of 1 / 10,000 second exposure with respect to the gamma value at the time of 100 second exposure was expressed as a relative value, and the gradation change at the time of high illuminance exposure was determined. As relative values). In order to further compare with the conventional liquid development, after exposing each sample as described above,
The film was processed under the development conditions of 38 ° C. and 185 seconds using the processing CN-16 for color negative film manufactured by Fuji Photo Film Co., Ltd., and the sensitivity and the gradation change at the time of high illuminance exposure were determined as described above. Table 7 shows the results.

[0140]

[Table 7]

As is apparent from the results, tabular grains having a large average equivalent circle equivalent diameter are used without doping a metal complex having more than half of the coordination numbers of metal atoms as ligands. In particular, softening during high illuminance exposure during thermal development is remarkable. However, it can be seen that these points can be remarkably improved at the time of thermal development by using the emulsion of the present invention containing a metal complex having more than half the number of coordination numbers of metal atoms as ligands. . This improvement effect is an effect that is uniquely recognized in a system in which a photosensitive material containing a developing agent is thermally developed, and is a novel one that is not expected from conventionally known techniques. Thus, according to the present invention, a silver halide color photographic light-sensitive material having a high sensitivity and an appropriate gradation can be obtained even when the processing is carried out simply and quickly and with less environmental load.

Example 2 In Example 1, a sample was prepared and tested in the same manner as in Example 1 except that the following emulsion preparation was changed. Good results were obtained. The effect was confirmed. In the emulsions 1-B, 1-D, 1-F and 1-H, [Ru (trz) ₆ ]
^4- (trz = 1,2,4-triazole) is 1 to the total silver content of the grains.
[Fe (Im) ₆ ] ²⁺ (im = imidazole), [Zn (pz) ₆ ] instead of a 1.9 M aqueous KBr solution containing only × 10 ⁻⁵ mol / mol silver
²⁺ (pz = pyrazole), [Fe (bpy) ₃ ] ²⁺ (bpy = 2,2'-bipyridi
ne) and [Ru (phen) ₃ ] ²⁺ (phen = 1,10 phenanthroline), respectively, using a 1.9 M aqueous KBr solution containing only 1 × 10 ⁻⁵ mol / mol silver with respect to the total silver content of the grains. .9M AgN
It was added simultaneously with 269 cc of an O ₃ aqueous solution. For comparison, instead of the above [Fe (bpy) ₃ ] ^2+, a compound in which the number of heterocyclic compounds coordinated to an Fe atom is reduced from three to two ((a) below) is [Ru (Trz) ₆ ] Even when used in Example 1 in an equimolar amount instead of ^4- , the same good results were obtained and the effect of the present invention was confirmed. On the other hand, [Fe
In (bpy) ₃ ] ²⁺ , a comparative compound ((b) below) in which the number of heterocyclic compounds coordinated to an Fe atom is reduced from three to one is [Ru (trz) ₆ ] ^4- When an equimolar amount was used in Example 1 instead, the sensitization was not obtained, but rather the sensitization was lowered, and the effect of the present invention could not be realized.

[0143]

Embedded image

Example 3 A sample was prepared in the same manner as in Example 1 except that the support was replaced with the support manufactured by the following method. Further, a test similar to that of Example 1 was performed, but similarly good results were obtained, and the effect of the present invention was confirmed. 1) Support The support used in this example was produced by the following method. Polyethylene-2,6-naphthalate polymer 1
00 parts by weight and Tinuvin P. 326 (Ciba
After drying 2 parts by weight of Geigy Ciba-Geigy, 3
After being melted at 00 ° C., it was extruded from a T-die, stretched 3.3 times at 140 ° C., stretched 3.3 times at 130 ° C., and heat-set at 250 ° C. for 6 seconds. Thus, a PEN film having a thickness of 90 μm was obtained. The PEN film has a blue dye, a magenta dye and a yellow dye (public technical report: I-1, I-4,
I-6, I-24, I-26, I-27, II-5) were added in appropriate amounts. further,
Wound around a 20 cm diameter stainless steel core, 110
A heat history of 48 ° C. for 48 hours was given to make the support less likely to have curl.

2) Coating of Undercoat Layer The support was provided on both sides with corona discharge treatment and UV discharge treatment.
After the glow discharge treatment, each component in the undercoat layer
The weight per unit area of each is 0.1 g of gelatin
/ M^Two, Sodium α-sulfodi-2-ethylhexylsa
Succinate 0.01 g / m^Two, Salicylic acid 0.04 g /
m^Two, 0.2 g / m of p-chlorophenol ^Two, (CH_Two=
CHSO_TwoCH_TwoCH_TwoNHCO)_TwoCH_Two0.012g /
m^Two, Polyamide-epichlorohydrin polycondensate 0.0
2g / m^Two(10cc / m^Two, Barco
And an undercoat layer was provided on the high temperature side during stretching. Dry
Was carried out at 115 ° C for 6 minutes.
The temperature of all the feeding devices is 115 ° C). 3) Coating of back layer The following set as the back layer is formed on one side of the support after the undercoat.
Coating, an antistatic layer, a transparent magnetic recording layer and a slip layer.
Was. 3-1) Coating of antistatic layer Each component in the antistatic layer has a weight per unit area.
Tin oxide-antimony oxide having an average particle size of 0.005 μm
Dispersion of fine particle powder of composite (specific resistance is 5Ωcm)
(Secondary aggregate particle diameter of about 0.08 μm)
m^Two, Gelatin 0.05g / m^Two, (CH_Two= CHSO_TwoC
H_TwoCH_TwoNHCO)_TwoCH_Two0.02 g / m^Two, Poly (heavy
Total 10) Oxyethylene-p-nonylphenol 0.
005 g / m ^TwoIt applied so that it might become.

3-2) Coating of Transparent Magnetic Recording Layer The weight per unit area of each component in the magnetic recording layer was 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight). ) -Coated cobalt-γ-iron oxide (specific surface area 43 m ² / g, major axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 emu)
/ G, Fe ^{+ 2} / Fe ⁺³ = 6/94, surface treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06
g / m ² to diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was carried out with an open kneader and a sand mill),
C ₂ H ₅ C (CH ₂ CONH—C ₆ H ₃ (C
0.3 g / m ² of H ₃ ) NCO) ₃ was applied with a bar coater using acetone, methyl ethyl ketone, cyclohexanone, and dibutyl phthalate as a solvent, and a film thickness of 1.2
A μm magnetic recording layer was obtained. C ₆ H ₁₃ CH as slip agent
In propyloxy trimethoxysilane (15 _{wt%) - (OH) C 10} H 20 COOC 4 0 H 81 50mg / m 2, silica particles (1.0 .mu.m) 3- poly (polymerization degree: 15) as a matting agent polyoxyethylene The coated and coated abrasive aluminum oxide (0.20 μm and 1.0 μm) was added to 50
mg / m ² and 10 mg / m ² .
Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.). The X-light (blue filter) increases the DB color density of the magnetic recording layer by about 0.1, and the saturation magnetization moment of the magnetic recording layer is 4.2.
emu / g, coercive force 7.3 × 10 ⁴ A / m, squareness ratio 6
5%.

3-3) Preparation of Sliding Layer The weight per unit area of each component in the sliding layer is as follows:
Hydroxyethyl cellulose (25 mg / m ² ), C ₆ H
₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (6 mg /
m ² ) and 1.5 mg / m ^{2 of} silicone oil BYK-310 (manufactured by BYK Japan KK). The coating solution was prepared by mixing the above components in xylene / propylene glycol monomethyl ether (1/1) at 105 ° C.
And melt at room temperature with propylene monomethyl ether (10
), And further dispersed in acetone (average particle size: 0.01 μm). Drying is 1
The test was performed at 15 ° C. for 6 minutes (115 ° C. for all rollers and transport devices in the drying zone). The sliding layer has a dynamic friction coefficient of 0.10.
(5 mmφ stainless steel hard ball, load 100 g, speed 6 cm / min), static friction coefficient 0.08 (clip method), and dynamic friction coefficient between the emulsion surface and the sliding layer were 0.15, which were excellent characteristics.

[0148]

According to the silver halide photographic emulsion of the present invention, excellent photographic characteristics with a small change in gradation at the time of high illuminance exposure can be obtained while having high sensitivity. Therefore, according to the color photographic light-sensitive material using the silver halide photographic emulsion, it is possible to realize a color image formation simply and quickly and with less environmental load.

[Brief description of the drawings]

FIG. 1 is an electron micrograph showing the shape of tabular grains in a photographic emulsion of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 7/392 G03C 7/392 Z 7/407 7/407 7/46 7/46

Claims (11)

[Claims] 1. Among the included silver halide grains, all tabular grains have an average equivalent circle diameter of 2.0 to 4.0 μm, and the number of the grains exceeds half the coordination number of metal atoms. It is characterized in that it contains one or more metal complexes having a heterocyclic compound (when the heterocyclic compound is a chelate compound, the number of coordinating atoms is the number of heterocyclic compounds) as a ligand. Silver halide photographic emulsion. 2. The average equivalent circle diameter of all tabular grains is 2.
2. A silver halide color photographic emulsion according to claim 1, wherein said emulsion has a thickness of 5 to 4.0 .mu.m. 3. The average equivalent circle diameter of all tabular grains is 3.
2. The silver halide color photographic emulsion according to claim 1, wherein the thickness is 0 to 4.0 [mu] m or less. 4. The metal complex contained as a central metal is magnesium, calcium, strontium, barium, iron, cobalt, nickel, ruthenium, rhodium,
4. The silver halide photographic emulsion according to claim 1, which is a complex containing palladium, osmium, iridium, platinum, zinc, cadmium or mercury. 5. The silver halide photographic emulsion according to claim 1, wherein the average aspect ratio of all tabular grains is 8 to 40. 6. The silver halide emulsion is an emulsion wherein tabular grains containing 10 or more dislocation lines per grain substantially only in the fringe portion of the grains occupy 100 to 50% (number) of all grains. The silver halide photographic emulsion according to any one of claims 1 to 5, wherein 7. A silver halide photographic light-sensitive material comprising a silver halide photographic emulsion according to claim 1 on a support. 8. A silver halide color photographic light-sensitive material according to claim 7, comprising a compound which forms a dye by a coupling reaction with a developing agent and an oxidized form of the developing agent. 9. The developing agent according to the following general formulas (1) to (4):
9. The silver halide color photographic light-sensitive material according to claim 8, which is at least one compound selected from the group consisting of: Embedded image Embedded image Embedded image Embedded image In the formula, R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group. Group, arylthio group, alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group,
Alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, alkylcarbonyl group,
Represents an arylcarbonyl group or an acyloxy group;
₅ represents an alkyl group, an aryl group or a heterocyclic group. Z
Represents a group of atoms forming an aromatic ring (including a heteroaromatic ring). When Z is a benzene ring, the total value of Hammett constant (σ) of the substituent is 1 or more. R ₆ represents an alkyl group. X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom. R ₇ and R ₈ represent a hydrogen atom or a substituent;
₇ and R ₈ may combine with each other to form a double bond or a ring. Further, each of the general formulas (1) to (4) contains at least one ballast group having 8 or more carbon atoms in order to impart oil solubility to the molecule. 10. After exposing the light-sensitive material, a processing material comprising a support and a constituent layer containing a processing layer containing a base and / or a base precursor, and a back layer of both the light-sensitive material and the processing material are coated on the support. After supplying water equivalent to 1/10 to 1 times the total amount of water required for the maximum swelling of all the coating films except for the photosensitive layer surface of the photosensitive material or the processing layer surface of the processing material, the photosensitive layer surface of the photosensitive material and the processing material 10. The silver halide color according to claim 8 or 9, wherein an image can be formed by heating the layers at a temperature of 60C or more and 100C or less and for 5 seconds or more and 60 seconds or less. Photosensitive material. 11. A processing material comprising a support layer and a processing layer containing a processing layer containing a base and / or a base precursor coated on the support after imagewise exposing the light-sensitive material according to claim 8, 9 or 10; The total amount of water required for the maximum swelling of all coating films excluding the back layer of both the photosensitive material and the processing material is 1 /
After supplying water equivalent to 10 to 1 times to the photosensitive layer surface of the photosensitive material or the processing layer surface of the processing material, the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material are brought into close contact with each other and overlapped.
A color image forming method in which an image is formed in a photosensitive material by heating at a temperature of not less than 100 ° C. and not more than 5 seconds and not more than 60 seconds.