JPH11295836A - Silver halide color photographic sensitive material and its developing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the color photographic sensitive material capable of forming an image in an easy and rapid process small in load to the environment and capable of forming an image high in sensitivity and good in the characteristics in low illuminance reciprocity law failure. SOLUTION: The photosensitive material is formed by coating a support with at least one photosensitive silver halide emulsion layer containing a photosensitive silver halide emulsion and a color developing agent and a coupler, and a nonphotosensitive layer, and at least one kind of emulsion contains silver halide grains having silver halide phase containing silver iodide formed by releasing iodide ions from an iodide ion releasing agent during forming silver halide grains, and the total flat silver halide grains in the silver halide grains have an average aspect ratio of 2-50 and an average grain thickness of 0.05-0.3 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silver halide color photographic material for recording an image (hereinafter sometimes simply referred to as "photosensitive material") and a developing method thereof.

[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 quantities 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, an APS system based on a new concept 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 beyond the conventional way of enjoying photographs is becoming familiar.

[0003] The principle of color photography that is currently widespread employs color reproduction by a subtractive color method. In a general color negative, a light-sensitive layer using a silver halide emulsion, which is a light-sensitive element having photosensitivity in the blue, green, and red regions, is provided on a transparent support. So-called color couplers for forming complementary colors of yellow, magenta and cyan dyes 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.

For 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, minilab systems incorporating this technology have also been announced. Under such circumstances, there is an increasing demand for a color negative image forming method that is simpler. First,
The processing bath for performing the color development, bleaching and fixing described above requires precise control of the composition and temperature thereof.
Requires specialized knowledge and skilled operation. 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 such a background, there is a demand for reducing the environmental load and improving simplicity by constructing a system that does not use a color developing agent or a bleaching agent used in current color image forming systems. Is growing more and more. In view of these viewpoints, many improved techniques have been proposed. For example, IS &T's 48th Annual Con
On page 180 of ference Proceedings, 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. Fuji Photo Film Co., Ltd. has provided a pictography system as a system that does not require a processing solution containing a color developing agent. This system supplies a small amount of water to a photosensitive material containing a base precursor,
A development reaction is caused by bonding to the image receiving member and heating. This method is environmentally advantageous in that the above-mentioned treatment bath is not used. However, since this method fixes the formed dye to the dye fixing layer and uses it for viewing as a dye image, development of a system that can be used as a recording material for photographing has been desired.
In particular, with the digital lab system that has developed rapidly in recent years,
There is an increasing need for a system and a recording medium for digitizing captured image information simply and quickly. For example, Fuji Photo Film Co., Ltd. Digital Lab System Frontier (input machine "High-speed scanner / image processing workstation" Scannrer & Image Processor SP-1000 and output machine "laser printer / paper processor" La
It would be expected that the performance of the system would be higher if the imaging negative of input information such as ser Processor LP-1000P could be processed more simply and quickly.

In response to such demands, there is a heat-development method as a photographic negative which can be processed simply, quickly and with less environmental load.
No. 0582 and the like. Since these systems are photographic materials, the silver halide emulsions used are required to have higher sensitivity. Further, high levels of demands have been made for improvements in the relationship between sensitivity and granularity, improvement in sharpness, and good reciprocity characteristics.

One of the techniques for sensitizing silver halide emulsions is to use tabular grains. In conventional liquid developing photographic systems, tabular grains have already been disclosed in US Pat.
No. 4,226, No. 4,439,520, No. 4,4
No. 14,310, No. 4,433,048, No. 4,
Nos. 414,306 and 4,459,353.
Nos. 9-99433, 62-209445, and the like disclose their production methods and use techniques, including an increase in sensitivity including an improvement in the efficiency of color sensitization by a sensitizing dye, an improvement in the sensitivity / granularity relationship,
Advantages such as improvement in sharpness and covering power due to specific optical properties of tabular grains are known, and it is desired to use silver halide tabular grains having a smaller grain thickness and a high aspect ratio.

A technique using tabular grains in a heat development system is disclosed in US Pat.
No. 48101, JP-A-61-77048, JP-A-62
-78555 and JP-A-62-79447. However, in view of the above, 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 quick image recording with a low environmental load, Examination of the use of grains revealed that tabular grain emulsions tended to suffer from low illuminance failure when used in the heat development method as compared with conventional liquid development, and in particular when the grain thickness was reduced, they became significantly worse and became a practical problem. I understood. Therefore, there has been a demand for a photographic material which can achieve both high sensitivity and good low illuminance reciprocity characteristics even if the processing is simple, quick and has a small load on the environment.

[0009]

As is apparent from the above description, a first object of the present invention is to provide a color photographic light-sensitive material capable of forming an image easily, quickly and with less environmental load. To provide. It is still another object of the present invention to provide an excellent color photographic light-sensitive material which has high sensitivity even with simple and rapid processing, and has good low illuminance reciprocity characteristics.

[0010]

The above objects of the present invention have been effectively achieved by the following present invention. That is, (1) at least one photosensitive material obtained by coating a support with at least one photosensitive silver halide emulsion layer containing a photosensitive silver halide emulsion, a color developing agent, and a coupler;
A silver halide emulsion is a tabular grain in which a silver halide phase containing silver iodide is formed by generating iodide ions from an iodide ion releasing agent during grain formation;
Further, all the tabular grains of the silver halide emulsion have an average aspect ratio of 2 to 50 and an average grain thickness of 0.05 to 0.05.
A silver halide color photographic light-sensitive material comprising silver halide tabular grains having a thickness of from 0.3 to 0.3 μm. (2) At least one photosensitive silver halide emulsion layer containing a light-sensitive silver halide emulsion and a dye-donating compound which releases or diffuses a diffusible dye corresponding to or inversely to silver development is coated on a support. In the light-sensitive material, at least one silver halide emulsion is formed of tabular grains having silver iodide-containing silver halide phases formed by generating iodide ions from an iodide ion releasing agent during grain formation. there are, all the tabular grains in the silver halide emulsion further has, to an average aspect ratio of 2 to a 50, the average grain thickness is 0.
A silver halide color photographic light-sensitive material comprising silver halide tabular grains having a size of from 0.05 to 0.3 μm. (3) The silver halide color photographic light-sensitive material as described in (1) or (2) above, wherein the average grain thickness of all tabular grains of the silver halide emulsion is 0.05 to 0.2 μm. (4) The silver halide color photographic light-sensitive material as described in (1) or (2) above, wherein the average grain thickness of all tabular grains of the silver halide emulsion is 0.05 to 0.15 μm. (5) 100 to 80 of all grains of the silver halide emulsion
% (Number) is occupied by silver halide tabular grains containing 10 or more dislocation lines per grain, wherein the silver halide photographic light-sensitive material according to any one of the above (1) to (4), material. (6) 100 to 50 of all grains of the silver halide emulsion
% (Number) is occupied by tabular silver halide grains containing 50 or more dislocation lines per grain, wherein the silver halide photographic light-sensitive material according to any one of the above (1) to (4), material.

(7) 10% of all grains of the silver halide emulsion
The silver halide according to the above (5) or (6), wherein 0 to 80% (number) is occupied by silver halide tabular grains in which dislocation lines are localized substantially only in the fringe portions of the grains. Photosensitive material. (8) 100 to 80 of all grains of the silver halide emulsion
% (Number) is occupied by silver halide tabular grains in which dislocation lines are localized substantially only at the apexes of the grains. . (9) The halogen according to any one of the above (1) to (8), wherein the variation coefficient of the silver iodide content distribution between grains of the silver halide emulsion is 3 to 20%. Silver halide photographic material. (10) The halogenation according to any one of the above (1) to (9), wherein the coefficient of variation of the equivalent circle equivalent diameter distribution of all tabular grains of the silver halide emulsion is 3 to 25%. Silver photographic photosensitive material. (11) The silver halide emulsion wherein the hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.5 to 1 occupy 100 to 70% of the projected area of all grains. The silver halide photographic material as described in any one of (1) to (9) above, wherein (12) The tabular grain of the silver halide emulsion as described in any one of (1) to (11) above, wherein the tabular grains contain one or more kinds of photographically useful metal ions or complexes in the grains. Silver halide photographic material. (13) The silver halide photographic material as described in any one of (1) to (12) above, wherein the iodide ion releasing agent is represented by the following general formula (1).

[0012]

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In the formula (1), R represents a monovalent organic residue which releases an iodine atom in the form of an iodide ion by reaction with a base and / or a nucleophile. (14) The silver halide photographic material as described in any one of (1) to (13) above, wherein the iodide ion releasing agent is used in the presence of an iodide ion releasing regulator.

(15) The developing agent is represented by the following general formula (2):
The silver halide color photographic light-sensitive material according to any one of (1) to (14), which is at least one compound of the compounds represented by (6).

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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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,
Aryloxy group, alkylthio 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, and R ₅ represents a substituted or unsubstituted 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 a benzene ring, the total value of Hammett constant (σ) of the substituent is 1
That is all. R ₆ represents a substituted or unsubstituted 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, and R ₇ and R ₈ may combine with each other to form a double bond or a ring. (16) 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 whole 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 processing of the photosensitive layer surface of the photosensitive material and the processing of the processing material Laminate the layers and apply 60
The method for developing a photosensitive material according to any one of the above (1) to (15), wherein an image is formed by heating at a temperature of not less than 100 ° C. and not more than 5 seconds and not more than 60 seconds.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to construct a photosensitive material used for recording an original scene and reproducing it as a color image in the present invention, color reproduction by a subtractive color method can be basically used. 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 each having a complementary color with its own photosensitive wavelength region are provided in each photosensitive layer. The color information of the original scene can be recorded by incorporating a color coupler capable of forming a color image. The ornamental image 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.

It is also possible to provide a relationship other than the above-described complementary color 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. As the light-sensitive material of the present invention, a light-sensitive layer having photosensitivity in three or more wavelength regions can be provided.

In a color negative film used in conventional photography, a silver halide emulsion is not only improved to achieve a desired granularity, but also developed during a coupling reaction with an oxidized form of a developing agent. Techniques such as using so-called DIR couplers that release inhibitory compounds have been incorporated. In the photosensitive material of the present invention,
Excellent granularity is obtained even without using a DIR coupler. In addition, the combination of the DIR compounds results in increasingly better granularity.

The emulsion of the present invention will be described below. The silver halide emulsion of the present invention contains tabular grains. In the present invention, a tabular grain is a silver halide grain 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. This tabular grain, when viewed from above,
It has a triangular shape, a hexagonal shape, or a shape in which these corners are rounded. In the case of the hexagonal shape, opposing sides have outer surfaces parallel to each other. The twin plane spacing of the tabular grains of the present invention may be 0.012 μm or less as described in US Pat.
As described in No. 9585, the distance between the (111) 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%, particularly preferably 100 to 95%. When 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. The emulsion of the present invention has an adjacent side ratio (maximum side length /
It is preferable that hexagonal tabular grains having a minimum side length of 1.5 to 1 occupy 100 to 50% of the projected area of all grains in the emulsion. More preferably, 100 to 7
0%, particularly preferably 100-80%. 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 occupies 100 to 70%,
Particularly preferably, it accounts for 100 to 80%. Mixing of tabular grains other than the above hexagons is not preferred 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 0.05 to 0.2 μm, even more preferably from 0.05 to 0.15 μm. . The average grain thickness is the arithmetic average of the grain thickness 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 effects of the present invention, which is not preferable. The average equivalent circle diameter of the tabular grains of the present invention is preferably 0.5 to 5 μm, more preferably 0.8 to 4 μm, and particularly preferably 1.
It is 0 to 3 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 0.5 μm, it is difficult to obtain the effects of the present invention, which is not preferable. If the thickness exceeds 5 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 average aspect ratio of all tabular grains of 2 to 5
It is preferably 0, more preferably 5 to 4
0, more preferably 8 to 40, particularly preferably 1
2 to 40. The average aspect ratio is the arithmetic average of the aspect ratios of all tabular grains in the emulsion. If the average aspect ratio is less than 2, the advantages of tabular grains cannot be fully utilized, which is not preferable. Those with more than 50 are difficult to prepare.

The emulsion of the present invention is preferably monodisperse. In the emulsion of the present invention, the coefficient of variation of the equivalent circle equivalent diameter distribution of all tabular grains is preferably 35% or less, more preferably 25 to 3%, and particularly preferably 2 to 3%.
It is 0 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. If the variation coefficient of the equivalent circle equivalent diameter distribution of all tabular grains exceeds 35%, it is not preferable in terms of homogeneity between grains. Emulsions below 3% are difficult to prepare. In the present invention, the particle thickness and aspect ratio in the above range, the degree of monodispersion may be selected according to the purpose,
It is preferable to use monodisperse tabular grains having a small grain thickness and a high aspect ratio. Various methods can be used for forming tabular grains. For example, US Pat.
No. 494,789 or U.S. Pat. No. 5,496,694 can be used.

In order to form monodisperse tabular grains having a high aspect ratio, it is important to form twin nuclei of a small size in a short time. Therefore, low temperature, high pBr, low P
H, nucleation is preferably performed in a short time under a low gelatin content, and gelatin types such as low molecular weight, low methionine content, phthalated and trimellited are preferred. After nucleation, normal crystals, single twins and non-parallel multiple twins are eliminated by physical ripening,
Selectively leave parallel double twin nuclei. It is preferable to further ripen the remaining parallel double twin nuclei to increase the monodispersity. It is also preferable to carry out physical ripening in the presence of PAO (polyalkylene oxide) described in, for example, US Pat. No. 700,220 or US Pat. No. 5,147,771 for improving 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, those having a low methionine content, those having undergone phthalation and trimellitization, and the like are 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. In general, increasing the aspect ratio of tabular grains and increasing monodispersity cannot always be optimized by the same factors. At this time, it is not efficient to perform experiments on all combinations of many factors to find the optimum conditions, and it is often not easy due to interaction. In these cases,
By applying the Taguchi method, it is possible to efficiently optimize the factors and find stable (highly robust) conditions against various fluctuation factors. The Taguchi method is described in detail in Genichi Taguchi's book (eg, "Experimental Design Method").

In the present invention, enhancing the robustness of emulsion grain formation is preferred from the viewpoint of eliminating performance differences between emulsion batches and during scale-up. For example, the instability of grain formation due to the intensity of stirring and mixing in the reaction vessel may not reproduce photographic performance at the time of scale-up of the preparation, or may cause a difference in performance between emulsion batches due to accidental fluctuation. As will be described later, one of the intentions of using an iodide ion releasing agent at the time of forming emulsion grains of the present invention is to improve the robustness of emulsion grain formation.

In forming the emulsion silver halide grains 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. When the silver halide grains in the present invention have a phase containing iodide or chloride, these phases may be uniformly distributed or localized in the grains. Other silver salts, for example, silver rhodan, 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 80 mol% or more, more preferably 90 mol% or more. The preferred range of the silver iodide content of the emulsion grains in the present invention is from 1 to 2
0 mol%, more preferably 2 to 15 mol%,
Particularly preferably, it is 3 to 10 mol%. If it is less than 1 mol%, it is not preferable because effects such as enhancement of dye adsorption and increase in intrinsic sensitivity are hardly obtained. If it exceeds 20 mol%, the developing speed is generally slow, which is not preferable.

The variation coefficient of the silver iodide content distribution among the grains of the emulsion grains in the present invention is preferably 30% or less, more preferably 25 to 3%, and particularly preferably 20 to 3%. If it exceeds 30%, it is not preferable in terms of homogeneity between particles. The coefficient of variation of the silver iodide content distribution is a value obtained by dividing the standard deviation of the silver iodide content of each emulsion grain by the average silver iodide content between grains. 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 of the present invention comprises tabular grains in which a silver halide phase containing silver iodide is formed by generating iodide ions from an iodide ion releasing agent during grain formation. The present invention uses silver iodide while generating iodide ions from an iodide ion releasing agent in place of the conventional method of adding free iodide ions during epitaxial growth in the process of introducing dislocation lines into tabular grains described below. The effect of the present invention was remarkable when a silver halide phase was formed. That is, when tabular grains are used in a heat-developing silver halide color photographic light-sensitive material containing a color developing agent,
The present inventors have found that low illuminance failure is more likely to occur than in conventional liquid development, and particularly worse when the grain thickness is reduced, but unexpectedly good results can be obtained by using the emulsion of the present invention. Was.

The tabular grains in the present invention preferably have dislocation lines. Hereinafter, introduction of dislocation lines into tabular grains will be described in detail. A dislocation line is a slip plane on a crystal.
This is a linear lattice defect at the boundary between the already slipped area and the area that has not slipped yet. 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 observing dislocation lines directly using a transmission electron microscope, place the silver halide grains taken out of the emulsion with care not to apply enough pressure to generate dislocation lines on the grains, and place them on a mesh for electron microscope observation. 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, US Pat. No. 4,806,46
Nos. 1, 498, 516, 5, 496, 694, 5, 476, 760, 5, 567, 580, JP-A-4-149541 and JP-A-4-149737 describe silver halide grains. There is a description about a technology for controlling and introducing dislocation lines. Tabular grains with dislocation lines introduced in these patents are compared with tabular grains without dislocation lines,
It shows that it has excellent photographic characteristics such as sensitivity and pressure. 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%, particularly preferably from 0 to 10 mol%, but may be selected according to the purpose.
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 15 mol% of the silver quantity of the host grains. It is 10 mol%, 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 5 times the total grain silver amount as viewed from the grain formation.
It is preferably present in the range of 60 mol%, more preferably 10 to 50 mol%, particularly preferably 20 to 40 mol%.
In the range of 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 covered with the host grains or may be formed only in a specific portion. It is preferable to control the position of the dislocation lines within. In the present invention, it is particularly preferable to form the high silver iodide content phase at the edge or the apex 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, pAg, solvent concentration, gelatin concentration, ionic strength, etc. 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 the present invention, an iodide ion releasing agent, which will be described in detail later, is used in forming the high silver iodide content phase on the host grains. After the epitaxial growth is formed, dislocation lines are introduced when a silver halide shell is formed outside the host tabular grains. 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%, most preferably 0.1 to 3 mol%. If it is less than 0.1 mol%, it is difficult to obtain effects such as enhancement of dye adsorption and acceleration of development, which is not preferable. If it exceeds 12 mol%, the developing speed is undesirably slow. The amount of silver used for the silver halide shell growth is preferably from 10 to 50 mol%, more preferably from 20 to 40 mol%, of the total silver amount of the grains.

The preferred temperature in the above-mentioned dislocation line introduction step is 30 to 80 ° C., more preferably 35 to 75 ° C.
° C, particularly preferably 35 to 60 ° C. To control the temperature 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, the position and the 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 as described above.

When the tabular grains in the present invention have dislocation lines, their positions can be selected from, for example, those limited to the apexes and fringe parts of the grains or introduced over the entire main plane part. However, it is preferable to limit to a fringe portion or a vertex portion. 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, when the silver iodide content of the fringe portion or the apex portion of the grain is measured by the method described in JP-A-7-219102 using an analytical electron microscope, the silver iodide content of 2 mol% or more is measured. The formation of tabular grains having a silver 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, more preferably 5 mol% or more. For this purpose, it is preferable to form silver iodide-containing epitaxial growth on the host tabular grain substantially limited to the edge or top of the grain,
It is preferable to perform epitaxial growth using a method of releasing iodide ions from the silver iodide ion releasing agent of the present invention. If an iodide ion is supplied by adding an aqueous solution of potassium iodide, silver iodide is contained only at the edge or top of the grain because the grain grows in a highly supersaturated, non-uniform region generated near the addition port. It is difficult to perform epitaxial growth (deposition on a grain edge portion, a vertex portion, and a main plane). Also, if fine grains containing silver iodide prepared separately are added, if the added fine grains are to be dissolved, re-dissolution of the host grains and the silver iodide-containing phase deposited on the host during that time, Epitaxial growth is hardly observed at a specific part of the particle (mainly laminated on the main plane of the particle).

On the other hand, in the method using the iodide ion-releasing agent of the present invention, silver iodide is formed at the edge or top of the grain under the condition that the solubility of the host grains and the silver iodide-containing phase deposited on the host grains is low. Conditions are selected so that iodide ions can be released quickly and without locality while controlling with an iodide ion releasing agent. Therefore, the iodide ion supply method of the present invention realizes "uniform high supersaturation" which cannot be achieved by the conventional method, and forms uniform epitaxial growth within and between grains. The iodide ion release rate will be described later in detail. 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 grain fringe portion or the vertex is compared with the average silver iodide content in the grain central region. 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. In the present invention, the dislocation linear density introduced into tabular grains is 1
It can be selected depending on the case such as 10 or more, 30 or more, 50 or more per particle, but it is preferable to introduce dislocation lines at high density. If the dislocation lines are dense,
Alternatively, when dislocation lines are observed crossing each other, 1
The number of dislocation lines per grain may not be clearly enumerated. However, even in these cases, the number can be counted to about 10, 20, or 30. The silver halide grains of the present invention desirably have a uniform dislocation dose distribution between grains. In the present invention, 1
The 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 50 or more dislocation lines per grain preferably occupy 100 to 50% (number) of all grains, more preferably 100 to 80%. . The silver halide tabular grains of the present invention desirably have a uniform dislocation line introduction position in the grains. In the present invention, when dislocation lines are introduced into the grain fringe portions, the higher the proportion of silver halide tabular grains in which dislocation lines are substantially localized only in the grain fringe portions, the more preferable in terms of grain homogeneity. The emulsion preferably occupies 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, the area of the fringe portion of the tabular grains is preferably 0.02 to 0.2 μm, more preferably 0.05 to 0.15 μm.
m. In other ranges, it is difficult to increase the intrinsic sensitivity. In the present invention, when a dislocation line is introduced at the apex of the grain, the higher the proportion of silver halide tabular grains in which the dislocation line is substantially localized only at the apex of the grain, the more preferable in terms of grain homogeneity. 100 to 80% of all particles (number)
The emulsion preferably occupies 1% by weight, more preferably 1% by weight.
00 to 70%, more preferably 100 to 80
Account for%. In the present invention, when determining the ratio of the particles containing dislocation lines and the number of dislocation lines, it is preferable to obtain the dislocation lines by directly observing at least 100 particles,
More preferably 200 particles or more, particularly preferably 300 particles
Observe for more than particles.

Hereinafter, the iodide ion releasing agent used during grain formation in the present invention will be described in detail. In a liquid development photographic system, halogen ions (iodide ions) are used as a halogen ion source instead of the conventional halogen salt aqueous solution.
The shape and structure of the particles within and between the particles using the release agent,
With respect to the technology for forming silver halide grains having a uniform distribution of silver iodide content, Japanese Patent Publication No. 7-111549,
JP-A-5-341418, JP-A-5-346431, JP-A-5-323487, JP-A-6-11780, and JP-A-6-11
No. 781, No. 6-11782, No. 6-11784,
6-27564, 6-138595, 6-2
No. 30495, No. 6-242527, No. 6-25030
9, 6-250310, 6-250311,
6-250313, 6-258745, 6-2
No. 73876, No. 6-313933, No. 7-2191
02, 8-62754, 8-95181, U.S. Patent Nos. 5,389,508, 5,418,124
Nos. 5, 482, 826, 5, 496, 694
Nos. 5, 498, 516, 5, 580, 713
Nos. 5,527,664, and the like, which have known advantages such as an increase in sensitivity, an improvement in sensitivity / fog relation, and an improvement in pressure property.

The inventors of the present invention preferably carry out uniform chemical sensitization within and between individual silver halide grains in order to impart good reciprocity characteristics. Thinking that it is necessary to form silver halide particles,
When a silver halide emulsion formed by using an iodide ion releasing agent was applied to the silver halide color photographic light-sensitive material of the present invention, a remarkable improvement effect was observed, and the result was unexpected. Was. In the present invention, it is preferable to use an iodide ion releasing agent represented by the following formula (1) represented by Chemical Formula 13.

[0046]

Embedded image In the formula (1), R represents a monovalent organic residue which releases an iodine atom in the form of an iodide ion by reaction with a base and / or a nucleophile. When the compound represented by the formula (1) is described in more detail, R is, for example, 1 to 30 carbon atoms.
An alkyl group, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 3 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, A heterocyclic group having 4 to 30 carbon atoms,
An acyl group having 30 carbon atoms, a carbamoyl group, an alkyl or aryloxycarbonyl group having 2 to 30 carbon atoms,
Preferred are 30 alkyl or arylsulfonyl groups and sulfamoyl groups. R is preferably the above group having 20 or less carbon atoms, and particularly preferably the above group having 12 or less carbon atoms.
The number of carbon atoms is preferably in the above range from the viewpoint of solubility and the amount of addition.

Further, R is preferably substituted, and preferred substituents include the following.
The substituent may be further substituted with another substituent. For example, a halogen atom (eg, fluorine, chlorine, bromine, iodine), an alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl), an alkenyl group (eg, allyl) , 2-butenyl, 3-pentenyl), an alkynyl group (eg, propargyl, 3-pentynyl), an aralkyl group (eg, benzyl, phenethyl), an aryl group (eg, phenyl, naphthyl, 4-methylphenyl), a heterocyclic group ( For example, pyridyl, furyl, imidazolyl, piperidyl, morpholyl), alkoxy group (eg, methoxy, ethoxy, butoxy), aryloxy group (eg, phenoxy, naphthoxy), amino group (eg, unsubstituted amino, dimethylamino, ethylamino) ,
Anilino), acylamino group (eg, acetylamino, benzoylamino), ureido group (eg, unsubstituted ureido, N-methylureide, N-phenylureido), urethane group (eg, methoxycarbonylamino, phenoxycarbonylamino), sulfonyl An amino group (eg, methylsulfonylamino, phenylsulfonylamino), a sulfamoyl group (eg, sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl), a carbamoyl group (eg, carbamoyl,
Diethylcarbamoyl, phenylcarbamoyl), sulfonyl group (eg, methylsulfonyl, benzenesulfonyl), sulfinyl group (eg, methylsulfinyl, phenylsulfinyl), alkyloxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl group ( For example, phenoxycarbonyl), acyl group (eg, acetyl, benzoyl, formyl, pivaloyl), acyloxy group (eg, acetoxy, benzoyloxy), phosphoric amide group (eg, N, N-diethylphosphoramide), alkylthio group (Eg, methylthio, ethylthio), arylthio group (eg, phenylthio group), cyano group, sulfo group (including its salt), carboxyl group, hydroxy group,
A phosphono group and a nitro group.

More preferred substituents for R include a halogen atom, an alkyl group, an aryl group, a 5- or 6-membered heterocyclic group containing at least one O, N or S, an alkoxy group,
Aryloxy group, acylamino group, sulfamoyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, aryloxycarbonyl group, acyl group, sulfo group (including salts thereof), carboxyl group, hydroxy group and nitro group. A particularly preferred substituent of R is a hydroxy group, a carbamoyl group, a lower alkylsulfonyl group or a sulfo group (including a salt thereof) when substituting the alkylene group in R, and a substituting group for the phenylene group in R. A sulfo group (including a salt thereof).

Specific examples of the compound represented by the formula (1) of the present invention are shown below, but the compound of the present invention is not limited to these.

[0050]

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[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

The iodide ion releasing agent of the present invention can be synthesized according to the following synthesis method. J. Am. Chem.
Soc. , 76 , 3227-8 (1954); Or
g. Chem. , 16 , 798 (1951), Che.
m. Ber. , 97 , 390 (1964), Org. S
ynth. , V, 478 (1973); Chem.
Soc. , 1951 , 1851, J. Mol. Org. Che
m. , 19 , 1571 (1954); Chem. S
oc. , 1952 , 142; Chem. Soc. ,
1955 , 1383, Angew, Chem. , In
t. Ed. , 11 , 229 (1972), Chem. C
ommu. , 1971 , 1112.

The iodide ion releasing agent of the present invention releases iodide ions by reacting with an iodide ion release regulator (base and / or nucleophile). The nucleophile used in this case is preferably The following chemical species may be mentioned. For example, hydroxide ion, sulfite ion, hydroxylamine, thiosulfate ion, metabisulfite ion, hydroxamic acids, oximes, dihydroxybenzenes, mercaptans, sulfinates, carboxylates, ammonia, amines, Examples include alcohols, ureas, thioureas, phenols, hydrazines, hydrazides, semicarbazides, phosphines, and sulfides. In the present invention, the release rate and timing of iodide ions can be controlled by controlling the concentrations of bases and nucleophiles, the method of addition, and the temperature of the reaction solution. The base is preferably an alkali hydroxide.

The preferred concentration range of the iodide ion releasing agent and the iodide ion release controlling agent used for generating iodide ions is 1 × 10 ^{−7 to} 20 M, more preferably 1 × 10 ^{−5 to} 10 M, More preferably, 1 × 10 ^-4 or more
5M, particularly preferably 1 × 10 ^{−3 to} 2M. If the concentration is more than 20 M, the amount of the iodide ion releasing agent having a large molecular weight and the amount of the iodide ion releasing controlling agent to be added become too large with respect to the capacity of the particle forming container. Also,
If the concentration is less than 1 × 10 ⁻⁷ M, the reaction rate of releasing iodide ions becomes slow, and it is difficult to rapidly generate an iodide ion releasing agent, which is not preferable. The preferred temperature range is 30
To 80 ° C, more preferably 35 to 75 ° C, particularly preferably 35 to 60 ° C. When the temperature is higher than 80 ° C., the reaction rate of iodide ion release generally becomes extremely high, and when the temperature is lower than 30 ° C., the reaction rate of iodide ion release generally becomes extremely slow.

In the present invention, when a base is used for releasing iodide ions, a change in solution pH may be used. At this time, the preferable pH range for controlling the release rate and timing of iodide ions is 2 to 12,
The pH is more preferably from 3 to 11, particularly preferably from 5 to 10, and most preferably from 7.5 to 10.0. Even under neutral conditions at pH 7, hydroxide ions determined by the ionic product of water act as regulators. Further, a nucleophile and a base may be used in combination. At this time, the pH may be controlled within the above range, and the release rate and timing of iodide ions may be controlled.

The preferred range of the amount of iodide ions released from the iodide ion releasing agent is 0.1 to 20 mol%, more preferably 0.3 to 20 mol%, based on the total amount of silver halide.
15 mol%, particularly preferably 1 to 10 mol%,
You can choose according to your purpose. If it exceeds 20 mol%, the developing speed is generally slow, which is not preferable. When releasing iodine atoms in the form of iodide ions from an iodide ion releasing agent,
All iodine atoms may be released, or some may remain without being decomposed. The release rate of iodide ions from the iodide ion releasing agent will be described with specific examples. In the present invention, for example, in the process of introducing dislocation lines into tabular grains, forming a silver halide phase containing silver iodide at the edge of the tabular grains while rapidly generating iodide ions can reduce dislocation lines at a high density. It is preferable to introduce the If the supply rate of iodide ions is too slow, that is, if the time for forming a silver halide phase containing silver iodide is too long, the silver halide phase containing silver iodide is redissolved during that time, and the dislocation linear density Will decrease.

On the other hand, if the supply rate of iodide ions is too high, the dislocation dose distribution tends to be non-uniform within and between grains. Therefore, it is important to generate iodide ions rapidly and without locality (non-uniform distribution). The region where the locality of iodide ions is large is formed when an iodide ion releasing agent or an iodide ion release controlling agent used in combination with the iodide ion releasing agent is added to the reaction solution in the particle forming container. This is because the iodide ion release reaction is too fast for local concentration locality of the resulting additive. The time required for the released iodide ions to deposit on the host particles is extremely fast, and since the particle growth occurs in the region near the addition port where the iodide ion has a high locality, non-uniform particle growth within and between the particles occurs. Occur. Therefore, it is necessary to select an iodide ion release rate that does not cause locality of iodide ions. In the conventional method (for example, by adding an aqueous solution of potassium iodide), the iodide ions are added in a free state even if the aqueous solution of potassium iodide is diluted and added. There is a limit to trying to reduce it. That is,
In the conventional method, it was difficult to form particles without causing non-uniformity between particles.

According to the present invention, iodide ions can be released in a reaction solution for forming silver halide grains while controlling the release rate of the iodide ions. It is based on finding a way to reduce liability. According to this method, iodide ions can be generated rapidly and without causing locality in a reaction solution for forming silver halide grains, and the iodide ions can be generated more in the grains and between grains than in the conventional method. It has become possible to introduce dislocation lines homogeneously and at high density. That is, the method for supplying iodide ions in the formation of silver halide grains of the present invention comprises:
In other words, "Iodide Ion Controlled Rele
ase method (Controlled Release o
f Iodid Ion). " Controlled Release of Iodide Ion of the Present Invention
The se method is intended to eliminate instability in grain formation with respect to the intensity of stirring and mixing in the reaction vessel when dislocation lines are introduced into the tabular grains, to improve robustness of photographic performance, and to improve reproducibility of photographic performance at the time of scale-up. Was also effective.

In the present invention, the iodide ion release rate can be determined by controlling the temperature, the concentration of the iodide ion releasing agent and the concentration of the iodide ion release controlling agent as described above, and these conditions are determined according to the purpose. Can be selected appropriately. When the reaction for producing iodide ions from the iodide ion releasing agent of the present invention is represented by a secondary reaction which is substantially proportional to the iodide ion releasing agent concentration and the iodide ion releasing controlling agent concentration (water, 40 ° C), and in the present invention, the second order rate constant is preferably 1000 to 5 x 10
^-4 (M ^-1 · sec ^-1 ), more preferably 100 to 5 × 10 ^-3 (M ^-1 · sec ^-1 ), and even more preferably 10 to 5 × 10 ^-2 (M ^-1). · Sec ^-1 ), particularly preferably from 10 to 0.1 (M ^-1 · sec ^-1 ).

"Substantially the second order reaction" means that the correlation coefficient is 1.0 to 0.8. When the concentration of the iodide ion releasing agent is in the range of 10 ^-4 to 10 ^-5 M and the concentration of the iodide ion releasing agent is in the range of 10 ^-1 to 10 ^-4 M,
A typical second-order reaction rate constant k (M ⁻¹ · se) measured under conditions at 40 ° C. that can be regarded as a pseudo first-order reaction
c ^-1 ) are as follows. Compound No. Iodide ion release regulator k 11 Sulfite ion 1.3 1 hydroxide ion 1 × 10 ⁻³ or less 2 sulfite ion 0.29 58 Same as above 0.49 63 Same as above 1.522 hydroxide ion 720 k If it exceeds 1,000, the release is too early to control, and if it is less than 5 × 10 ^-4, it is too late to obtain the effect of the present invention.

For controlling iodide ion release in the present invention, the following method is preferred. That is, by changing the pH of the reaction solution, the concentration of the nucleophilic substance, the temperature, etc., from the already uniformly distributed iodide ion releasing agent added to the reaction solution in the particle forming container, the reaction is usually performed at a low level. By changing the pH from high to low, iodide ions are released while controlling the entire reaction solution uniformly. It is preferable that the alkali for raising the pH at the time of releasing the iodide ion and the nucleophilic substance used together are added in a state where the iodide ion releasing agent is uniformly distributed throughout.

More specifically, the present invention relates to a silver halide containing silver iodide (for example, silver iodide, silver iodobromide,
In producing silver chloroiodobromide (silver chloroiodide) grains, iodide ions which react with silver ions are rapidly generated in a reaction system. Most commonly, the iodide ion of the invention is present in a reaction system in which silver ions are already present, for example by the addition of silver nitrate, or an aqueous gelatin solution containing, for example, silver iodobromide silver halide grains as a reaction medium. The release agent may be optionally replaced with another source of halide ions (eg,
KBr) and evenly distribute in the system (eg, by stirring). At this time, the pH of the reaction system is usually weakly acidic. In this state, the iodide ion releasing agent does not rapidly release iodide ions.

Next, an alkali and / or a nucleophilic substance (for example, sodium hydroxide or sodium sulfite) is added to the reaction system as an iodide ion release regulator, so that the pH of the reaction system is changed to the alkali side (preferably). Is 7.
5 to 10). With the addition of the alkali and / or nucleophile, iodide ions start to be rapidly released from the iodide ion releasing agent, and react with silver ions or perform halogen conversion with silver halide grains to convert silver iodide. A region of the silver halide grains is generated. As mentioned,
The reaction temperature is 30 to 80 ° C., usually 35 to 75 ° C., more preferably 35 to 75 ° C., more preferably 35 to 6 ° C., which is usually used for producing silver halide.
0 ° C. The combination of the iodide ion-releasing agent and the iodide ion-releasing regulator and the concentration thereof are selected in view of the range of the second-order reaction constant of the iodide ion releasing reaction from the iodide ion-releasing agent. The addition of the alkali and / or the nucleophilic substance is carried out while stirring the reaction system vigorously in order to uniformly distribute the alkali in the reaction system (that is, to make silver iodide uniform). Is preferably performed.

Hereinafter, metal ion doping of silver halide grains will be described. The silver halide grains of the emulsion of the present invention may contain one or more kinds of photographically useful metal ions or complexes (hereinafter referred to as "metal (complex) ions") in the grains. The useful metal (complex) ions are those doped into grains for the purpose of improving the photographic characteristics of the photosensitive silver halide emulsion. These compounds act as transient or permanent traps for electrons or holes in silver halide crystals, and provide high sensitivity, high contrast,
Effects such as reciprocity property improvement and pressure property improvement can be obtained. In the present invention, the metal doped in the emulsion grains is iron, ruthenium, rhodium, palladium, cadmium,
First to third transition metal elements such as rhenium, osmium, iridium, platinum, chromium, vanadium, gallium,
Ampholytic metal elements such as indium, thallium and lead are preferred. These metal ions are doped in the form of a complex salt or a single salt.

In the case of a complex ion, a hexacoordinate halogeno complex or cyano complex using a halogen ion or cyanide (CN) ion as a ligand is preferably used. Nitrosyl (NO) ligands, thionitrosyl (NS) ligands,
Carbonyl (CO) ligand, thiocarbonyl (NC
O) ligands, thiocyanate (NCS) ligands, selenocyanate (NCSe) ligands, tellurocyanate (CNTe) ligands, dinitrogen (N ₂ ) ligands, azide (N ₃ ) ligands, further bipyridyl ligands, cyclopentadienyl Ligand, 1,2-
Complexes having organic ligands such as dithiorenyl ligands, imidazole ligands and the like can also be used.

As the ligand, the following polydentate ligand may be used. That is, any of a bidentate ligand such as a bipyridyl ligand, a tridentate ligand such as diethylenetriamine, a tetradentate ligand such as triethylenetetraamine, and a hexadentate ligand such as ethylenediaminetetraacetic acid can be used. May be used. The number of ligands is preferably 6, but may be 4. For organic ligand ligands, see US Pat.
Nos. 7021, 5360712 and 5462849 are also preferably used. It is also preferred to incorporate metal ions as oligomers, as described in US Pat. No. 5,249,391.

When incorporating metal (complex) ions into silver halide, it is important that the size of the metal (complex) ions be compatible with the silver halide interstitial distance. In addition, it is essential that a compound of a metal (complex) ion and silver or a halide ion co-precipitate with silver halide in order to be doped into silver halide. Therefore, the metal (complex) ion of the compound with silver or halide ion
Ksp (common logarithm of reciprocal of solubility product) is p
Ksp (silver chloride 9.8, silver bromide 12.3, silver iodide 16.1). Therefore, the pKsp of a compound of a metal (complex) ion with silver or a halogen ion is 8 to 20.
Is preferred. The doping amount of the metal complex into the silver halide grains is generally in the range of 10 ^-9 to 10 ^-2 mol per mol of silver halide. Specifically, the metal complex that provides a transient shallow electron trap during the exposure process is silver halide 1
The metal complex which provides a deep electron trap in the photosensitizing process in the range of 10 ^-6 to 10 ^-2 mol per mol is preferably used in the range of 10 ^-9 to 10 ^-5 mol per mol of silver halide. The metal (complex) ion content of the emulsion particles can be confirmed by atomic absorption, polarized Zeeman spectroscopy and ICP analysis. The ligand of the metal complex ion is infrared absorption (especially FT-IR
).

The above-mentioned doping of the metal (complex) ions into the silver halide grains is carried out in such a manner that the surface phase or internal phase of the grains or the metal ions as described in US Pat. Any of shallow surface phases (so-called subsurface) may be selected depending on the purpose. Also, a plurality of metal ions may be doped,
They may be doped in the same phase or in different phases. These compounds may be added by mixing the metal salt solution with a halide aqueous solution or a water-soluble silver salt solution during grain formation, or by directly adding the metal salt solution. Further, silver halide emulsion fine particles doped with the metal ion may be added. When the metal salt is dissolved in water or a suitable solvent such as methanol or acetone, an aqueous hydrogen halide solution (eg,
HCl, HBr), thiocyanic acid or a salt thereof, or an alkali halide (eg, KCl, NaCl,
It is preferable to use a method of adding KBr or NaBr). It is also preferable to add an acid, an alkali or the like, if necessary, in the same manner.

When a metal ion of a cyano complex is doped into emulsion grains, the reaction between gelatin and the cyano complex may generate cyan, thereby inhibiting gold sensitization. In such a case, it is preferable to use a compound having a function of inhibiting the reaction between gelatin and a cyano complex, as described in, for example, JP-A-6-308653. 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 zinc ion that coordinates with gelatin.

In one preferred embodiment of the present invention,
On a transparent support, at least photosensitive silver halide grains,
A light-sensitive material comprising at least three types of photosensitive layers, each containing a color-developing agent, a coupler and a binder, wherein the photosensitive wavelength region and the absorption wavelength region of a dye formed from the color-developing agent and the coupler are different from each other; And / or using a processing material having a processing layer containing a base precursor, and 0.1 to 1 times the amount required for maximally swelling the entire coating film excluding the back layer of both the photosensitive material and the processing material.
In the presence of water equivalent to twice the amount of the photosensitive material and the processing material, the photosensitive layer and the processing layer are superposed on each other.
To form an image based on at least three non-diffusible dyes on the photosensitive material, and obtain a color image on another recording material based on the image information.

The emulsion of the present invention and other photographic emulsions used in combination with the emulsion of the present invention are described below. Specifically, US Pat. No. 4,500,626 No. 5
Column 0, No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17,029
No. 17, 643 (December 1978)
Mon.) p. 22-23, No. 18,716 (Jan. 1979)
(January) p. 648, No. 307, 105 (1989, January)
January) pages 863 to 865, JP-A-62-253,159.
No. 64-13,546, JP-A-2-236,54
No. 6, No. 3-110, 555 and "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glafkides, C.
hemie etPhisque Photographique, Paul Montel, 1967)
Duffin, Photographic Emulsion Chemistry, GFDuffin, Photographic Emulsion Chemistry, F
ocal Press, 1966), "Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VLZelikman et a
l., Making and Coating Photographic Emulusion, Foca
l Press, 1964) and the like.

The silver halide used in the present invention may be any of silver iodobromide, silver bromide, silver chlorobromide, silver iodochloride, silver chloride and silver iodochlorobromide. The size of silver halide grains is 0.1 to 2 μm, particularly 0.2 to 0.2 μm, in terms of the diameter of a sphere having the same volume.
1.5μ is preferred. The shape of the silver halide grains may be those having a shape of normal crystals such as cubic, octahedral or tetradecahedral, and those having a hexagonal or rectangular tabular shape. Is preferably 8 or more, more preferably 20 or more tabular grains, and in such tabular grains, 50% or more, preferably 80% or more, and more preferably 90% of the projected area of all grains.
It is preferable to use an emulsion occupying the above. Also, U.S. Patent Nos. 5,494,789 and 5,503,970
No. 5,503,971, No. 5,536,632, etc., particles having a thickness smaller than 0.07 μm and a higher aspect ratio can also be preferably used. Also, U.S. Patent Nos. 4,400,463 and 4,7,
Nos. 13,323, 5,217,858 and the like, high silver chloride tabular grains having a (111) plane as a main plane, and US Pat. Nos. 5,264,337, 5,2.
High silver chloride tabular grains having a (100) plane as a main plane described in JP-A Nos. 92,632 and 5,310,635 can also be preferably used. Examples of actually using these silver halide grains are disclosed in Japanese Patent Application Nos. 8-46822 and 8-8622.
-97344 and 8-238672. It is preferable that the emulsion of the present invention is usually subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization, a chalcogen sensitization method using a sulfur, selenium or tellurium compound, a noble metal sensitization method using gold, platinum, iridium or the like, or a compound having an appropriate reducing property during grain formation is used. Thus, a so-called reduction sensitization method for obtaining high sensitivity by introducing a reducing silver nucleus can be used alone or in various combinations. As spectral sensitization, it is adsorbed on silver halide grains,
So-called spectral sensitizing dyes such as cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar dyes, hemicyanine dyes, styryl dyes, or hemioxonol dyes, which have sensitivity in their own absorption wavelength range, are used alone or in combination. It is also preferable to use together with a supersensitizer. The silver halide emulsion of the present invention, azaindenes, triazoles, tetrazole,
It is preferable to add various stabilizers such as nitrogen-containing heterocyclic compounds such as purines, mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, and mercapto compounds such as mercaptothiadiazoles. Photographic additives for silver halide emulsions are
Disclosure Magazine No. 17643 (December 1978
No. 18716 (November 1979), N
o307105 (November 1989), No.389
No. 57 (September 1996) can be preferably used. The photosensitive silver halide is 0.05 to 20 g / m ^{2 in} terms of silver, preferably 0.1 to 1 g / m ² .
0 g / m ^{2 is} used.

The binder of the light-sensitive material is preferably hydrophilic, and examples thereof include the research disclosure described in the preceding section and the method disclosed in JP-A-64-13546.
And those described on pages 1 to 75. Among them, gelatin and a combination of gelatin with another water-soluble binder such as polyvinyl alcohol, modified polyvinyl alcohol, cellulose derivative, acrylamide polymer and the like are preferable. Binder coating amount is 1-2
0 g / m ^2, preferably from 2 to 15 g / m ^2, more preferably suitably 3~12g / m ^2. Among them, gelatin is 50% to 100%, preferably 70% to 100%.
%.

As the color developing agent, p-phenylenediamines or p-aminophenols may be used, but the compounds represented by the general formulas (2) to (6) are preferably used.

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The compound represented by the general formula (2) is a compound generally called sulfonamidophenol. In the general formula (2), R _{1 to} R ₄ each represent 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-group).
-Butyl group), an aryl group (for example, phenyl group, tolyl group, xylyl group), an alkylcarbonamide group (for example, acetylamino group, propionylamino group, butyroylamino group), an arylcarbonamide group (for example, 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), arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenyl) Carbamoyl group,
Ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, dibutylsulfamoyl group) , Piperidylsulfamoyl 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), Xycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, propionyl group, butyroyl group), arylcarbonyl group (for example, benzoyl group) Group, alkylbenzoyl group) or acyloxy group (eg, acetyloxy group, propionyloxy group, butyroyloxy group)
Represents Among R _{1 to} R ₄ , R ₂ and R ₄ are preferably a hydrogen atom. Also, Hammett's constant σ of R _{1 to} R ₄
It is preferable that the sum of the p values is 0 or more.

R ₅ is an alkyl group (for example, methyl, ethyl, butyl, octyl, lauryl, cetyl,
A stearyl group), an aryl group (eg, phenyl, tolyl, xylyl, 4-methoxyphenyl, dodecylphenyl, chlorophenyl, trichlorophenyl, nitrochlorophenyl, triisopropylphenyl, 4-dodecyloxyphenyl, 3,5-di-
(Methoxycarbonyl) group) or a heterocyclic group (eg, a pyridyl group).

The compound represented by the general formula (3) is a compound generally called sulfonylhydrazine. The compound represented by the general formula (5) is a compound generally called carbamoylhydrazine. In the general formulas (3) and (5), R ₅ is an alkyl group (for example, a methyl group, an ethyl group, a butyl group, an octyl group, a lauryl group, a cetyl group,
Stearyl group), aryl group (for example, phenyl group, tolyl group, xylyl group, 4-methoxyphenyl group, dodecylphenyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, nitrochlorophenyl group,
Represents a triisopropylphenyl group, a 4-dodecyloxyphenyl group, a 3,5-di (methoxy) carbonyl group), or a heterocyclic group (eg, a pyridyl group). Z represents an atomic 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.

When Z is a benzene ring, examples of the substituent include an alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), a halogen atom (eg, chloro group, bromo group), and an alkylcarbamoyl group (eg, methylcarbamoyl group, Dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, piperidylcarbamoyl, morpholylcarbamoyl), arylcarbamoyl (for example, phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl) Carbamoyl group, alkylsulfamoyl group (eg, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dib Rusurufamoiru group, piperidyl sulfamoyl group, morpholinocarbonyl Rusuru sulfamoyl group),
Arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, Ethanesulfonyl group), arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group ( For example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, propionyl group, butyroyl group), or arylcarbonyl group (for example, benzoyl group, alkylbenzoyl group) Although the like, the sum of the Hammett constants σ values of the substituents is 1 or more.

The compound represented by the general formula (4) is a compound generally called sulfonylhydrazone. The compound represented by the general formula (6) is a compound generally called carbamoylhydrazone. In the general formulas (4) and (6), R ₅ represents an alkyl group (for example, a methyl group, an ethyl group, a butyl group, an octyl group, a lauryl group, a cetyl group,
Stearyl group), aryl group (for example, phenyl group, tolyl group, xylyl group, 4-methoxyphenyl group, dodecylphenyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, nitrochlorophenyl group,
Represents a triisopropylphenyl group, a 4-dodecyloxyphenyl group, a 3,5-di (methoxy) carbonyl group), or a heterocyclic group (eg, a pyridyl group). 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 (2) to (6) are shown, but the compounds of the present invention are not limited thereto.

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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 .

When the color developing agent is used, a coupler which forms a dye by a coupling reaction with an oxidized form of the color developing agent is used for the photosensitive material. Preferred examples thereof include compounds generally referred to as active methylene, 5-pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole. Examples are research and
Disclosure No. 38957 (September 1996
Month) What is cited on pages 616 to 624 can be preferably used. Particularly preferred examples include pyrazoloazole couplers described in JP-A-8-110608, and pyrrolotriazole couplers described in JP-A-8-122994 and Japanese Patent Application No. 8-45564. . These couplers, each color 0.05~10mmol / m ^2, preferably using a 5 mmol / m ² 0.1. Use of colored couplers for correcting unnecessary absorption of coloring dyes, residues of photographically useful compounds that react with oxidized developing agents, such as compounds (including couplers) that release development inhibitors, etc. Can be.

In another embodiment of the present invention, at least one layer of a photosensitive silver halide emulsion, a coloring material which releases or diffuses a diffusible dye corresponding to or reversely corresponds to silver development, and a binder is provided. The light-sensitive material can be in the form of a light-sensitive material comprising a light-sensitive halogenated emulsion layer and a light-insensitive layer. The coloring material used at that time contains a dye part in its own structure,
A compound capable of releasing or diffusing a diffusible dye corresponding to or inversely corresponding to silver development. Simultaneously with or subsequent to the development, part or all of the diffusible dye is removed from the photosensitive material. An image is obtained on the photosensitive material by the residual color material after the development. This compound can be represented by the following general formula (LI). ((Dye) mY) nZ (LI) Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, and Z represents an image A difference in the diffusivity of the compound represented by ((Dye) m-Y) nZ corresponding to or opposite to a photosensitive silver salt having a latent image, or (Dye) m-
Y, and released (Dye) m-Y and ((Dy)
e) mY) represents a group having the property of causing a difference in diffusibility with nZ, m represents an integer of 1 to 5,
n represents 1 or 2, and when m and n are not 1, both Dyes may be the same or different. General formula (L
Specific examples of the dye-donating compound represented by I) include the compounds described in P10 to P12 of JP-A-9-112265.
Can be mentioned. The compounds of the formula (1) release or diffuse a diffusible dye in a manner corresponding to the development of silver halide, and release or diffuse a diffusible dye in accordance with the development of a silver halide. .

Also, as described in US Pat. Nos. 4,362,806, 3,719,489 and 4,375,507, they react with silver ions or organic silver ion complexes to release diffusible dyes. Compounds can also be used.

The light-sensitive material is usually composed of three or more light-sensitive layers having different color sensitivity. Each photosensitive layer has at least one
Including a silver halide emulsion layer, a typical example comprises a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is blue light,
A unit photosensitive layer having color sensitivity to either green light or red light. In a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally arranged in order from the support side to red color sensitivity. Layer, a green color sensitive layer, and a blue color sensitive layer in this order. However, even if the above installation order is reversed according to the purpose,
Further, the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

In the present invention, as a coloring layer using an oil-soluble dye which can be decolorized by the treatment, a yellow filter layer,
A magenta filter layer and an antihalation layer can be used. Accordingly, for example, when the photosensitive layer is provided in the order of a red photosensitive layer, a green photosensitive layer, and a blue photosensitive layer from the side closest to the support, a yellow filter layer and a green photosensitive layer are provided between the blue photosensitive layer and the green photosensitive layer. A magenta filter layer can be provided between the red photosensitive layer and the red photosensitive layer, and a cyan filter layer (antihalation layer) can be provided between the red photosensitive layer and the support. These colored layers may be in direct contact with the emulsion layer or may be arranged so as to be in contact with an intermediate layer such as gelatin. The amount of the dye to be used is 0.03 to 3.0 with respect to the transmission density of each layer for blue, green and red light, respectively.
0, more preferably 0.1 to 1.0. Specifically, although it depends on the ε and the molecular weight of the dye, 0.0
It may be used from 05 to 2.0 mmol / m ^2, more preferably 0.05 to 1.0 mmol / m ^2.

The dyes used are described in Japanese Patent Application No. 8-329.
124 is a cyclic ketomethylene compound (e.g., 2-
Pyrazolin-5-one, 1,2,3,6-tetrahydropyridin-2,6-dione, rhodanin, hydantoin,
Thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolopyridine, hydroxypyridine, pyrazolidinedione, 2,5-dihydrofuran-2-one, Pyrrolin-2-one) or a methylene group flanked by electron-withdrawing groups (eg, -CN,
-SO ₂ R ₁ , -COR ₁ , -COOR ₁ , -CON
_{(R 2) 2, -SO 2} N (R 2) 2, -C [= C (C
N) ₂ ] R ₁ , -C [= C (CN) ₂ ] N (R ₁ ) ₂ (R ₁
Represents an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, or a heterocyclic group, and R ₂ represents a hydrogen atom or R ₁
An acid nucleus and a basic nucleus (eg, pyridine, quinoline, indolenine, oxazole, imidazole, thiazole, benzoxazole, benzimidazole, benzothiazole, Oxazolines, naphthoxazoles, pyrroles), aryl groups (eg, phenyl, naphthyl) and heterocyclic groups (eg, pyrrole,
Indole, furan, thiophene, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran, oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine , Tetrazole, oxazole, coumarin, chroman) and a compound having a methine group, or (NC)
_{2 C = C (CN) -R} 3 (R 3 is an aryl group, a heterocyclic group).

The light-sensitive material of the present invention may be used by mixing two or more dyes in one colored layer. For example, three kinds of dyes of yellow, magenta and cyan can be mixed and used in the above-mentioned antihalation layer. The compound of the present invention is preferably used in a state where oil droplets obtained by dissolving a decolorizable dye in oil and / or an oil-soluble polymer are dispersed in a hydrophilic binder. An emulsification dispersion method is preferable as the preparation method, and for example, a method described in US Pat. No. 2,322,027 can be used. In this case, US Patent 4,
555, 470, 4, 536, 466, 4, 5
Nos. 87, 206, 4, 555, 476, 4, 59
No. 9,296, Japanese Patent Publication No. 3-62, No. 256, etc., a high boiling point oil, if necessary, having a boiling point of 50 ° C. to 160 ° C.
It can be used in combination with an organic solvent having a low boiling point of ° C. Further, two or more high boiling oils can be used in combination. In addition, an oil-soluble polymer can be used in place of or in combination with oil, and examples thereof include PCT International Publication No. W
O88 / 00723. The amount of the high boiling oil and / or the polymer is 0.01 g to 10 g, preferably 0.1 g, per 1 g of the dye used.
Use up to 5 g. As a method of dissolving the dye in the polymer, it is also possible to use a latex dispersion method,
Specific examples of the process and the latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) 2,5.
No. 41, 274, No. 2, 541, 230, No. 5
3-41091 and European Patent Publication No. 029104.

In dispersing the oil droplets in the hydrophilic binder, various surfactants can be used. For example, surfactants described in JP-A-59-157,636, pp. 37-38, and publicly known technique No. 5 (March 22, 1991, published by Aztec Co., Ltd.), pp. 136-138, can be used. Also, Japanese Patent Application Nos. 5-204, 325
No. 6-19247, West German Published Patent No. 932,
A phosphate ester type surfactant described in No. 299A can also be used. As the hydrophilic binder, a water-soluble polymer is preferable. Examples include gelatin, proteins of gelatin derivatives, or natural compounds such as cellulose derivatives, starch, gum arabic, dextran, polysaccharides such as pullulan, and synthetic high molecular compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers. . These water-soluble polymers can be used in combination of two or more. Particularly preferred is a combination with gelatin. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and may be used in combination.

The dye decolorizes during processing in the presence of the decoloring agent. Decoloring agents include alcohols or phenols, amines or anilines, hydroxyamines,
Sulfinic acids or salts thereof, sulfurous acid or salts thereof, thiosulfuric acid or salts thereof, carboxylic acids or salts thereof, hydrazines, guanidines, aminoguanidines, amidines, thiols, cyclic or linear active methylene compounds, cyclic or Examples include a chain active methine compound and an anionic species generated from these compounds. Of these, those preferably used are hydroxyamines, sulfinic acids, sulfurous acid, guanidines,
Aminoguanidines, heterocyclic thiols, cyclic or chain active methylene, and active methine compounds are preferable, and guanidines and aminoguanidines are particularly preferable. It is believed that the above-described decolorizing agent comes into contact with the dye during processing and decolorizes the dye by nucleophilic addition to the dye molecules. Preferably, the silver halide light-sensitive material containing the dye is heated by superposing the film surfaces together in the presence of water and a processing member containing a decolorant or a decolorant precursor after imagewise exposure or simultaneously with imagewise exposure. Thereafter, by peeling off both, a color-developed image is obtained on the silver halide light-sensitive material and the dye is decolorized. In this case, the density of the dye after decoloring is 1/3 or less, preferably 1/5 or less of the original density. The amount of the decoloring agent used is 0.1 to 200 times, preferably 0.5 to 100 times the mole of the dye.

The total thickness of the photosensitive layers is 1 to 20 μm, preferably 3 to 15 μm. The silver halide, the color developing agent and the coupler may be contained in the same photosensitive layer or in different layers. In addition to the photosensitive layer, a protective layer, an undercoat layer, an intermediate layer,
A non-photosensitive layer such as a yellow filter layer and an antihalation layer may be provided, and a back layer may be provided on the back side of the support. The thickness of the entire coating film on the photosensitive layer side is 3 to 25 µ, preferably 5 to 20 µ.

The light-sensitive material includes a hardener, a surfactant, a photographic stabilizer, an antistatic agent, a slipping agent, a matting agent,
Latex, formalin scavengers, dyes, UV absorbers and the like can be used. Examples of these are disclosed in the aforementioned Research Disclosure and Japanese Patent Application No. 8-301.
No. 03, etc. Incidentally, particularly preferred examples of the antistatic agent is _{ZnO, TiO 2, SnO 2,} Al 2 O 3, In 2 O 3, SiO 2, Mg
Metal oxide fine particles such as O, BaO, MoO ₃ and V ₂ O ₅ .

As a support for the photosensitive material, a photographic support described in “Basics of Photographic Engineering—Silver-Salt Photography”, edited by The Photographic Society of Japan, Corona Co., Ltd., pp. 223-240 (1979) is preferred. Specific examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, syndiotactic polystyrene, and celluloses (eg, triacetyl cellulose). These supports can be subjected to heat treatment (crystallinity and orientation control), uniaxial and biaxial stretching (orientation control), blending of various polymers, surface treatment, etc. to improve optical and physical properties. it can. Further, as a support, for example,
No. 124645, No. 5-40321, No. 6-3509
It is preferable to record photographic information and the like using a support having a magnetic recording layer described in JP-A Nos. 2 and 6-31875.

On the back surface of the support of the light-sensitive material, JP-A-8-
It is also preferred to apply a water-resistant polymer as described in 292514. The polyester support particularly preferably used for the light-sensitive material having the magnetic recording layer is disclosed in Published Technical Report 94-6023 (Invention Association; 199).
4.3.15). The thickness of the support is 5 to 200 µ, preferably 40 to 120 µ.

As a method of developing the photographed photosensitive material of the present invention, a thermal developing system incorporating a color developing agent is preferable, which is characterized in that it is quick and simple and has a low environmental load. It is also possible to form an image by developing the light-sensitive material described above with an activator method using an alkali processing liquid or a processing liquid containing a developing agent / base.

The heat treatment of the photosensitive material is known in the art.
For example, the basics of photo engineering (Corona, 1970)
Pages 553-555, published April 1978, video information 4
Page 0, Nabletts Handbook of Photography and Reprogra
phy 7th Ed. (Vna Nostrand and Reinhold Company)
Nos. 3,152,904, 3,301,678, 3,392,020, 3,457,075, British Patent 1,131,10
8, No. 1,167,777, and Research Disclosure Magazine, June 1978, pp. 9-15 (RD-
17029).

Activator processing refers to a processing method in which a color developing agent is incorporated in a photosensitive material and development is performed using a processing solution containing no color developing agent. The processing solution in this case is characterized in that it does not contain a color developing agent contained in a normal developing solution component, and may contain other components (for example, an alkali, an auxiliary developing agent, etc.). Regarding the activator treatment, European Patent No. 545,
No. 491A1, No. 565, 165A1, and the like. The method of developing with a processing solution containing a developing agent / base is described in RD. No. 17643, pp. 28-29,
No. 18716, 651 left column to right column, and No. 3
07105, pages 880-881.

Next, a processing material and a processing method used in the case of heat development processing in the present invention will be described.
In the present invention, a processing material different from the photosensitive material can be used for developing the photographed photosensitive material. The treatment material contains at least a base and / or a base precursor. The most preferable one is a basic metal compound which is hardly soluble in water described in EP 210,660 and U.S. Pat. No. 4,740,445, and a metal ion constituting the basic metal compound is mixed with water. In this method, a base is generated by a combination of compounds capable of forming a complex as a medium. In this case, it is preferable to add the basic compound which is hardly soluble in water to the light-sensitive material and the complex-forming compound to the processing material, and vice versa. A preferred combination of compounds is a system using zinc hydroxide fine particles as a photosensitive material and a picolinic acid salt such as guanidine picolinate as a processing material. A mordant may be used as the treatment material, and in this case, a polymer mordant is preferable. Processing materials include Japanese Patent Application No. 7-32245.
As described in No. 4, a physical development nucleus such as colloidal silver or palladium sulfide, and a silver halide solvent such as hydantoin are included, and at the same time of development, the silver halide of the photosensitive material is solubilized. It may be fixed to the processing material. The processing material may further contain a development stopping agent, a printout preventing agent, and the like.

The processing material may have a protective layer, an undercoat layer, a back layer and other auxiliary layers in addition to the processing layer. Preferably, the treatment material is provided with a treatment layer on a continuous web, and is supplied from a delivery roll and wound onto another roll without being cut after being used for treatment. An example is described in Japanese Patent Application No. 7-240445. The support of the processing material is not limited, and a plastic film or paper as described for the photosensitive material is used. The thickness is 4μ ~ 1
It is 20μ, preferably 6-70μ. Japanese Patent Application 8-52
No. 586, a film on which aluminum is deposited can also be preferably used. In the present invention, a photosensitive material photographed by a camera or the like is exposed to water in the presence of water equivalent to 0.1 to 1 times the amount required for maximally swelling the entire coating film excluding the back layer of both the photosensitive material and the processing material. It is preferable that the material and the processing material are overlaid so that the photosensitive layer and the processing layer face each other, and developed by heating at a temperature of 60 ° C. to 100 ° C. for 5 seconds to 60 seconds.

As a method for 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. Further, as described in Japanese Patent Application No. 8-196945, a plurality of nozzle holes for jetting water are arranged at regular intervals in a straight line along a direction intersecting the direction of transport of the photosensitive material or the processing material. It is also preferable to spray water using a water application device having a nozzle that has been moved and an actuator that displaces the nozzle toward a photosensitive material or a processing material on a transport path. A method of applying water with a sponge or the like is also preferable. As a heating method in the development process, contact with a heated block or plate,
A heat roller, a heat drum, an infrared and far infrared lamp, or the like may be used. In the present invention, another bleach-fixing step for further removing silver halide and developed silver remaining in the light-sensitive material after development is not essential. However, a fixing step and / or a bleaching step may be provided in order to reduce the load of reading image information and to enhance image storability. In this case, ordinary liquid treatment may be used, but it is preferable to perform a heat treatment together with another sheet coated with a treatment agent as described in Japanese Patent Application No. 8-89977.

In the present invention, after an image is obtained on a photosensitive material, a color image is obtained on another recording material based on the information. As a method, a photosensitive material such as color paper may be used, and normal projection exposure may be used. It is preferable to output to another recording material. The material to be output may be a sublimation type thermosensitive recording material, a full color direct thermosensitive recording material, an ink jet material, an electrophotographic material, or the like, in addition to a photosensitive material using silver halide.

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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. Example 1 (1) Preparation of emulsion

[Tabular Silver Iodobromide Emulsion 1-A (Comparative Emulsion)] (Step 1) 1193 cc of an aqueous solution containing 1 g of low molecular weight gelatin (molecular weight: 15,000) and 0.9 g of KBr was stirred while maintaining the temperature at 40 ° C. 0.23 M AgNO ₃ aqueous solution 17
17cc of a 0.23M KBr aqueous solution containing 10 mol% of cc and KI were simultaneously added by a double jet for 30 seconds.
After adjusting the pAg to 9.72, the pAg was increased to 75 in 40 minutes.
After heating to 35 ° C. and adding 35 g of gelatin (lime-processed gelatin), 116 cc of a 1.5 M aqueous solution of AgNO ₃ and a 1.8 M aqueous solution of KBr were accelerated while maintaining the pAg at 8.29 (at the end). (3 times the flow rate at the start) was added at the same time for 11.5 minutes. Next, 1.9 M AgNO ₃
While maintaining a pAg of 7.72 and accelerating the flow rate of 302 M aqueous solution of KBr containing 3.3 mol% of KI and 302 cc of the aqueous solution (final flow rate is 5.2 times that of the start time), 1
Added for 9.5 minutes. Further, 96 cc of a 1.5 M AgNO ₃ aqueous solution and 80 cc of a 1.8 M KBr aqueous solution were simultaneously and quantitatively added over 3 minutes.

(Step 2) Then, the temperature was lowered to 55 ° C.
After simultaneously adding 153 cc of an aqueous solution of AgNO ₃ M and 415 cc of an aqueous solution of KI 0.12 M for 5 minutes, sodium benzenethiosulfonate and K ₂ IrCl ₆ were each added to 3.8 × 10 ⁻ of the total silver of the grains. ⁶ mol / mol silver, 4
After adding only × 10 ⁻⁸ mol / mol silver as a solution, 228 cc of a 1.5 M AgNO ₃ aqueous solution and K ₄ [Fe (CN) ₆ ] were added at 2 × 10 ⁻⁵ mol / mol to the total silver amount of the grains. 1.8 containing only molar silver
An aqueous KBr solution of M was added simultaneously for 20 minutes in a fixed amount while keeping the pAg at 8.59. (Step 3) Thereafter, the emulsion is cooled to 35 ° C., washed with water by a conventional flocculation method, and an aqueous solution containing zinc nitrate in an amount of 1 × 10 ⁻³ mol / mol silver with respect to the total silver content of the grains is used. After the addition,
The pH was increased and 75 g of gelatin was added to disperse the mixture.
5, adjusted to pAg = 8.2 and stored.

In the resulting emulsion, tabular grains accounted for more than 98% of the total projected area of all grains, and the average equivalent spherical diameter was 0.85 μm. Hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.5 to 1 accounted for 80% or more of the projected area of all grains.
The average grain thickness of all tabular grains was 0.32 μm, the average aspect ratio of all tabular grains was 3.5, and the coefficient of variation of equivalent tabular equivalent diameter of all tabular grains was 17%. The particle shape was determined by taking a transmission electron microscope photograph by a replica method. 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 each of the 200 grains in the emulsion (sample tilt angle −10 for each grain).゜, -5 ゜, 0 ゜, +
Observation was made in 5 ways, 5 ° and + 10 °. 50 per particle
The ratio (number%) of the tabular grains having more than one dislocation line to all grains is 83%, and the proportion of tabular grains having dislocation lines localized substantially only in the fringe portion of the grains ( (Number%) was 43%. Further, the coefficient of variation of the silver iodide content distribution between grains was 26%.

Next, preparation of tabular silver iodobromide emulsions 1-B to 1-R will be described. The grain characteristics were examined in the same manner as in the case of Emulsion 1-A. Table 9 shows the results. In the emulsions 1-B to 1-R, the proportion of tabular grains in the total projected area of all grains exceeded 98%, as in the emulsion 1-A, and the average equivalent spherical diameter was 0.85 μm. The ratio of hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.5 to 1 in the total projected area of all grains is as follows in emulsion 1-B.
1-H, 1-J-L, and 1-N-R were 80% or more as in 1-A. (Table 9 shows emulsions 1-E,
For 1-G, 1-K, and 1-O (comparative emulsions), the ratio (number%) of tabular grains having 10 to 49 dislocation lines per grain to all grains was 1 For -J, 1-N, and 1-R (each of the emulsion of the present invention), the ratio (number%) of tabular grains in which dislocation lines are localized substantially only at the corners of grains relative to all grains is shown. ing. )

[Tabular silver iodobromide emulsion 1-B (comparative emulsion)]
Emulsion 1-A was prepared in the same manner except that (Step 2) was changed as follows. “(Step 2) After that, the temperature was lowered to 40 ° C., an aqueous solution containing 19 g of the compound (58), which is an iodide ion releasing agent, was added, and then 77 cc of a 0.8 M aqueous sodium sulfite solution was quantitatively added for 1 minute to adjust the pH. The temperature was raised to 55 ° C. over 5 minutes and the pH was returned to 5.5 after 2 minutes, after which sodium benzenethiosulfonate and K ₂ IrCl _{6 were} added. Was added as a solution in an amount of 3.8 × 10 ⁻⁶ mol / mol silver to 4 × 10 ⁻⁸ mol / mol silver with respect to the total silver content of the grains, and then 1.5 M AgNO ₃
1.8 M KB containing 269 cc of a water solution and 2 × 10 ⁻⁵ mol / mol silver based on the total silver content of K ₄ [Fe (CN) ₆ ]
r aqueous solution at the same time with pAg of 8.59
Added for 0 minutes. The shape of the obtained grains was almost the same as that of Emulsion 1-A.

[Tabular silver iodobromide emulsion 1-C (comparative emulsion)]
Emulsion 1-A was prepared in the same manner (step 1) except for the following changes. "302 cc of 1.9 M AgNO ₃ aqueous solution
And 2.2 M KBr aqueous solution containing 3.3 mol% of KI
Instead of keeping the Ag at 7.72, it was added at an accelerated flow rate keeping it at 8.29. In the obtained grains, the average grain thickness of all tabular grains was 0.28 μm, the average aspect ratio of all tabular grains was 4.3, and the variation coefficient of equivalent tabular equivalent diameter of all tabular grains was 20%.

[Tabular silver iodobromide emulsion 1-D (invention emulsion)] Emulsion 1-B was prepared in the same manner as in (Step 1) except for the following changes. "1.9 M AgNO ₃ aqueous solution 30
A 2.2 M aqueous KBr solution containing 2 cc and 3.3 mol% of KI was added while accelerating the flow rate while keeping the pAg at 8.29 instead of keeping the pAg at 7.72. The shape of the obtained grains was almost the same as that of Emulsion 1-C.

[Tabular silver iodobromide emulsion 1-E (comparative emulsion)]
Emulsion 1-A was prepared in the same manner except that (step 1) was changed as follows. "(Step 1) 1 g of low molecular weight gelatin (molecular weight 15,000)
19.3 cc of an aqueous solution containing 0.9 g of KBr and KBr at 40 ° C.
While maintaining the solution at a concentration of 0.23M AgNO ₃ aqueous solution 3
7.5 cc and 37.5 cc of a 0.23 M aqueous KBr solution were simultaneously added by a double jet for 30 seconds. Then pA
g was adjusted to 9.88, the temperature was raised to 75 ° C. in 40 minutes, and ripening was performed for 20 minutes. 35 g of gelatin (lime-processed gelatin) and 8 cc of a 5.1 M aqueous NaCl solution were added, and then 1.5 M of a 1.5 M NaCl aqueous solution was added. AgNO ₃ aqueous solution of 116 cc and 1.
While maintaining the pAg at 8.01 and accelerating the flow rate of the 8M KBr aqueous solution (the flow rate at the end is three times that at the start), 1
Added for 1.5 minutes. Next, 2.2 M KB containing 302 cc of a 1.9 M AgNO ₃ aqueous solution and 3.3 mol% of KI.
While increasing the flow rate while maintaining the pAg of the r aqueous solution at 7.86 (the flow rate at the end is 5.2 times that at the start), 19.5 at the same time
Minutes. Further, a 1.5 M AgNO ₃ aqueous solution 9
6 cc and 80 cc of a 1.8 M aqueous KBr solution were simultaneously added at a constant rate over 3 minutes. In the obtained grains, the average grain thickness of all tabular grains was 0.18 μm, the average aspect ratio of all tabular grains was 8.4, and the variation coefficient of equivalent tabular equivalent diameter of all tabular grains was 15%.

[Tabular silver iodobromide emulsion 1-F (emulsion of the present invention)] Emulsion 1-B was prepared in the same manner except that (step 1) was changed as follows. "(Step 1) 1 g of low molecular weight gelatin (molecular weight 15,000)
19.3 cc of an aqueous solution containing 0.9 g of KBr and KBr at 40 ° C.
While maintaining the solution at a concentration of 0.23M AgNO ₃ aqueous solution 3
7.5 cc and 37.5 cc of a 0.23 M aqueous KBr solution were simultaneously added by a double jet for 30 seconds. Then pA
g was adjusted to 9.88, the temperature was raised to 75 ° C. in 40 minutes, and ripening was performed for 20 minutes. 35 g of gelatin (lime-processed gelatin) and 8 cc of a 5.1 M aqueous NaCl solution were added, and then 1.5 M of a 1.5 M NaCl aqueous solution was added. AgNO ₃ aqueous solution of 116 cc and 1.
An 8M aqueous KBr solution was added at the same time for 11.5 minutes while maintaining the pAg at 8.01 and accelerating the flow rate (the flow rate at the end was three times that at the start). Next, 2.2 M K containing 3.3 mol% of KI and 3.3 cc of 1.9 M AgNO ₃ aqueous solution.
At the same time, while increasing the flow rate while maintaining the pAg at 7.86 (the flow rate at the end is 5.2 times the flow rate at the start), the Br aqueous solution is simultaneously cooled to 1
Added for 9.5 minutes. Further, 96 cc of a 1.5 M AgNO ₃ aqueous solution and 80 cc of a 1.8 M KBr aqueous solution were simultaneously and quantitatively added over 3 minutes. The shape of the obtained grains was almost the same as that of Emulsion 1-E.

[Tabular silver iodobromide emulsion 1-G (comparative emulsion)]
Emulsion 1-E was prepared in the same manner (step 1) except for the following changes. "116 cc of 1.5 M AgNO ₃ aqueous solution
And an aqueous 1.8 M KBr solution were added while accelerating the flow rate while maintaining the pAg at 8.36 instead of 8.01. 302 cc of a 1.9 M AgNO ₃ aqueous solution and a 2.2 M KBr aqueous solution containing 3.3 mol% of KI were added while keeping the pAg at 8.36 instead of 7.86. "
The obtained grains had an average grain thickness of all tabular grains of 0.13.
μm, the average aspect ratio of all tabular grains was 13.6, and the coefficient of variation of the equivalent circle equivalent diameter of all tabular grains was 18%.

[Tabular silver iodobromide emulsion 1-H (emulsion of the present invention)] The emulsion 1-F was prepared in the same manner as in the step 1 except for the following changes. "1.5 M AgNO ₃ aqueous solution 11
6cc and 1.8M KBr aqueous solution, pAg 8.01.
, Instead of keeping at 8.36, and adding while accelerating the flow rate. 302 cc of 1.9 M AgNO ₃ aqueous solution and KI
Of a 2.2 M KBr aqueous solution containing 3.3 mol% of pAg
Was added at 8.36 instead of 7.86. The shape of the obtained grains was almost the same as that of Emulsion 1-G.

[Tabular silver iodobromide emulsion 1-I (emulsion of the present invention)] An emulsion 1-B (step 1) was prepared in the same manner as (Emulsion 1-B) except that the following changes were made. "(Step 1) 1 g of oxidized gelatin and KBr.
While stirring 1193 cc of an aqueous solution containing 9 g at 30 ° C., 37.5 cc of a 0.23 M AgNO ₃ aqueous solution and 37.5 cc of a 0.23 M KBr aqueous solution were simultaneously added by a double jet for 2 seconds. Then, after adjusting the pAg to 9.88, the temperature was raised to 75 ° C. in 40 minutes, and ripening was performed for 35 minutes. After 35 g of gelatin (trimellitized gelatin) and 8 cc of a 5.1 M NaCl aqueous solution were added,
116 cc of 1.5 M AgNO ₃ aqueous solution and 1.8 M K
The Br aqueous solution was added at the same time for 11.5 minutes while maintaining the pAg at 8.29 and accelerating the flow rate (the flow rate at the end was 3 times that at the start). Next, a 1.9 M AgNO ₃ aqueous solution 302
A 2.2 M aqueous KBr solution containing 3.3 mol% of cc and KI was added at the same time for 19.5 minutes while accelerating the flow rate while maintaining the pAg at 8.29 (the flow rate at the end was 5.2 times that at the start). did. Further, 96 cc of a 1.5 M AgNO ₃ aqueous solution and 80 cc of a 1.8 M KBr aqueous solution were simultaneously and quantitatively added over 3 minutes. In the shape of the obtained grains, the average grain thickness of all tabular grains was 0.13 μm, the average aspect ratio of all tabular grains was 13.4, and the variation coefficient of equivalent tabular equivalent diameter of all tabular grains was 13%. In addition, adjacent side ratio (maximum side length /
Hexagonal tabular grains having a minimum side length of 1.2 to 1 accounted for 80% or more of the projected area of all grains.

[Tabular silver iodobromide emulsion 1-J (invention emulsion)] Emulsion 1-H was prepared in the same manner as in step 2 except for the following changes. "Instead of cooling down to 40 ° C, 60 ° C
Temperature to release iodide ions and then AgN
The addition of the O ₃ aqueous solution and the KBr aqueous solution was also performed at 60 ° C. as it was. The shape of the obtained grains was almost the same as that of Emulsion 1-G.

[Tabular silver iodobromide emulsion 1-K (comparative emulsion)]
Emulsion 1-G was prepared in the same manner (step 1) except for the following changes. "1 g of oxidized gelatin instead of 1 g of low molecular weight gelatin, and 2.2 M KB containing 302 cc of a 1.9 M AgNO ₃ aqueous solution and 3.3 mol% of KI.
The r aqueous solution was added while maintaining the pAg at 8.51 and accelerating the flow rate instead of 8.36. In the obtained grains, the average grain thickness of all tabular grains was 0.10 μm, the average aspect ratio of all tabular grains was 20.2, and the variation coefficient of equivalent tabular equivalent diameter of all tabular grains was 22%.

[Tabular silver iodobromide emulsion 1-L (emulsion of the present invention)] The emulsion 1-H was prepared in the same manner as in the step 1 except for the following changes. "Using 1 g of oxidized gelatin instead of 1 g of low molecular weight gelatin, 1.9 M AgNO
₃ 2.2 cc containing 302 cc of an aqueous solution and 3.3 mol% of KI
Was added while accelerating the flow rate while maintaining the pAg at 8.51 instead of 8.36. The shape of the obtained particles was almost the same as that of Emulsion 1-K.

[Tabular Silver Iodobromide Emulsion 1-M (Emulsion of the Present Invention)] (Emulsion 1-I) was prepared in the same manner as in emulsion (Step 1) except for the following changes. "1.9 M AgNO ₃ aqueous solution 30
250 cc of a 2.2 M aqueous KBr solution containing 2 cc and 3.3 mol% of KI is used instead of keeping the pAg at 8.15 at 8.5.
The addition was carried out while keeping the flow rate at 8 and accelerating the flow rate. "The shape of the obtained grains is such that the average grain thickness of all grains is 0.10 μm.
m, the average aspect ratio of all tabular grains was 20.5, and the coefficient of variation of the equivalent circular equivalent diameter of all tabular grains was 15%. Hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.2 to 1 account for 70% of the projected area of all grains.
Or more.

[Tabular Silver Iodobromide Emulsion 1-N (Emulsion of the Present Invention)] Emulsion 1-L was prepared in the same manner as in (Step 2) except for the following changes. "Instead of cooling down to 40 ° C, 60 ° C
Temperature to release iodide ions and then AgN
The addition of the O ₃ aqueous solution and the KBr aqueous solution was also performed at 60 ° C. as it was. The shape of the obtained particles was almost the same as that of Emulsion 1-K.

[Tabular silver iodobromide emulsion 1-O (comparative emulsion)]
Emulsion 1-G was prepared in the same manner (step 1) except for the following changes. "Instead of 1 g of low molecular weight gelatin, 1 g of oxidized gelatin was used. In addition, 1.5 M AgN
116 cc of an O ₃ aqueous solution and a 1.8 M aqueous KBr solution were pA
g was maintained at 8.51 instead of 8.36 while increasing the flow rate and adding. Further, 2.2 M KNO containing 302 cc of a 1.9 M AgNO ₃ aqueous solution and 3.3 mol% of KI.
Instead of maintaining the pAg of the aqueous Br solution at 8.36, AgBr ultrafine particles (1.5 M
(Ag amount equal to 116 cc of AgNO ₃ aqueous solution) and a 1M aqueous KBr solution were added while the pAg was maintained at 8.51 and the flow rate was accelerated. In the obtained grains, the average grain thickness of all tabular grains was 0.07 μm, the average aspect ratio of all tabular grains was 34.5, and the variation coefficient of equivalent tabular equivalent diameter of all tabular grains was 27%.

[Tabular silver iodobromide emulsion 1-P (invention emulsion)] Emulsion 1-H was prepared in the same manner as in (Step 1) except for the following changes. "1 g of oxidized gelatin was used in place of 1 g of low molecular weight gelatin. Also, 116 cc of 1.5 M AgNO ₃ aqueous solution and 1.8 M KBr aqueous solution were kept at 8.51 instead of keeping pAg at 8.36. The flow rate was increased and the 1.9 M AgN was added.
2.2 containing 302 cc of O ₃ aqueous solution and 3.3 mol% of KI
Instead of keeping the pAg of the aqueous KBr solution of M at 8.36,
AgBr ultrafine particles (silver amount equivalent to 116 cc of a 1.5 M AgNO ₃ aqueous solution) and a 1 M aqueous KBr solution which were simultaneously prepared in another reaction vessel were added while the pAg was kept at 8.51 and the flow rate was accelerated. The shape of the obtained particles was almost equivalent to that of Emulsion 1-O.

[Tabular silver iodobromide emulsion 1-Q (emulsion of the present invention)] Emulsion 1-I was prepared in the same manner as in step 1 except for the following changes. "1.5 M AgNO ₃ aqueous solution 11
A 6 cc and 1.8 M aqueous KBr solution was added while accelerating the flow rate while maintaining the pAg at 8.44 instead of 8.29. Next, instead of adding 302 cc of a 1.9 M aqueous solution of AgNO ₃ and cc of a 2.2 M aqueous solution of KBr containing 3.3 mol% of KI while accelerating the flow rate while maintaining the pAg at 8.29, another reaction vessel was used. AgBr ultrafine particles (silver amount equal to 116 cc of a 1.5 M AgNO ₃ aqueous solution) and a 1 M aqueous KBr solution which were simultaneously prepared were added while maintaining the pAg at 8.44 while accelerating the flow rate. In the shape of the obtained grains, the average grain thickness of all tabular grains was 0.07 μm, the average aspect ratio of all tabular grains was 35, and the variation coefficient of equivalent tabular equivalent diameter of all tabular grains was 20%.

[Tabular silver iodobromide emulsion 1-R (inventive emulsion)] Emulsion 1-P was prepared in the same manner as in (Step 2) except for the following changes. "Instead of cooling down to 40 ° C, 60 ° C
Temperature to release iodide ions and then AgN
The addition of the O ₃ aqueous solution and the KBr aqueous solution was also performed at 60 ° C. as it was. The shape of the obtained particles was almost equivalent to that of Emulsion 1-O.

(2) Chemical sensitization For emulsions 1-A to 1-R, 56 ° C., pH = 5.8, p
Under the condition of Ag = 8.4, the following red-sensitive spectral sensitizing dyes I and II
After the addition of III and III, a mixed solution of potassium thiocyanate and chloroauric acid was added, and then sodium thiosulfate, the following selenium sensitizer and compound I were added to perform spectral sensitization 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.

[0147]

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[0148]

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(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 Color Developing Agent and Coupler> The oil phase component and the aqueous phase component having the compositions shown in Table 1 are each dissolved to form a uniform solution at 60 ° C. The oil phase component and the aqueous phase component were combined and emulsified and dispersed in a 1-liter stainless steel container at 10,000 rpm for 20 minutes using a dissolver stirrer with a 5 cm diameter disperser. Thereafter, warm water in the amount shown in Table 1 was added as post-water and mixed at 2000 rpm for 10 minutes. Thus, an emulsified dispersion of a coupler of three colors of cyan, magenta and yellow and a color developing agent was prepared.

[0151]

[Table 1]

[0152]

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[0153]

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<Preparation of Dye Dispersion for Yellow Filter and Antihalation Layer> As shown in Table 2, a high boiling solvent (7) and cyclohexanone were added to the leuco dyes Y, M and C and the developer A and dissolved at 60 ° C. Then, a uniform solution was prepared, and 1.0 g of surfactant (8) was added to 100 cc of this solution.
190 cc of a 6.6% aqueous solution of lime-processed gelatin heated to about 60 ° C. is added, and the mixture is homogenized with a homogenizer for 10 minutes.
The mixture was stirred and dispersed at rpm. Thus, a dye dispersion for the yellow filter layer, the intermediate layer and the antihalation layer was prepared.

[0155]

[Table 2]

[0156]

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The emulsions 1 to 1-R (including the red-sensitive spectral sensitizing dyes I, II and III) are contained in an emulsified dispersion containing a color developing agent and a coupler for a cyan color-forming layer having the composition shown in Table 1. ) Was added to obtain a coating solution for high sensitivity of the cyan coloring layer. Emulsions of other color-forming layers (for magenta and yellow color-forming layers and cyan color-forming low- and medium-speed layers) were prepared in the same manner as in the tabular emulsion preparation method described in JP-A-1-329231. Was adjusted. These emulsions A
To F are shown in Table 6. Emulsions A to F and the emulsified dispersions containing the color developing agents and couplers shown in Table 1 were combined as shown in Tables 3 to 5 to prepare coating solutions for color forming layers other than the cyan sensitive color forming layer. . Green-sensitive emulsions (for the magenta color-forming layer) include the following sensitizing dyes for green-sensitive emulsions IV, V, and VI as spectral sensitizing dyes, and blue-sensitive emulsions (for the yellow-coloring layer) include sensitizing dyes for blue-sensitive emulsions. VII was used. Using the above-mentioned dispersion or coating solution, coated samples having a color multilayer constitution shown in Tables 3 to 5 were prepared.

[0158]

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[0159]

[Table 3]

[0160]

[Table 4]

[0161]

[Table 5]

[0162]

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[0163]

[Table 6]

The prepared sample was stored at 25 ° C. and a relative humidity of 65% for 7 days and then cut. Next, processing materials P-1 and P-2 shown in Tables 7 and 8 below were produced.

[0165]

[Table 7]

[0166]

[Table 8]

[0167]

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[0168]

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[0169]

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<Evaluation> The photosensitive materials of Samples 101 to 118 were exposed to light at 1000 lux for 1/100 second through an optical wedge. Apply 40 ° C warm water to the exposed surface of the photosensitive material.
After applying 5 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, the sample exposed with the green filter has a wedge-shaped image of magenta color, and the sample exposed with the red filter has a wedge-shaped image of cyan. An image was obtained. These color samples were subjected to the second process (fixing process) using the processing material P-2. In the second step, 10 cc / m is added to the processing material P-2.
² was applied, the film was bonded to the photosensitive material after the first treatment, and heated at 60 ° C. for 30 seconds. The transmission density of a color sample obtained by using the emulsion of the present invention and the comparative emulsion in a high-sensitivity cyan coloring layer was measured with a red filter to obtain a so-called characteristic curve. Further, the exposure time was changed from 1/100 second to 10 seconds, and the same exposure amount was exposed, and a characteristic curve at the time of low illuminance exposure was also obtained. The reciprocal of the exposure amount corresponding to the density 0.15 higher than the fog density of the characteristic curve was defined as the relative sensitivity, and was expressed as a relative value with the value of the sample 101 at the time of 1/100 second exposure being 100. In order to make a comparison with the conventional liquid development, a sample similarly exposed at an exposure time of 1/100 seconds and 10 seconds was subjected to 38 ° C. using a processing CN-16 for color negative film manufactured by Fuji Photo Film Co., Ltd. Processing was performed under development conditions of 185 seconds. Table 10 shows the results.

[0171]

[Table 9]

[0172]

[Table 10]

As is evident from the results, when a tabular emulsion having a small grain thickness is prepared and used without using an iodide ion releasing agent, low illuminance failure occurs particularly during thermal development. However, particles were formed using the iodide ion releasing agent of the present invention,
An excellent sample with high sensitivity and low illuminance failure can be obtained only by using a tabular emulsion having a small grain thickness.

Example 2 A sample was produced in the same manner as in Example 1 except that the support was replaced with the support produced 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 After corona discharge treatment, UV discharge treatment, and further glow discharge treatment on both sides of the support, the weight of each component in the undercoat layer per unit area was gelatin. 0.1g /
m ² , 0.01 g / m ^{2 of} sodium α-sulfodi-2-ethylhexyl succinate, 0.04 g / m ² of salicylic acid
² , p-chlorophenol 0.2 g / m ² , (CH ₂ =
CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.012
g / m ^2, polyamide - so that the epichlorohydrin polycondensates 0.02 g / m ^2, by coating an undercoat solution (1
0 cc / m ² , using a bar coater) and an undercoat layer was provided on the high temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

3) Coating of Back Layer An antistatic layer having the following composition, a transparent magnetic recording layer, and a sliding layer were coated as a back layer on one surface of the support after the undercoat.

3-1) Coating of antistatic layer The weight of each component in the antistatic layer per unit area is tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm (specific resistance is 5 Ω · cm). )) (A secondary aggregated particle diameter of about 0.08 μm)
m ² , gelatin 0.05 g / m ² , (CH ₂ ＣＨCHSO
₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g / m ² ,
Poly (degree of polymerization 10) oxyethylene-p-nonylphenol was applied to give 0.005 g / m ² .

3-2) Coating of Transparent Magnetic Recording Layer The weight of each component in the magnetic recording layer per unit area 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, the surface of which is treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06
g / m ² , diacetyl cellulose (dispersant) 1.2 g /
_{^{m 2, C 2 H 5 C}} (CH 2 CONH-C 6 H 3 (C
H ₃₎ NCO) _{3 ^{(hardener) 0.3g / m 2, C 6}} H 13
CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (slip agent) 50 m
g / m ² , silica particles (matting agent) (particle size: 1.0 μm)
Abrasive aluminum oxide coated with 50 mg / m ² and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (particle size 0.2
(0 μm and 1.0 μm) Coating with a bar coater using acetone, methyl ethyl ketone, cyclohexanone, and dibutyl phthalate as a solvent so that the concentration becomes 10 mg / m ² (dispersion of iron oxide was performed by an open kneader and a sand mill), and a film was formed. A magnetic recording layer having a thickness of 1.2 μm was obtained. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.). The increase in the color density of the DB of the magnetic recording layer in the X-light (blue filter) is about 0.1, the saturation magnetization moment of the magnetic recording layer is 4.2 emu / g, and the coercive force is 7.3 × 10 ⁴ A /. m and the squareness ratio were 65%.

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 (6mg / m
² ) Silicone oil BYK-310 (manufactured by BYK Japan KK) was applied at 1.5 mg / m ² . The coating solution was prepared by melting the above-mentioned components in xylene / propylene glycol monomethyl ether (1/1) at 105 ° C., pouring and dispersing the mixture in propylene monomethyl ether (10-fold amount) at room temperature, and further dispersed in acetone. (Average particle size: 0.01 μm). 115 for drying
For 6 minutes (115 ° C. for all rollers and conveyors in the drying zone). The sliding layer has a dynamic friction coefficient of 0.10 (5 m
Stainless steel ball of mφ, load 100g, speed 6cm
/ Min), a coefficient of static friction of 0.08 (clip method) and a coefficient of dynamic friction between the emulsion surface and the sliding layer of 0.15.

Example 3 In the high-speed cyan color developing layer of Example 1, the emulsion 1-
Instead of using A to 1-R, Emulsion D containing I, II and III as sensitizing dyes was used.
A sample was prepared in the same manner as in Example 1 except that an emulsion was prepared in which the sensitizing dye of -R was replaced with the sensitizing dyes IV to VI for green-sensitive emulsion, and this was used for the high-sensitivity layer of the magenta coloring layer. When the same evaluation as in Example 1 was performed, good results were obtained, and the effect of the present invention was confirmed. Instead of using emulsions 1-A to 1-R in the high-sensitivity layer of the cyan color forming layer of Example 1, emulsion D containing I, II and III as sensitizing dyes was used. A sample was prepared in the same manner as in Example 1 except that an emulsion was prepared in which the sensitizing dye of 1-R was replaced with the sensitizing dye for blue-sensitive emulsion VII, and this emulsion was used for the high-sensitivity layer of the yellow coloring layer. When the same evaluation as in Example 1 was performed, good results were obtained, and the effect of the present invention was confirmed.

Example 4 In the emulsions 1-A to 1-R of Example 1, the average sphere equivalent diameter was 0.65 μm for the medium-speed layer and 0.49 μm for the low-speed layer.
The sensitizing dyes I to III are used for red-sensitive emulsions, sensitizing dyes IV to VI are used for green-sensitive emulsions, and sensitizing dyes are used for blue-sensitive emulsions. Using VII, a red-sensitive, green-sensitive and blue-sensitive emulsion for the medium-speed layer and an emulsion for the low-speed layer were prepared, and the same procedures as in Example 2 were carried out except that these emulsions were used in the respective layers in Example 2. A sample was prepared. Further, the same evaluation as in Example 2 was performed, but good results were obtained, and the effect of the present invention was confirmed.

Example 5 In Example 1, compounds (2), (11) and (63) were used in place of the iodide ion releasing agent of compound (58), and the temperature, pH, nucleophile species and concentration were used. Was prepared and particles were formed while controlling the iodide ion release rate. As in the case of the compound (58), good results were obtained, and the effect of the present invention was confirmed. In addition, the iodide Contr of the present invention
When dislocation lines are introduced into tabular grains using the old release method, the variation in grain formation and photographic performance with respect to the intensity of stirring and mixing in the reaction vessel during the introduction of dislocation lines compared to the conventional method in which an aqueous KI ion solution is added. Was extremely small, and a result with high robustness was obtained.

Example 6 In the preparation of each emulsion of Example 1, 2 × 10 ⁻⁵ mol / mol silver K ₄ [Fe (C) was used based on the total silver content of the grains when the outermost shell was formed.
N) ₆ ] is added together with the aqueous halogen solution,
_The same amount of K ₄ [Ru (CN) ₆ ] was added together with the aqueous halogen solution instead of ₄ [Fe (CN) ₆ ], but good results were obtained as in Example 1, confirming the effect of the present invention. .

[0184]

As described above, according to the present invention, it is possible to provide a heat-developable silver halide color photographic light-sensitive material capable of forming an image simply, quickly and with less environmental load. Further, it is possible to provide an excellent color photographic light-sensitive material method which can provide high sensitivity and good low illuminance reciprocity suitability even with simple and rapid processing.

Claims (16)

[Claims] 1. A light-sensitive material comprising a support having thereon at least one light-sensitive silver halide emulsion layer containing a light-sensitive silver halide emulsion, a color developing agent and a coupler, at least one silver halide emulsion. Are tabular grains in which a silver halide phase containing silver iodide is formed by generating iodide ions from an iodide ion releasing agent during grain formation, and all tabular grains of the silver halide emulsion are A silver halide color photographic light-sensitive material comprising silver halide tabular grains having an average aspect ratio of 2 to 50 and an average grain thickness of 0.05 to 0.3 μm. 2. A support comprising at least one photosensitive silver halide emulsion layer containing a light-sensitive silver halide emulsion and a dye-donating compound which releases or diffuses a diffusible dye corresponding to or inversely corresponds to silver development. In a light-sensitive material comprising at least one silver halide emulsion, a silver halide phase containing silver iodide is formed by generating iodide ions from an iodide ion releasing agent during grain formation. Grains, and further all tabular grains of the silver halide emulsion are:
A silver halide color photographic light-sensitive material comprising silver halide tabular grains having an average aspect ratio of 2 to 50 and an average grain thickness of 0.05 to 0.3 µm. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the average grain thickness of all tabular grains of the silver halide emulsion is 0.05 to 0.2 μm. 4. The silver halide color photographic light-sensitive material according to claim 1, wherein the average grain thickness of all tabular grains of the silver halide emulsion is 0.05 to 0.15 μm. 5. The silver halide emulsion according to claim 1, wherein 100 to 80% (number) of all grains of the silver halide emulsion are occupied by tabular silver halide grains having 10 or more dislocation lines per grain. 5. The silver halide photographic light-sensitive material according to any one of items 1 to 4, 6. The silver halide emulsion according to claim 1, wherein 100 to 50% (number) of all the grains of the silver halide emulsion are occupied by silver halide tabular grains having 50 or more dislocation lines per grain. 5. The silver halide photographic light-sensitive material according to any one of items 1 to 4, 7. A silver halide emulsion wherein 100 to 80% (number) of all grains of the silver halide emulsion are occupied by silver halide tabular grains having dislocation lines localized substantially only in the fringe portions of the grains. The silver halide photographic light-sensitive material according to claim 5 or 6. 8. The silver halide emulsion wherein 100 to 80% (number) of all grains are occupied by silver halide tabular grains having dislocation lines localized substantially only at the apex of the grains. The silver halide photographic light-sensitive material according to claim 5 or 6. 9. The halide according to claim 1, wherein the coefficient of variation of the silver iodide content distribution between grains of the silver halide emulsion is 3 to 20%. Silver photographic photosensitive material. 10. The silver halide according to claim 1, wherein the variation coefficient of the equivalent circle equivalent diameter distribution of all tabular grains of the silver halide emulsion is 3 to 25%. Photosensitive material. 11. In the silver halide emulsion, hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.5 to 1 occupy 100 to 70% of the projected area of all grains. The silver halide photographic material according to any one of claims 1 to 9, which is an emulsion. 12. The method according to claim 1, wherein the tabular grains of the silver halide emulsion contain one or more photographically useful metal ions or complexes in the grains. Silver halide photographic material. 13. The method according to claim 1, wherein the iodide ion releasing agent is represented by the following general formula (1).
5. The silver halide photographic material according to any one of the above. Embedded image In the formula (1), R represents a monovalent organic residue which releases an iodine atom in the form of an iodide ion by reaction with a base and / or a nucleophile. 14. The silver halide photographic light-sensitive material according to claim 1, wherein the iodide ion releasing agent is used in the presence of an iodide ion releasing regulator. 15. The developing agent according to the following general formula (2)
15. The silver halide color photographic light-sensitive material according to claim 1, which is at least one of the compounds represented by (6). Embedded image 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, alkylcarbamoyl, arylcarbamoyl, carbamoyl, alkylsulfamoyl, arylsulfamoyl, sulfamoyl, cyano, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl, aryloxycarbonyl , An alkylcarbonyl group, an arylcarbonyl group, or an acyloxy group, and R ₅ represents a substituted or unsubstituted 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 a substituted or unsubstituted 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, and R ₇ and R ₈
And may combine with each other to form a double bond or a ring. 16. A method comprising the steps of: exposing the photosensitive material to light and exposing a processing material comprising a support and a constituent layer including a processing layer containing a base and / or a base precursor, and a back layer 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 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 are processed. The photosensitive layer according to any one of claims 1 to 15, wherein an image is formed by bonding the surfaces of the processing layers of (1) to (3) and heating the same at a temperature of 60 ° C to 100 ° C for 5 seconds to 60 seconds. Material development method.