JPH10228070A - Silver halide color photographic sensitive material and color image forming method using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sensitive material fit for easy rapid processing, having high sensitivity and ensuring low fog. SOLUTION: The top of a substrate is coated with photographic constituent layers including at least on photosensitive layer contg. photosensitive silver halide emulsions, a developing agent, a compd. forming a dye by coupling reaction with the oxidized body of the developing agent and a binder to obtain the objective silver halide color photographic sensitive material forming an image in which part or all of unreacted silver halide remains by heat development and subjected to the reading of the image. At least one of the photosensitive silver halide emulsion contains one or more kinds of ions selected from among metallic ions and metallic complex ions with <=0.2eV depth as electron trap and flat platy photosensitive silver halide particles having <=0.2μm average thickness and an average aspect ratio of 3-100.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material and a color image forming method using the same. The present invention relates to a silver halide color photographic light-sensitive material for high-sensitivity photography capable of forming an image stable to light and a color image forming method using the same.

[0002]

2. Description of the Related Art A photographic method using silver halide is superior to other photographic methods such as electrophotography and diazo photography in photographic characteristics such as sensitivity, gradation control and resolution, and thus has been the most widely used. Has been used for At present, high quality color images can be easily and inexpensively obtained using silver halide. For example, a color photograph (color print) is obtained by optically printing image information of a developed photographic film on color photographic paper. In particular, the negative-positive method using a negative film and color paper, using a negative film with a wide exposure latitude, the photographer's failure due to exposure mistakes is small,
The feature is that many prints can be obtained at low cost. Due to such features, this process has been highly developed in recent years, and is a so-called mini lab which is a small and simple printer processor installed in a color lab or a store, which is a large-scale centralized base for producing large amounts of color prints with high efficiency. With the spread of, anyone can easily enjoy color photos.

More recently, an APS system using a color negative film capable of magnetically recording various information using a support coated with a magnetic material has been announced. This A
With the PS system, handling of the film is simplified,
Since information at the time of photographing is magnetically recorded, high quality prints can be obtained. On the other hand, there is also provided a tool that can read a processed negative film with a scanner and edit and process image information.

In a general color film photosensitive material, a silver halide photosensitive layer having sensitivity to three primary colors of light, blue, green and red, is coated on a transparent support. The photosensitive layer contains a coupler capable of forming a complementary color of yellow, magenta or cyan by coupling with an oxidized form of the developing agent. The principle of color development by color development is that an aromatic primary amine developing agent contained in a color developing agent develops or reduces the exposed silver halide particles to generate developed silver, and at the same time, the developing agent generated The oxidant undergoes a coupling reaction with a so-called coupler in the color film light-sensitive material to form a dye, thereby producing color. And, metallic silver (developed silver) generated by development,
By removing unreacted silver halide by bleaching and fixing, respectively, a dye image is obtained. Next, optical exposure is performed through a color negative film after development processing on a color photographic paper, which is a color photographic material in which a photosensitive emulsion layer having a similar combination of a photosensitive wavelength region and a coloring hue is coated on a reflective support. By performing the same color development and bleaching / fixing processes, a color print composed of a dye image reproducing the original scene (at the time of photographing) can be obtained.

Recently, a method of photoelectrically reading a captured image recorded on the color negative film with a scanner or the like, performing image processing to obtain image information for writing, and recording the image information on another hard copy material is also available. Are known.
In particular, the image information is converted into a digital signal, and the recording light (particularly, laser light) modulated in accordance therewith is scanned and exposed to a photosensitive material such as a color photographic paper to reproduce an original (at the time of shooting) scene. . An example of such a digital photo printer is described in JP-A-7-15593 and the like. A digital photo printer system using color paper is sold as Fuji Photo Film's digital lab system frontier. By digitally processing an image, underexposure and defocusing of a negative film can be instantaneously corrected, and a high-quality color image can be obtained more easily.

[0006] Although systems for obtaining such color prints are now widespread, demands for simpler, less environmentally harmful, and faster methods are increasing. The first reason is that the processing bath for performing the above-described color development / development and bleaching / fixing processing requires precise control of its composition and temperature, and requires specialized knowledge and skilled operations. Is required. Secondly, the processing solution in the processing bath contains a substance that needs to be regulated for discharge due to environmental problems such as a color developing agent and an iron chelate compound as a bleaching agent. This is because dedicated equipment is often required. Third, although the development process in recent years has been shortened, these development processes require time, and it cannot be said that it is still insufficient for the demand for quickly reproducing a recorded image. .

[0007] From such a background, a color image excellent in simplicity and immediateness is reduced without using a color developing agent or a bleaching / fixing agent used in an existing color image forming system, thereby reducing the burden on the environment. There is an increasing demand for building forming systems. For example, an instant system having an alkaline processing liquid in a photosensitive material, and a system capable of easily and quickly obtaining an image by thermal development processing by heating or the like have been developed from the viewpoint of environmental protection. Such photothermographic materials are described in “Basics of Photographic Engineering (Non-Silver Photography), Corona”, p.
255 pages, JP-B-43-4921, JP-B-43-49
No. 24, etc.

As products using the instant system, Fuji Photo Film Co., Ltd. sells instant color films ACE and FI-800GT, Polaroid Co., Ltd., and Polaroid. As a product using thermal development, in the color system, Fuji Photo Film Co., Ltd. has commercially available devices such as Pictography 3000, Pictrostat 100, 200 and 300, and a donor photosensitive material dedicated to the system. And image receiving materials are commercially available. This method is called a pictocolor method. In these systems, a color image is formed on an image receiving element, and the unreacted silver halide is in a separate sheet or a layer separated by a light-shielding layer, so that a bleaching / fixing step is not required.

Regarding the reduction of the environmental load of the bleach-fixing process, IS &T's 48th Annual Conf
page 180 of the issue Processes
A system that removes developed silver and unreacted silver halide by removing the dye generated in the development reaction to the mordant layer and then peeling it off, eliminating the need for a bleach-fix bath that was essential for conventional color photographic processing. Is disclosed. A technique of incorporating a fixing agent into a photosensitive material as an image stabilizer is disclosed in US Pat.
No. 12260, JP-A-57-150842 and JP-A-57-150842.
Although it is disclosed in JP-A-154173 and JP-A-8-69097, it tends to cause desensitization, decrease in maximum density, and deterioration of raw storage stability. Further, a bleach-fixing sheet is disclosed in JP-A-62-115.
No. 45 and the like. However, in the techniques proposed in these, development processing in a processing bath containing a color developing agent is still necessary, and it cannot be said that environmental problems have been solved.

The one using the instant system is a recording material for photographing, and an image can be obtained immediately. However, the degree of freedom in the format size is poor. However, there is a problem that it takes much time, is accompanied by deterioration of image quality, and is expensive. Since the above-mentioned heat development of the pictocolor method is used for fixing the formed dye to the image receiving material and appreciating this as a dye image, it is not used as a recording material for photography. Did not. Therefore, there has been a long-felt need for a recording material for photographing that simplifies both the development and bleaching / fixing steps at once, and has a low environmental load and can obtain a large number of prints at low cost.

Then, using a developing agent, a compound which forms a dye by a coupling reaction with an oxidized form of the developing agent, and a silver halide emulsion for high-sensitivity photographic exposure, utilizing a base generation method of a pictocolor method, When an attempt was made to perform heat development, a color image was obtained. However, in this color image, unreacted silver halide emulsion grains remain. Even if the color image is optically exposed as it is, only a low-quality color image that cannot withstand viewing is obtained. Recent advances in scanners (eg, Fujifilm Frontier) have made it easy to obtain high-quality images without the need for a fixing process. Disappeared.

In the case of an image with reduced contrast, even if an attempt is made to reproduce the original scene on a photosensitive material for printing, only an image that cannot withstand viewing is obtained, and image information read by a scanner or the like is corrected and reproduced in a hard copy. However, only low-quality images can be obtained. Deterioration of image storability makes it difficult to repeatedly read an image, which is problematic. This increase in density during image storage is due to the fact that the remaining silver halide is photolyzed to metallic silver and blackened (printout), and the resulting developing agent oxide reacts with the coupler. (Hereinafter referred to as "post-development"). Even when a color image is used as in the present system, by preventing printout, color development can be suppressed. Naturally, this printout process is more likely to occur in emulsions with high sensitivity, so prevention of printout is a serious problem in photographic light-sensitive materials.

Various image stabilizers have been disclosed for preventing printout. For example, Research Disclosure Magazine (hereinafter abbreviated as “RD”), 17029, Section 8 (1987), RD29963 (1989), and R
D22435 (1982), U.S. Pat.
No. 4,288,536, No. 5,358,843, No. 5,300,420, No. 536,000, No. 44
59350, JP-A-6-130544, JP-A-8-
No. 184936. These compounds are
Halogen compound, mercapto compound and its precursor, N
In the case of high-sensitivity emulsions such as the present system, the addition of an amount that maintains image stability after processing causes problems such as desensitization, lowering of the maximum density, and devitrification. When added to such an extent that it is not allowed to occur, the image stabilizing ability is weak.

JP-A-8-137073 discloses a photothermographic material using a silver halide emulsion prepared using a polymer having a thioether structure in a side chain as a protective colloid at the time of grain formation. It is disclosed that it is effective. However, in the case of a high-sensitivity photographic material such as a binder for a silver halide photosensitive layer, prevention of printout is insufficient.

As described above, simple and rapid processing by thermal development is performed using a high-sensitivity photographic photosensitive material to form a color image with unreacted silver halide remaining. Degradation of image stability after processing, such as increased stain, increased color, and reduced contrast, has been a significant obstacle.

[0016]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention does not require a bleaching / fixing step,
It is an object of the present invention to provide a silver halide color photographic light-sensitive material for high-sensitivity photography capable of easily and quickly forming a stable image with respect to light with little load on the environment and a color image forming method using the same.

[0017]

The present invention is based on the following findings as a result of intensive studies by the present inventors to achieve the above object. That is, according to the present invention, when an image based on a non-diffusible dye is formed on a photosensitive material, an image having excellent granularity and sharpness is obtained. Based on this image information, another image such as a color paper or a heat-developed color print material is obtained. It is a finding that when output on a recording material, a very good color image can be obtained.

Means for solving the above problems are as follows. That is, <1> at least one photosensitive layer containing a photosensitive silver halide emulsion, a developing agent, a compound that forms a dye by a coupling reaction with an oxidized form of the developing agent, and a binder on a support. A silver halide color photographic light-sensitive material in which a photographic component layer containing a silver halide is coated and developed by heating to form an image in which some or all of the unreacted silver halide remains and the image is read. , At least one of the photosensitive silver halide emulsions has a depth of 0.
A plate-like photosensitive material containing at least one selected from a metal ion and a metal complex ion as an electron trap of 2 eV or less, having an average thickness of 0.2 μm or less, and an average aspect ratio of 3 to 100. A silver halide color photographic light-sensitive material comprising silver halide grains. <2> The metal ions and metal complex ions which are electron traps having a depth of 0.2 eV or less are Pb ions and ions containing a cyan ligand and Re, Os, Ru, Fe, Ir, or Co. <1> The silver halide color photographic light-sensitive material described in <1>. <3> The photosensitive silver halide emulsion contains 50 parts of silver chloride.
The silver halide color photographic light-sensitive material according to <1> or <2>, which contains at least mol%. <4> The developing agent is represented by the following general formula (1), general formula (2), general formula (3), general formula (4) or general formula (5)
The silver halide color photographic light-sensitive material according to any one of <1> to <3>, wherein

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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In the general formulas (1) to (5), R _{1 to} R ₄ are
Hydrogen atom, halogen atom, alkyl group, aryl group, alkylcarbonamide group, arylcarbonamide group,
Alkylsulfonamide, arylsulfonamide, alkoxy, aryloxy, alkylthio, arylthio, alkylcarbamoyl, arylcarbamoyl, carbamoyl, alkylsulfamoyl, arylsulfamoyl, sulfamoyl, cyano Group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, or acyloxy group. R ₅ represents a substituted or unsubstituted alkyl group, aryl group or 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. R ₇ and R ₈ may be bonded to each other to form a double bond or a ring.

<5> After exposing the silver halide color photographic light-sensitive material, 1/1 of the total water amount required for the maximum swelling of all the coating films in the silver halide color photographic light-sensitive material.
0 to 1 times the amount of water is interposed between the silver halide color photographic light-sensitive material and the processing material containing a base and / or a base precursor on a support, and heat development is carried out in a state where both are adhered to each other. To form a color image on the silver halide color photographic light-sensitive material, while leaving some or all of the unreacted silver halide in the silver halide color photographic light-sensitive material, In a color image forming method for reading a color image on a photographic light-sensitive material and forming a color image based on the read image information, the silver halide color photographic light-sensitive material may be any one of the above <1> to <
<4> A color image forming method, characterized in that the material is the silver halide color photographic light-sensitive material described in any one of <4> and <4>. <6> After exposing the silver halide color photographic light-sensitive material, 1/10 to 1 times the amount of water required for the maximum swelling of all the coating films in the silver halide color photographic light-sensitive material is replaced with the halogen. The silver halide color photographic light-sensitive material is interposed between a processing material containing a base and / or a base precursor on a support, and heat development is performed in a state where both are adhered to each other. To form a color image, while leaving some or all of the unreacted silver halide in the silver halide color photographic light-sensitive material,
In a color image forming method for reading a color image on the silver halide color photographic material with a scanner and printing out the image based on the image information, the silver halide color photographic material may be any one of the above <1> to <4>. A color image forming method, which is the silver halide color photographic light-sensitive material described in any one of the above.

In the present invention, since the photosensitive material and the base are isolated until the time of development, rapid development processing is possible while satisfying the high storage stability required for the photographic material. The present invention, compared with the case of using a dye-releasing compound,
Since a colorless color developing agent and a coupler are used, they are advantageous in terms of sensitivity, which is extremely important as a photographic material. Also,
In the present invention, image information is photoelectrically read by measuring the density of transmitted light from image information in which developed silver and residual silver halide are present, and a print image is output based on the signal. The output material does not have to be a photosensitive material,
For example, a sublimation type thermosensitive recording material, an ink jet material, an electrophotographic material, a full color direct thermosensitive recording material, or the like may be used. In the present invention, after forming a color image by thermal development, without performing an additional process of removing the remaining silver halide and developed silver, the image information is transmitted by diffuse light and transmission density measurement using a CCD image sensor. It is preferable that the image is photoelectrically read, converted into a digital signal, subjected to image processing, and output using a heat development color printer, for example, a photography 3000 of Fuji Photo Film Co., Ltd.
In the present invention, good prints can be obtained quickly without using any processing solution used in conventional color photography. Also, since the digital signal can be arbitrarily processed and edited, the photographed image can be freely modified, deformed, processed, etc. and output.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A photosensitive silver halide emulsion used in a silver halide color photographic light-sensitive material of the present invention will be described. In order to enhance the image storage stability after the heat development processing without performing the fixing processing, which is the object of the present invention,
An emulsion comprising tabular photosensitive silver halide grains containing at least one selected from metal ions and metal complex ions, having an average thickness of 0.2 μm or less and an average aspect ratio of 3 to 100. Is used. By the way, conventionally, a technique of including a metal ion and / or a metal complex ion (hereinafter sometimes referred to as “metal ion or the like”) in silver halide emulsion grains is well known among those skilled in the art. However, these techniques require processing using a processing solution containing a developing agent for the purpose of increasing sensitivity, adjusting reciprocity, controlling gradation, improving storage stability of latent images, and reducing temperature dependence during exposure. The above-described metal ions and the like are used as a photosensitive material for photographing and a photosensitive material for printing by heat development, and are completely different from the technology relating to the silver halide color photographic photosensitive material of the present invention. In a high-sensitivity photosensitive material for photography, which is subjected to heat development, high sensitivity is obtained by adding a metal ion, which is a shallow electron trap, to an emulsion composed of tabular photosensitive silver halide grains having a thickness of 0.2 μm or less. The effect of the present invention of improving the image storage stability after processing while maintaining the effect has not been known so far,
As a result of intensive studies by the inventors of the present invention, they have been found for the first time.

Next, metal ions and metal complex ions which are electron traps having a depth of 0.2 eV or less and which are used in the photosensitive silver halide emulsion of the present invention will be described. Such metal ions and metal complex ions, for example, Pb ^2+, include _{[M (CN) x L y} N z]. In the above formula, M is Re ⁺ , Os2 ⁺ , Ru2 ⁺ , Fe
Represents ²⁺ , Ir ³⁺ or Co ³⁺ . X represents 4, 5 or 6. L and N are halogen ions such as fluorine ion, chlorine ion, bromine ion and iodine ion, SCN ⁻ , NC
Represents an inorganic ligand such as S ⁻ , H ₂ O or the like; or an organic ligand such as pyridine, phenanthroline, imidazole, pyrazole and the like. y and z are numerical values, and their values are determined so as to satisfy x + y + z = 6. Usually, when a ligand is present, the coordination number is six.

The value of the depth of the electron trap by the metal ion or the like can be found in, for example, Phys. Stat. Sol (b), Vol. 88, p.
Kinetic measurements using ESR, as disclosed in US Pat. The depth of the electron trap depends on the type of central metal ion, the type of ligand, and the symmetry (O
h, D4h, C4v, etc.), and can vary with the halogen composition of the substrate. The depth of the electron trap, the energy level of the lowest unoccupied orbit of electrons of metal ions or metal complex ions,
It is determined depending on whether it is lower or higher than the bottom of the conduction band of silver halide. When the energy level is higher than the bottom of the conduction band of silver halide, the electrons are loosely bound by the Coulomb force of the central metal ion, so that a shallow electron trap is obtained.
If it is low, the energy difference from the conduction band corresponds to the depth of the electron trap, resulting in a relatively deep electron trap.

The addition amount of the metal ion and / or metal complex ion in the photosensitive silver halide emulsion is about 10 ^-9 to 10 ^-2 mol per mol of silver halide. In the photosensitive silver halide emulsion grains, the metal ions and / or metal complex ions (hereinafter sometimes referred to as “metal ions or the like”) are incorporated into the grains in a uniform state or a localized state. May be incorporated in a state where it is exposed on the surface of the particle, or may be incorporated in a state where it is not exposed on the surface of the particle but localized near the surface. In addition, in the case of epitaxial grains, the crystal may be a base crystal or a crystal at a junction. In the multi-structure type photosensitive silver halide emulsion grains having different phases of the halogen composition, the metal ions to be contained may be changed for each composition.

The metal ions and the like may be added by mixing a metal salt solution such as the metal ions with an aqueous halide solution or a water-soluble silver salt solution at the time of grain formation, and continuously adding them during grain formation. Silver halide emulsion fine particles doped with metal ions or the like can be added, or a metal salt solution of the metal ions or the like can be directly added before, during, or after grain formation. During particle formation, a solution of a metal salt such as the metal ion may be continuously added.

When the metal salt is dissolved in water or a suitable solvent such as methanol or acetone, an aqueous solution of hydrogen halide (eg, HCl, HBr) is used to stabilize the solution.
Thiocyanic acid or a salt thereof, or an alkali halide (eg, KCl, NaCl, KBr, NaBr)
Etc.) can be used. It is also preferable to add an acid, an alkali or the like as necessary from the viewpoint of stabilizing the solution.

The content of the metal ions and the like in the photosensitive silver halide emulsion is measured by, for example, atomic absorption, polarized Zeeman spectroscopy, ICP analysis and the like. Ligands of the metal complex ions, CN ⁻ , SCN ⁻ , NO ⁻
And the like in a photosensitive silver halide emulsion are confirmed by infrared absorption (especially FT-IR).

The halogen composition in the photosensitive silver halide emulsion usable in the present invention is preferably silver chloride, silver iodochloride, silver chlorobromide, silver iodochlorobromide, or silver iodobromide. Can be used. Further, other silver salts, for example, organic silver such as silver thiocyanate, silver sulfide, silver selenide, silver carbonate, silver phosphate, and silver benzotriazole may be solid-solved in the halide grains, and may be bonded. It may be. The halogen composition may be uniform or may be different between the inside of the grain and the grain surface. In the latter case, the silver halide emulsion grains are grains having a multiple structure or a multilayer structure. Further, silver halide emulsions having different compositions may be joined by epitaxial joining.

Incidentally, high silver chloride emulsions generally have the feature of having high development activity. In addition, since there is little haze, there is also a feature that when the processed photosensitive material is read by a scanner without being fixed, there is little deterioration of image information.

A structure having a localized phase having a different composition in a layered or non-layered form inside and / or on the surface of silver halide can also be used. The halogen composition of the localized phase is analyzed by an X-ray diffraction method, an analytical electron microscope, or the like. For example, C.R.Berry, S.J.Marino (CR Ber)
ry, S.R. J. Photographic by Marino
Science and Technology (Photogra
phic Science and Technology
gy) Vol. 2, p. 149 (1955) and Vol. 4, p. 22 (1
957) describes a method of applying X-ray diffraction to silver halide. The localized phase is located inside the particle or at the edge of the surface,
Although it may be present at the corners or on the surface, a preferred example is one in which the grains are epitaxially bonded at the corners.
JP-A-9-133540, JP-A-59-119350, JP-A-6-194768, European Patent 069
No. 9944 and the like.

As in the case of the present photographic light-sensitive material, a light-sensitive silver halide emulsion mainly containing silver iodobromide may contain silver chloride. The rate is preferably 8 mol% or less, more preferably 3 mol% or less. In the present invention, silver iodobromide having a laminated structure composed of a plurality of layers having different halogen compositions, and more silver iodide than any of the layer adjacent to the inner side of the grain and the layer adjacent to the surface of the grain. It is preferred to use photosensitive silver halide emulsion grains containing therein grains having at least one layer having a high content of the silver halide emulsion.

When a photosensitive silver halide emulsion composed of silver chlorobromide, silver chloride or the like is used, it may contain silver iodide. In that case, the content of silver iodide is 6 mol%. Or less, more preferably 2 mol% or less. When a high silver chloride emulsion is used, it is disadvantageous in terms of sensitizing dye adsorption. However, dye adsorption can be enhanced by making the surface rich in silver iodide or silver bromide.

The halogen composition on the surface of the photosensitive silver halide emulsion grains is measured by X-ray photoelectron spectroscopy (ESCA).

It is preferable that the halogen composition distribution (silver bromide content, silver iodide content, silver chloride content) between the photosensitive silver halide emulsion grains is narrow. The variation coefficient of the halogen composition distribution is preferably 3 to 30%, more preferably 3 to 25%, and particularly preferably 3 to 20%. The variation coefficient means a value obtained by dividing a variation (standard deviation) by an average. The halogen composition distribution in each photosensitive silver halide emulsion can be determined, for example, by using an X-ray microanalyzer (EP
MA).

The shape of the tabular photosensitive silver halide grains in the photosensitive silver halide emulsion is such that when the main surface (the outer surface having a large parallel area) is a (111) plane, two parallel twin planes are formed. One or more parallel multiple twins with an outer surface of (1
In the case of a (00) plane, there is no twin plane. The twin plane spacing can be set to 0.012 μm or less as described in US Pat. No. 5,219,720. Further, as described in JP-A-5-249585, (111) The value obtained by dividing the distance between the main planes by the twin plane spacing may be 15 or more. When the main plane is the (111) plane, the shape of the photosensitive silver halide emulsion grains as viewed from above is triangular, hexagonal, rounded, or circular. Even when the main plane is (111), the side surface connecting the main plane is
It may be a (111) plane, a (100) plane, a mixture of both, or a plane having a higher index. When the outer surface is the (100) plane, the shape of the photosensitive silver halide emulsion grains as viewed from above is as follows:
It has a rectangular shape.

The photosensitive silver halide emulsion used in the present invention has tabular photosensitive silver halide grains having a total projected area of 80%.
It preferably occupies １００100%, more preferably occupies 90-100%, and particularly preferably occupies 95-100%.

The average grain thickness of the tabular photosensitive silver halide grains in the photosensitive silver halide emulsion used in the present invention is preferably from 0.005 to 0.2 μm, more preferably from 0.01 to 0.2 μm.
0.15 μm is more preferred. The average grain thickness means the arithmetic average of the grain thicknesses of all tabular grains in the photosensitive silver halide emulsion.

The average equivalent projected area circle diameter of the tabular photosensitive silver halide grains in the photosensitive silver halide emulsion is preferably from 0.2 to 8 μm, more preferably from 0.3 to 5 μm, and more preferably from 0.4 to 5 μm. 4 μm is particularly preferred.

The ratio of the circle-equivalent diameter to the average thickness of the tabular photosensitive silver halide grains in the photosensitive silver halide emulsion is referred to as an aspect ratio. The average aspect ratio of the tabular photosensitive silver halide emulsion grains in the present invention is preferably from 3 to 100, and more preferably from 6 to 80. The average aspect ratio means the arithmetic average of the average aspect ratios of all tabular grains in the photosensitive silver halide emulsion.

When the projection surface of the tabular photosensitive silver halide grains in the photosensitive silver halide emulsion is rectangular, the ratio of the maximum length to the minimum length is 1%.
~ 2 tabular grains account for 50-100% of the projected area of all grains
And preferably 70 to 100%. The ratio is preferably a square tabular grain close to 1.

The shape of the photosensitive silver halide emulsion grains is determined by a carbon replica method in which the photosensitive silver halide emulsion grains and a reference latex sphere used as a size standard are simultaneously shadowed with a heavy metal or the like. It can be measured by observation with a transmission electron microscope.

It is preferred to use a monodispersed light-sensitive silver halide emulsion having a narrow grain size distribution. The monodispersed light-sensitive silver halide emulsion means one having a variation coefficient of grain size distribution of 30% or less. The use of the monodispersed light-sensitive silver halide emulsion is described in Surfer Science Series (Technical Applications of Dispersions) by Trevor Matanahan.
rfactant Science Series) 5
2, p. 373 (1994). Further, a polydispersed photosensitive silver halide emulsion having a wide grain size distribution may be used. In addition, as disclosed in JP-A-1-167743 and JP-A-4-223463, two or more types of monodisperse particles having substantially the same color sensitivity and different particle sizes are used for adjusting the gradation. A photosensitive silver halide emulsion may be used in combination. Two or more monodispersed photosensitive silver halide emulsions may be mixed in the same layer or may constitute separate layers. Two or more polydisperse photosensitive silver halide emulsions or a combination of a monodisperse photosensitive silver halide emulsion and a polydisperse photosensitive silver halide emulsion can also be used.

A method for preparing tabular grains using silver bromide, silver (iodo) bromide, and silver (salt) bromide comprising the (111) plane is described in JP-A-55-142329 and JP-A-58-113926. Nos. 58-113927 and 58-11392.
8, U.S. Pat. No. 4,914,014, U.S. Pat. No. 4,942,120, JP-A-2-222940, U.S. Pat. No. 5,136,641, and U.S. Pat.
No. 4306. Among these,
U.S. Pat. Nos. 5,147,771 to 5,177,659,
Tabular grain forming methods using the polyalkyl oxide compounds described in the specifications of JP-A-52110013 and JP-A-5252453 are preferred. To form tabular grains in a photosensitive silver halide emulsion having a high average aspect ratio,
It is important to generate twin nuclei of small size. For this purpose, low temperature, high pBr and low pH are used, the amount of gelatin is reduced, and methionine with a low or low molecular weight or a phthalated gelatin derivative is used. It is preferred to carry out the formation. After nucleation, tabular grain nuclei (parallel multiple twin nuclei) are obtained by physical ripening.
Only the nuclei of normal crystals, single twin nuclei, and non-parallel multiple twin nuclei are eliminated to selectively form parallel multiple twin nuclei. Thereafter, a soluble silver salt and a soluble halide salt or a small-sized silver halide fine grain emulsion is added, and the grains are grown to prepare a photosensitive silver halide emulsion containing tabular grains.

A method for preparing silver bromide or (salt) silver bromide tabular grains consisting of (100) faces is described in US Pat.
No. 063951, JP-A-58-9 by A. MIGNOT
No. 5337.

Tabular grains composed of a high silver chloride emulsion composed of (111) planes are described in US Pat. No. 4,399,215, US Pat.
These are described in JP-A-400463, JP-A-5217858, JP-A-2-32 and the like. In the case of high silver chloride, since the (100) plane is usually the outer surface under the condition where there is no adsorbed substance, the adsorbed substance having plane selectivity is used for the (111) plane and twin nuclei are formed. In the physical ripening process, normal crystal nuclei, single twin nuclei, and non-parallel multiple twin nuclei are eliminated to selectively obtain parallel multiple twin nuclei, and then the grains are grown to form tabular grains. A light-sensitive silver halide emulsion is prepared.

The empirical rule for forming silver chloride tabular grains composed of (111) planes is described in Journal of Photographic Science.
36, p. 182 (1988).

Tabular grains composed of high silver chloride emulsion grains having (100) planes are described in US Pat. No. 4,946,772,
JP-A-5275930, JP-A-5264337, JP-A-5-281640, JP-A-5-313
273 and EP 0534395 A1. The point is the generation of nuclei that grow in a plate shape, and it is effective to add bromide ions or iodide ions in the early stage of grain formation, or to add a compound exhibiting selective adsorption to a specific surface. . After nucleation, physical ripening and grain growth are performed to prepare a photosensitive silver halide emulsion containing tabular grains. The grain growth is carried out by adding a soluble silver salt and a soluble halide salt, or a small-sized silver halide fine grain emulsion.

Such tabular grains have a larger surface area than normal crystals of the same volume, so that the adsorption amount of the sensitizing dye can be increased, which is advantageous in terms of color sensitization sensitivity. Therefore, since the volume of the particles can be reduced at the same sensitivity as compared with the normal crystal grains, the number of development start points increases with an increase in the number of particles, and the graininess, which is a critical performance in a photographic material for photography, is excellent. In addition, since the granularity is advantageous, the amount of coated silver can be reduced, which is excellent in suppressing radiation fog which is a problem of a photosensitive material for high-sensitivity photography. The reduction in the amount of coated silver is effective in reducing the haze that causes deterioration of image information when the processed photosensitive material is read by a scanner without being fixed, as described later. Since tabular grains have a large specific surface area, they have the feature of having high development activity. Further, since the tabular grains are aligned and aligned at the time of coating, the photosensitive material can be made thinner, and the sharpness is excellent.
As described above, tabular grains are essential emulsion grains in a photographic material for photography. As long as the pressure property and the monodispersibility of the particle distribution are not impaired, it is preferable that the average aspect ratio of the tabular grains is large in terms of sensitivity, granularity, activity, reduction of the amount of coated silver, and the like.

The tabular photosensitive silver halide grains in the photosensitive silver halide emulsion used in the present invention may have dislocation lines. The dislocation line, on the sliding surface of the crystal,
A linear lattice defect at the boundary between an already slipped area and an unslid area.

Regarding the dislocation lines of the crystals of the photosensitive silver halide emulsion, 1) C.I. R. Berry, J.M. Appl. P
hys. , 27, 636 (1956), 2) C.I. R. B
erry, D.E. C. Skilman, J .; Appl. P
hys. , 35, 2165 (1964), 3) J. F.
Hamilton, Photo. Sci. Eng. , 1
1, 57 (1967), 4) T.I. Shiozawa,
J. Soc. Photo. Sci. Jap. , 34,16
(1971), 5) T.I. Shiozawa, J .; So
c. Photo. Sci. Jap. , 35, 213 (19
72), etc., which can be analyzed by an X-ray diffraction method or a direct observation method using a low-temperature transmission electron microscope.

When the dislocation lines are directly observed using a transmission electron microscope, the photosensitive silver halide emulsion grains should be kept under pressure not to generate the dislocation lines. The silver halide grains taken out from the grains can be placed on a mesh for observation with an electron microscope, and observed 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 photosensitive silver halide emulsion grains, the more difficult it is for an electron beam to pass. Therefore, it is clearer to use a high-pressure electron microscope (200 kV or more for a thickness of 0.25 μm). Can be observed.

JP-A-63-220238 describes a technique for introducing dislocation lines in silver halide grains while controlling the dislocation lines. It is shown that the tabular grains into which the dislocation lines are introduced have excellent photographic characteristics such as sensitivity and reciprocity law as compared with the tabular grains without the dislocation lines.

In the case of tabular grains, the position and number of dislocation lines of each grain as viewed from the direction perpendicular to the main plane are determined from the photograph of the grains taken with an electron microscope as described above. Can be.

When the tabular grains in the light-sensitive silver halide emulsion used in the present invention have dislocation lines, their positions are limited to, for example, the apexes and fringe portions of the grains, or are introduced over the entire main plane portion. Any of these can be appropriately selected from among them, but it is particularly preferable to limit to the fringe portion.

In the present invention, the fringe portion means the outer periphery of the tabular grains. More specifically, the fringe portion is the first point in the distribution of silver iodide from the sides to the center of the tabular grains as viewed from the side. Is outside the point where the silver iodide content exceeds or falls below the average silver iodide content of the whole grain.

In the present invention, when the tabular grains have dislocation lines, the density of the dislocation lines is arbitrary and can be appropriately selected depending on the case, such as 10 or more, 30 or more, 50 or more per grain. .

The light-sensitive silver halide emulsion containing tabular light-sensitive silver halide grains and the silver halide emulsion other than the present invention used together therewith in the present invention are described below. In the following description, both emulsions are sometimes collectively referred to as "silver halide emulsion" for convenience.
General methods for preparing silver halide emulsions are described in Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafki
des, Chimie et Physique Photographique Paul Monte
l, 1967) Duffin, Photographic Emulsion Chemistry, published by Focal Press (GF Duffin, Photographic Emulsion C)
hemistry (Focal Press, 1966), "Production and Coating of Photographic Emulsion", by Zerikman et al., Published by Focal Press, Inc.
L. Zelikman et al. Making and Coating Photographi
c Emulsion. Focal Press, 1964).

The latent image forming position of the silver halide emulsion grains is as follows.
The surface may be the inside, the inside, or an extremely shallow inside (shallow inner surface). The method for preparing the silver halide emulsion may be any of an acidic method, a neutral method and an ammonia method. The pH may be as high as possible without causing fogging.
As a method of reacting the soluble silver salt with the soluble halogen salt, a one-sided mixing method, a simultaneous mixing method, or a combination thereof can be used. A method of forming grains in a state where silver ions are excessive (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid layer in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal system and a nearly uniform grain size distribution and halogen composition can be obtained. Also, as described in U.S. Pat. No. 4,879,208, it is preferable to add an ultrafine grain emulsion prepared in situ during emulsion preparation to an emulsion preparation tank and then grow the grains by physical ripening. This ultrafine particle emulsion may be prepared in advance.

In preparing a silver halide emulsion, it is preferable to adjust pAg and pH during grain formation. pAg
PH and pH adjustments are described in Photographic Science and Engineering.
and Engineering) Volume 6, pp. 159-165 (196
2); Journal of Photographic Science, Vol. 12, 242-
251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

As the protective colloid used in the preparation of the emulsion in the present invention, gelatin is preferably used, but other hydrophilic binders can also be used. The hydrophilic binder can be used alone or in combination with gelatin. As the hydrophilic binder, for example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose and cellulose sulfates, sodium alginate, starch derivatives, polysaccharides , Carrageenan, polyvinyl alcohol or modified alkyl polyvinyl alcohol or polyvinyl-N-pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, or synthetic hydrophilic polymer such as a copolymer such as polyvinyl imidazole or polyvinyl pyrazole, The thioether polymer described in U.S. Pat. No. 3,615,624 can also be preferably used. In addition to lime-processed gelatin, acid-treated gelatin, demineralized gelatin, gelatin derivatives such as phthalated gelatin, carbamoyl gelatin, and esterified gelatin, and low-molecular gelatin can be preferably used when forming tabular grains.
Gelatin oxidized with an oxidizing agent such as hydrogen peroxide is also known to be effective in forming tabular grains. Gelatin treated with an enzyme as described in Bull. Soc. Photo. Japan No. 16, page 30 (1966) can also be used as low molecular weight gelatin. A hydrolyzate or enzymatic hydrolyzate of gelatin can also be used.

In forming the silver halide emulsion grains, it is also preferable to use a silver halide solvent. In this case, examples of the silver halide solvent include thiocyanates (US Pat. Nos. 2,222,264, 2,448,534 and 2,448,534). 3320
No. 069), thioether compounds (U.S. Pat. Nos. 3,271,157, 3,574,628, 3,704,130, 4,297,439, and 4276).
No. 347) and thione compounds (JP-A-53-144319, JP-A-53-82408, and JP-A-5-82408).
5-77737), imidazole compounds (see JP-A-54-100717), benzimidazoles (see JP-B-60-54662), and amine compounds (see JP-A-60-54662). 54-1
00717).
Ammonia can be used in combination with a silver halide solvent within a range that does not cause adverse effects. JP-B-46-7781
JP-A-60-222842, JP-A-60-122
A nitrogen-containing compound described in each publication such as 935 can be added to the silver halide grain forming step. Details of specific examples of the silver halide solvent are described in
No. 215272, pages 12-18.

A method of adding a chalcogenide compound during the preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. S, Se, Te
In addition, cyanide, thiocyanate, selenocyanate, carbonate, phosphate and acetate may be present.

During the formation of silver halide emulsion grains, the addition rate, amount or concentration of a silver salt solution (eg, an aqueous AgNO ₃ solution) and a halogen compound solution (eg, an aqueous KBr solution) are increased to increase the grain formation speed. May be faster. Thus, a method for rapidly forming silver halide grains is disclosed in British Patent No. 1,335,925 and US Pat.
Nos. 00, 3650757 and 4242445, JP-A-55-142329 and JP-A-55-158.
No. 124, No. 58-113927, No. 58-1139
No. 28, No. 58-111934, No. 58-11193
No. 6 describes each.

During or after grain formation, the surface of the silver halide grains may be substituted with a halogen which forms hardly soluble silver halide emulsion grains (halogen conversion). This halogen conversion process is described in “Die Grundlägen dia.
Die Grundlagen der Photographisc
hen Prozesse mit Silverhalogeniden) 662-669
And "The Theory of Photographic Process", 4th edition, pp. 97-98. In this method, the compound may be added in the form of a soluble halide solution or in the form of fine silver halide grains.

During and / or after grain formation, thiosulfonates, US Pat.
No. 64754, the dichalcogen compound described in each specification,
Inorganic metal complexes such as lipoic acid, cysteine, elemental sulfur, cobalt ammonia complexes may be added.

In the course of grain formation or physical ripening of the silver halide emulsion, a metal salt (including a complex salt) may be allowed to coexist. Examples of the metal salts include salts or complex salts of noble metals or metals such as cadmium, zinc, thallium, platinum, gallium, copper, nickel, manganese, indium, tin, calcium, strontium, barium, aluminum, and bismuth. These compounds may be used alone or in combination of two or more. The addition amount is 10 ⁻⁹ to 10 ⁻³ per mol of silver halide.
It is about a mole. These metals are preferably used as water-soluble salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, and six-coordinate complexes and four-coordinate complexes. As complex ions and coordination compounds, bromine ions,
Chlorine ion, cyan ion, nitrosyl ion, thiocyan ion, thionitrosyl ion, water, ammonia,
Oxo, carbonyl and the like and combinations thereof are preferably used. The amount of addition depends on the purpose of use, but is about 10 ^-9 to 10 ^-2 mol per mol of silver halide.
Further, the position of incorporation into the silver halide emulsion grains may be uniform inside the grains, or may be localized at the surface or inside of the grains, a localized silver bromide phase, or a high silver chloride grain base. These compounds can be added by mixing the metal salt solution with an aqueous halide solution or a water-soluble silver salt solution during grain formation and continuously adding the metal salt during grain formation, or by adding a metal ion-doped halogen. It can be carried out by adding silver halide emulsion fine particles, or by directly adding the metal salt solution before, during or after grain formation. During the formation of particles, the metal salt solution may be continuously added.

A method of adding a chalcogenide compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. S, Se, Te
In addition, cyanide, thiocyanate, selenocyanate, carbonate, phosphate and acetate may be present.

In the process of preparing a photosensitive silver halide emulsion in the present invention, it is preferable to carry out a desalting step of removing excess salt. A Nudel washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactants, anionic polymers (eg, sodium polystyrene sulfonate), A sedimentation method (flocculation) using a gelatin derivative (aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may be used. Alternatively, US Pat.
No. 05, JP-A-62-113137, JP-B-59-43727, U.S. Pat. No. 4,334,012.
The ultrafiltration apparatus described in the specification may be used, or a natural sedimentation method or a centrifugal separation method may be used. Normally,
The sedimentation method is preferably used.

The light-sensitive silver halide emulsion of the present invention can be used without chemical sensitization, but is usually used after being chemically sensitized. The chemical sensitization method used in the present invention includes:
Sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization, noble metal sensitization using gold, platinum, palladium and the like, and reduction sensitization can be used alone or in combination (for example, JP-A-3-110555 and Japanese Patent Application No. 4-75798. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159). Further, an anti-fogging agent described later can be added after the completion of chemical sensitization. Specifically, JP-A-5-45833, JP-A-62-404
The method described in JP-A-46-46 can be used.

These chemical sensitizations can be carried out in any step of the process for producing a photosensitive silver halide emulsion. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded inside the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the surface of the particle, and a type in which a chemical sensitizing nucleus is formed in the surface of the particle. Various chemical sensitization nuclei can be formed inside or on the surface of the grain or at a position shallow from the surface of the grain. For example, it is preferable to form a reduction sensitizing nucleus inside a grain and a chalcogen sensitizing nucleus and / or a gold chalcogen sensitizing nucleus on the surface of the grain, but various combinations are possible depending on the purpose.

As the sulfur sensitizer, an unstable sulfur compound is used. Specifically, thiosulfate (for example, hypo),
Known sulfur compounds such as thioureas (for example, diphenylthiourea, triethylthiourea, allylthiourea, etc.), allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanines, and mercaptos can be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion.
H, temperature, balance with other sensitizers, size of photosensitive silver halide emulsion grains, etc.
As a guide, 10 ^-9 per mole of the photosensitive silver halide emulsion is used.
It is preferred to use from 10 to 10 ^-1 mol.

In the selenium sensitization, a known unstable selenium compound is used, and specifically, a colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.) ), Selenoketones, selenoamides, aliphatic isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenocarboxylic acids and esters, selenophosphates, diethyl selenides, diethyl diselenides, phosphine selenides And the like can be used. The amount of addition varies depending on various conditions as in the case of the sulfur sensitizer, but as a guide, it is preferable to use 10 ^-10 to 10 ^-1 mol per mol of the photosensitive silver halide emulsion.

In the present invention, in addition to the above-described chalcogen sensitization, sensitization with a noble metal can be performed. First, in gold sensitization, the valence of gold may be +1 or +3, and various gold compounds are used. Representative examples include chloroauric acids, potassium chloroaurate, auric trichloride, potassium aurithiocyanate, potassium iodooleate, tetraauric acid, ammonium aurothiocyanate, pyridyl trichlorogold,
Gold sulfide, gold selenide, gold telluride and the like. Although the amount of the gold sensitizer to be added varies depending on various conditions, it is preferably used in the range of 10 ^-10 to 10 ^-1 mol per mol of silver halide. When to add the gold sensitizer,
At the same time as sulfur sensitization or selenium sensitization, tellurium sensitization,
It may be during, before, or after the sulfur sensitization, selenium sensitization, or tellurium sensitization step, or the gold sensitizer may be used alone. PAg, pH of emulsions subjected to sulfur sensitization, selenium sensitization, tellurium sensitization or gold sensitization in the present invention
The pAg is 5 to 11 and the pH is 3 to 1
The pAg is preferably used in the range of 0 to 6.8.
More preferably, it is used in the range of 9.0 and pH 5.5 to 8.5.

When gold sensitization is performed by using metal ions of a cyano complex at the time of grain formation, metal ions such as zinc ions that coordinate to gelatin are added before chemical sensitization or during dispersion of gelatin. Is preferred.

In the present invention, noble metals other than gold can be used as the chemical sensitizer. As a noble metal other than gold, for example, a sensitizer based on a metal salt such as platinum, palladium, iridium, and rhodium or a complex salt thereof can be used.
As the palladium compound, a divalent or tetravalent palladium salt can be used. For example, K ₂ PdCl ₄ , Na ₂ PdCl _{6 and the} like are preferable. Gold and noble metal compounds may be used in combination with thiocyanates or selenocyanates.

In the present invention, reduction sensitization can be further performed. The reduction sensitization is preferably performed during grain formation, after grain formation, and before or during chemical sensitization, or after chemical sensitization. Here, the reduction sensitization is
A method of adding a reduction sensitizer to a photosensitive silver halide emulsion,
Either silver ripening in which the emulsion grains are grown or ripened in a low pAg atmosphere of pAg 1 to 7, silver emulsion ripening or ripening in a high pH atmosphere of pH 8 to 11, or high pH ripening can be selected. Further, two or more methods can be used in combination.

The reduction sensitizer used in the present invention includes
Sulfites, ascorbic acid, stannous salts, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. In the present invention, these known compounds may be used alone or in a combination of two or more. Preferred examples of the reduction sensitizer include stannous chloride, thiourea dioxide, dimethylamine borane, L-ascorbic acid, and aminoiminomethanesulfuric acid. US Patent 5,38
The alkynylamine compounds described in the specification of JP-A-9,510 are also effective compounds. Since the addition amount of the reduction sensitizer depends on the emulsion conditions, it is necessary to select the addition amount, but an appropriate range is 10 ^-9 to 10 ^-2 mol per mol of silver halide. In addition to the method of adding the reduction sensitizer, or through the passage of hydrogen gas, by the nascent hydrogen by electrolysis,
A method of reduction sensitization can also be selected. The reduction sensitization can be used alone or in combination with the chalcogen sensitization or the noble metal sensitization.

The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters, amides and the like, and added during and / or after grain formation. When it is added during the formation of the particles, it may be added to the reaction vessel in advance, but it is more preferable to add it at an appropriate time during the formation of the particles. Alternatively, a reduction sensitizer may be added to an aqueous halide solution or a water-soluble silver salt solution, and these solutions may be used to precipitate photosensitive silver halide emulsion grains. In addition, the solution of the reduction sensitizer may be added in several portions as the grains grow, or it may be preferably added continuously for a long time.

In the present invention, it is preferable to apply so-called spectral sensitization for imparting sensitivity to a desired light wavelength region to the photosensitive silver halide emulsion. In particular, a silver halide color photographic light-sensitive material incorporates a light-sensitive layer having photosensitivity to blue, green and red in order to reproduce color faithfully to the original (at the time of photographing). These sensitivities are provided by spectrally sensitizing silver halide. For the spectral sensitization, a so-called spectral sensitizing dye which is adsorbed on silver halide grains and has sensitivity in its own absorption wavelength range is used.

Examples of the spectral sensitizing dye include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar dyes, hemicyanine dyes,
Examples include styryl dyes and hemioxonol dyes. Examples of these are described in U.S. Pat. No. 4,617,257, JP-A-59-180550, JP-A-64-13546, JP-A-5-45828, and JP-A-5-45834. The spectral sensitizing dye is used alone or in combination of a plurality of dyes. this is,
It is performed for the purpose of adjusting the wavelength distribution of spectral sensitivity and for supersensitization. With a combination of dyes exhibiting supersensitization, sensitivities far exceeding the sum of sensitivities that can be achieved alone can be obtained. It is also preferable to use a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits a supersensitizing effect. Diaminostilbene compounds and the like can be mentioned as examples of the supersensitizer. Examples of these include US Pat.
No. 6,156,641 and JP-A-63-23145.

The timing of adding these spectral sensitizing dyes and supersensitizers to the silver halide emulsion may be at any stage in the preparation of the emulsion which has been known to be useful. To be added to the emulsion after chemical sensitization, at the time of preparation of the coating solution, to be added at the end of chemical sensitization, to be added during chemical sensitization, to be added prior to chemical sensitization, and to be added after the completion of grain formation and before desalting. Various methods such as addition during the formation of particles or addition prior to the formation of particles can be used alone or in combination. It is preferable to add in a step before chemical sensitization in order to obtain high sensitivity. The addition amount of the spectral sensitizing dye and supersensitizing agent can vary widely depending on the shape and particle size, or impart desired to photographic properties of the particles, generally 1 mol of silver halide per 10 ^-8 10 ^-1 mole, preferably 10 The range is from ^-5 to 10 ^-2 mol. These compounds can be added in a state of being dissolved in an organic solvent such as methanol or fluorine alcohol, or in a state of being dispersed in water together with a surfactant or gelatin.

It is preferable to add various stabilizers to the silver halide emulsion for the purpose of preventing fogging and enhancing the stability during storage. Preferred stabilizers include azaindenes, triazoles, tetrazoles, nitrogen-containing heterocyclic compounds such as purines, mercaptotetrazole, mercaptotriazoles, mercaptoimidazoles, mercapto compounds such as mercaptothiadiazole, and the like. . Details of these compounds are described in James, "Theory of Photographic Process," published by Macmillan (TH.
James, The Theory of the P
photographic Process, Macmi
llan, 1977) pp. 396-399 and references cited therein.

These antifoggants or stabilizers can be added to the silver halide emulsion at any time during the preparation of the emulsion. To be added to the emulsion after chemical sensitization, at the time of preparation of the coating solution, to be added at the end of chemical sensitization, to be added during chemical sensitization, to be added prior to chemical sensitization, and to be added after the completion of grain formation and before desalting. Various methods such as addition during the formation of particles or addition prior to the formation of particles can be used alone or in combination. The addition amount of these antifogging agents or stabilizers varies depending on the halogen composition and purpose of the silver halide emulsion, but is generally from 10 ^-6 to 10 ^-1 mol, preferably from 10 ^-5 to 1 mol per mol of silver halide.
It is in the range of 10 ^-2 mol.

The photographic additives used in the light-sensitive material of the present invention as described above are described in Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17643 (December 1978) and No. 18716 (November 1979). And No. 307105 (November 1989), and the relevant portions are shown below.

Types of Additives RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column 866, sensitivity enhancer 648, right column, spectral sensitizer 23-24, page 648, right column 866-868 Supersensitizer Page 649 right column Brightener 24 page 648 page right column 868 page Antifoggant 24 pages 26 page 649 right column 868 pages 870 Stabilizer light absorber page 25 26 page 649 right column page 873 filter dyes 650 Page left column UV absorber Dye image stabilizer page 25 650 page left column 872 Hardener 26 page 651 left column 874-875 Binder page 26 651 page left 873-874 Plasticizer, lubricant 27 page 650 Page right column 876 Page Coating aid 26-27 Page 650 Right column 875-876 Surfactant Static inhibitor page 27 650 Right column 87 ～877 pages matting agent, pp. 878-879

The coating amount of the photosensitive silver halide emulsion used in the present invention is 1 mg / m ^{2 to} 10 g / m ^{2 in} terms of silver.
And preferably 0.1 to 5 g / m ² . In the silver halide color photographic light-sensitive material of the present invention, by incorporating a developing agent capable of generating a dye by coupling an oxidant generated by silver development with a coupler described below, a processing solution containing the developing agent can be obtained. This eliminates the need for use, reduces environmental impact, and enables simple and rapid processing.

In the silver halide color photographic light-sensitive material of the present invention, a hydrophilic binder is preferably used for the photographic constituent layer. Examples thereof include those described in the aforementioned Research Disclosure and JP-A-64-13546, pages (71) to (75). Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan and polyvinyl alcohol, denaturation. Polyvinyl alcohol (for example,
Alkyl-terminated Poval MP10 manufactured by Kuraray Co., Ltd.
3, MP203), synthetic polymers such as polyvinylpyrrolidone and acrylamide polymers. U.S. Pat. No. 4,960,681;
No. 45260, etc., the superabsorbent polymer, that is, -CO
OM or -SO ₃ M (M is a hydrogen atom or an alkali metal)
Or a copolymer of the vinyl monomers with each other or with another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.). . These binders can be used in combination of two or more kinds. Particularly, a combination of gelatin and the above binder is preferable. 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.

In the present invention, the coating amount of the binder is 1 to 20 g / m ² , and ² to 15 g / m ^2.
Is preferred, and 3 to 12 g / m ² is more preferred. Among these, the content of gelatin is 50% to 100%, preferably 70% to 100%.

In the present invention, as a developing agent, p-
Although phenylenediamines or p-aminophenols may be used, compounds represented by the above general formulas (1) to (5) are preferable.

The compound represented by the general formula (1) is a compound generally called sulfonamidophenol.

In the general formula (1), R _{1 to} R ₄ represent a hydrogen atom, a halogen atom (for example, chloro group, bromo group),
Alkyl group (eg, methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group), aryl group (eg, phenyl group, tolyl group, xylyl group), alkylcarbonamide group (eg, acetylamino group) , Propionylamino group, butyroylamino group), arylcarbonamide group (eg, benzoylamino group), alkylsulfonamide group (eg, methanesulfonylamino group, ethanesulfonylamino group), arylsulfonamide group (eg, benzenesulfonyl) Amino group, toluenesulfonylamino group), alkoxy group (for example, methoxy group, ethoxy group, butoxy group), aryloxy group (for example, phenoxy group), alkylthio group (for example,
Methylthio group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group, tolylthio group),
Alkylcarbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group,
Diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (for example, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfa Moyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, morpholylsulfamoyl group), aryl Sulfamoyl 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 (for example, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example,
Methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (eg, phenoxycarbonyl group), alkylcarbonyl group (eg, acetyl group, propionyl group, butyroyl group), arylcarbonyl group (eg, benzoyl group,
Represents an alkylbenzoyl group) or an acyloxy group (eg, an acetyloxy group, a propionyloxy group, a butyroyloxy group). Among R _{1 to} R ₄ , R ₂ and R
₄ is preferably a hydrogen atom. Further, the sum of the Hammett constants σ _p values of R _{1 to} R ₄ is preferably 0 or more.

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

The compound represented by the general formula (2) is a compound generally called sulfonylhydrazine. Also,
The compound represented by the general formula (4) is a compound generally called carbamoylhydrazine.

In the general formulas (2) and (4), Z represents a group of atoms forming an aromatic ring. The aromatic ring formed by Z needs to be sufficiently electron-attracting in order to impart silver developing activity to the present compound. For this reason, an aromatic ring which forms a nitrogen-containing aromatic ring or has an electron-withdrawing group introduced into a benzene ring is preferably used. As such an aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinoxaline ring and the like are preferable.

In the case of a benzene ring, the substituent is
Alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), halogen atom (for example, chloro group,
Bromyl 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) A famoyl group, a piperidylsulfamoyl group, a morpholylsulfamoyl group), an arylsulfamoyl group (for example, a phenylsulfamoyl group,
Methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group),
Sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group),
Arylsulfonyl group (for example, phenylsulfonyl group,
4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, Examples thereof include a propionyl group and a butyroyl group) and an arylcarbonyl group (for example, a benzoyl group and an alkylbenzoyl group). The sum of the Hammett constant σ values of the above substituents is 1 or more.

The compound represented by the general formula (3) is a compound generically called sulfonylhydrazone. Also,
The compound represented by the general formula (5) is a compound generally called carbamoylhydrazone.

In the above general formulas (3) and (5), R ₆ is
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 may combine with each other to form a double bond or a ring.

The specific examples of the compounds represented by formulas (1) to (5) are shown below, but the compounds of the present invention are not limited by these specific examples (D-1 to 60). is not.

[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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In the present invention, one or more of the above compounds are used in combination as the developing agent. In the present invention, a different developing agent may be used for each layer. The total amount of the developing agents used is 0.05 to 20 mm
ol / m ^2, preferably from 0.1 to 10 mmol / m ^2.

Next, the coupler according to the present invention will be described. The coupler means a compound that forms a dye by a coupling reaction with an oxidized form of the developing agent. Examples of the coupler preferably used in the present invention include compounds generally referred to as active methylene, 5-pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole. These couplers are available from Research Disclosure (RD) No. 38957.
(September 1996), pp. 616-624, “x. Dye image form
ers and modi fiers "can be preferably used.

These couplers can be divided into so-called 2-equivalent couplers and 4-equivalent couplers. 2 above
Examples of the group acting as an anionic leaving group of the equivalent coupler include a halogen atom (eg, chloro group, bromo group), an alkoxy group (eg, methoxy group, ethoxy group), an aryloxy group (eg, phenoxy group, 4-cyanophenoxy group, 4-alkoxycarbonylphenyl group), alkylthio group (for example, methylthio group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group, tolylthio group), alkylcarbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, Diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (for example, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbyl) Moyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidyl) Sulfamoyl 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), alkylcarbonyloxy Groups (eg, acetyloxy, propionyloxy, butyroyloxy), arylcarbonyloxy (eg, benzoyloxy, toluyloxy, anisyloxy), nitrogen-containing heterocyclic groups (eg, imidazolyl, benzotriazolyl) Is mentioned.

Examples of the group acting as a cationic leaving group of the 4-equivalent coupler include a hydrogen atom, a formyl group, a carbamoyl group and a substituted methylene group (substituents include an aryl group, a sulfamoyl group, and a carbamoyl group). , An alkoxy group, an amino group, a hydroxyl group, etc.), an acyl group, a sulfonyl group and the like.

In the present invention, in addition to the compounds described in RD No. 38957, couplers described below can be suitably used.

Examples of such couplers include active methylene couplers. Examples of the active methylene coupler include couplers represented by formulas (I) and (II) in EP 502,424A; and formula (1) in EP 513,496A. ), Couplers represented by (2);
A coupler represented by the formula (I) in claim 1 of EP 568,037A; a coupler represented by the formula (I) in column 1, lines 45 to 55 of US Pat. No. 5,066,576; A coupler according to claim 1 on page 40 of EP 498,381 A1; a formula on page 4 of EP 447,969 A1
A coupler represented by (Y); US Pat. No. 4,476,219, column 7
Couplers represented by formulas (II) to (IV) on lines 36 to 58 can be used.

Further, 5-pyrazolone-based magenta couplers are mentioned. Examples of the 5-pyrazolone-based magenta couplers include JP-A-57-35858 and JP-A-51-20.
The compound described in No. 826 can be suitably used.

Further, pyrazoloazole-based couplers may be mentioned. Examples of the pyrazoloazole-based coupler include imidazo [1,2-] described in US Pat.
b] pyrazoles, pyrazolo [1,5-b] [1,2,4] triazoles described in U.S. Pat. No. 4,540,654, and pyrazolo [5 described in U.S. Pat. No. 3,725,067. , 1-c] [1,2,4] triazoles are preferred, and among these, pyrazolo [1,2
5-b] [1,2,4] triazoles can be suitably used.

Further, a pyrazoloazole coupler in which a branched alkyl group is directly bonded to the 2, 3 or 6 position of a pyrazolotriazole group as described in JP-A-61-65245 is disclosed in JP-A-61-65245. Pyrazoloazole couplers containing a sulfonamide group in the molecule described therein, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254, JP-A-62-209457 or Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-63-307453, and pyrazolotriazole couplers having a carboxamide group in the molecule described in JP-A-2-201443 are also available. It can be suitably used.

Further, phenol couplers may be mentioned.
Preferable examples of the phenol coupler include U.S. Pat. Nos. 2,369,929 and 2,801,171.
No. 2,772,162, No. 2,895,82
No. 6,772,002 and the like, 2-alkylamino-5-alkylphenols, U.S. Pat.
772,162, 3,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,
729 and JP-A-59-166956.
5-diacylaminophenols, U.S. Pat. No. 3,44
No. 6,622, No. 4,333,999, No. 4,4
2-phenylureido-5-acylaminophenols described in JP-A-51,559 and JP-A-4,427,767.

Further, there may be mentioned naphthol couplers. Preferred examples of the naphthol couplers include US Pat. Nos. 2,474,293, 4,052,212, 4,146,396 and 4,146,396. No. 4,228,233,
2-carbamoyl-1-naphthol described in U.S. Pat. No. 4,296,200 and the like and U.S. Pat. No. 4,690,889.
And 2-carbamoyl-5-amide-1-naphthol.

Further, pyrrolotriazole couplers may be mentioned, and preferred examples of the pyrrolotriazole couplers are disclosed in European Patent Nos. 488,248A1 and 49.
The couplers described in 1,197A1 and 545,300 are exemplified.

Further, other couplers having a structure such as a fused phenol, imidazole, pyrrole, 3-hydroxypyridine, active methine, a 5,5-fused heterocycle, and a 5,6-fused heterocycle can be used. .

Examples of such fused phenol couplers include US Pat. Nos. 4,327,173 and 4,56.
The couplers described in 4,586, 4,904,575 and the like can be used. U.S. Pat. Nos. 4,818,672 and 5,
No. 051,347 and the like can be used. Pyrrole-based couplers are disclosed in JP-A-4-188.
No. 137, 4-190347 and the like. As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 and the like can be used. As active methine couplers, US Pat. Nos. 5,104,783 and 5,16
The couplers described in 2,196 and the like can be used.

As the 5,5-fused heterocyclic coupler,
Pyrrolopyrazole couplers described in U.S. Pat. No. 5,164,289 and pyrroleimidazole couplers described in JP-A-4-174429 can be used.
Examples of 5,6-fused heterocyclic couplers include pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, and EP 556. The couplers described in No. 700 can be used.

In the present invention, in addition to the above-mentioned couplers, German Patent Nos. 3,819,051A and 3,82.
No. 3,049, U.S. Pat. Nos. 4,840,883, 5,024,930, 5,051,347, 4,481,268, and EP 304,856A.
No. 2, 329,036 and 354, 549A2
No. 374, 781A2 and No. 379, 110A
No. 2, 386,930A1, JP-A-63-141
Nos. 055, 64-32260, 32261, JP-A-2-29747, JP-A-2-44340, and 2-
No. 110555, No. 3-7938, No. 3-16044
No. 0, No. 3-172839, No. 4-17247,
4-179949, 4-182645, 4-
Nos. 184437, 4-188138, 4-188
No. 139, No. 4-194847, No. 4-204532
And the couplers described in JP-A Nos. 4-207473 and 4-204732 can also be used. These couplers are used at 0.05 to 10 mmol / m ² , preferably at 0.1 to 5 mmol / m ² for each color.

Further, in the present invention, the following functional couplers may be contained. US 4,366,237, GB 2,12
Those described in 5,570, EP 96,873B and DE 3,234,533 are preferred. Examples of couplers for correcting unnecessary absorption of a coloring dye include yellow colored cyan couplers described in EP 456,257A1, yellow colored magenta couplers described in the EP, and magenta colored cyan couplers described in US Pat. No. 4,833,069. , US4,83
No. 7,136, (2), and colorless masking couplers represented by the formula (A) in claim 1 of WO92 / 11575 (especially the exemplified compounds on pages 36 to 45) and the like are preferred.

Compounds (including couplers) which react with the oxidized form of the developing agent to release photographically useful compound residues
Examples include the following. As the development inhibitor releasing compound, for example, EP 378,236A1
Compounds of formulas (I) to (IV) described on page 4, EP4
No. 36,938A2, page 7, compound represented by formula (I), EP 568,037A, compound represented by formula (1), EP44
Compounds represented by formulas (I), (II) and (III) described on pages 5 to 6 of U.S. Pat. Compounds represented by the formulas (I) and (I ') on page 5 of EP 310,125A2 and compounds represented by the formula (I) in claim 1 of JP-A-6-59411 are examples of the bleaching accelerator releasing compound. No. US 4,55 as a ligand releasing compound
And the compound represented by LIG-X described in claim 1 of 5,478. US 4,7 as leuco dye releasing compound
Compounds 1 to 6 in columns 3 to 8 of 49,641 are exemplified. Examples of the fluorescent color emitting compound include a compound represented by COUP-DYE in Claim 1 of US Pat. No. 4,774,181. US 4,656,123 as development accelerators or fogging agent releasing compounds
And the compounds represented by formulas (1), (2) and (3) in column 3 of Ex. No. 3, ExZK-2 on page 75, lines 36 to 38 of EP 450,637A2, and the like. As compounds which release a group which becomes a dye only after leaving, compounds represented by the formula (I) in claim 1, US Pat. Compounds represented by formulas (I), (II) and (III) described on pages 5 and 6 of Japanese Patent Application No. 4-325.
No. 564, a compound represented by the formula (I) of claim 1 and a ligand releasing compound, and a compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478. Such a functional coupler is preferably used in an amount of 0.05 to 10 times, and more preferably 0.1 to 5 times, the amount of the coupler that contributes to color development described above.

The hydrophobic additives such as the coupler and the developing agent can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, US Pat. No. 4,555,47
Nos. 0, 4,536,466 and 4,536,467
Nos. 4,587,206 and 4,555,476
No. 4, 599, 296, Tokuhei 3-62, 256
A high-boiling organic solvent as described in the above item can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C, if necessary. These dye-donating couplers, high-boiling organic solvents, and the like can be used in combination of two or more.

The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g per 1 g of the hydrophobic additive used. In addition, 1 cc or less is preferable for 1 g of the binder,
0.5 cc or less is more preferable, and 0.3 cc or less is particularly preferable. In the present invention, Japanese Patent Publication No. 51-39,853
And a dispersion method using a polymer described in JP-A-51-59,943, and a method of adding as a fine particle dispersion described in JP-A-62-30242.

In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used.
For example, JP-A-59-157,636, Nos. (37) to (38)
Page, and the surfactants described in Research Disclosure described above can be used. Also, Japanese Patent Application No. 5-204
Nos. 325 and 6-19247, West German Patent No. 1,9
The phosphate ester type surfactant described in No. 32,299A can also be used.

The silver halide color photographic light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. A typical example is a silver halide color photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Material. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light and red light.In a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally The red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer are provided in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

A non-light-sensitive layer may be provided between the light-sensitive layers containing the above-mentioned light-sensitive silver halide emulsion and as the uppermost layer and the lowermost layer. These may contain the aforementioned couplers, developing agents, DIR compounds, color mixture inhibitors, dyes, and the like. As described in DE 1,121,470 or GB 923,045, a plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers of a high-speed emulsion layer and a low-speed emulsion layer toward a support. It is preferable to arrange them so that the degree is low. Further, JP-A-57-112751, JP-A-62-200350, JP-A-62-200350
As described in JP-A-206541 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / In order of low sensitivity red photosensitive layer (RL), BH
/ BL / GL / GH / RH / RL or BH / BL / GH / GL / RL /
They can be installed in the order of RH. In addition, Tokiko Sho 55-34
As described in 932 gazette, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the farthest side from the support. Also, as described in JP-A-56-25738 and JP-A-62-63936, the layers can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Also,
As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer with the highest sensitivity, the middle layer is the silver halide emulsion layer with a lower sensitivity, and the lower layer is less sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Such different sensitivities 3
Even when it is composed of layers, as described in JP-A-59-202464, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer in the same color-sensitive layer from the side away from the support. May be arranged in this order. In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order.
The arrangement may be changed as described above even in the case of four or more layers.

In order to improve color reproducibility, US Pat. No. 4,663,27
1, 4,705,744, 4,707,436, JP-A-62-160448,
It is preferable to arrange a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL described in the specification of JP-A-63-89850, adjacent to or close to the main photosensitive layer. .
In the present invention, the silver halide, the dye-providing coupler and the developing agent may be contained in the same layer, or may be added separately to another layer as long as they can react. For example, when the layer containing the developing agent and the layer containing the photosensitive silver halide emulsion are formed as separate layers, the raw storage stability of the silver halide color photographic light-sensitive material can be improved.

The relationship between the spectral sensitivity of each layer and the hue of the coupler is arbitrary. However, when a cyan coupler is used for a red photosensitive layer, a magenta coupler is used for a green photosensitive layer, and a yellow coupler is used for a blue photosensitive layer, a conventional color paper can be used. Etc. can be directly projected and exposed. In the silver halide color photographic light-sensitive material of the present invention, various layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer are provided between the silver halide emulsion layers and the uppermost layer and the lowermost layer. May be provided, and various auxiliary layers such as a back layer can be provided on the side opposite to the support. Specifically, the layer structure described in the above patent, the undercoat layer described in U.S. Pat. No. 5,051,335, the layers described in JP-A-1-167,838 and JP-A-61-20,943 can be used. An intermediate layer having such a solid pigment, JP-A-1-120553, JP-A-5-34,
No. 884, 2-64,634, an intermediate layer having a reducing agent or a DIR compound, U.S. Pat.
Nos. 454 and 5,139,919, JP-A-2-23
An intermediate layer having an electron transfer agent as described in 5,044,
A protective layer having a reducing agent as described in JP-A-4-249,245 or a layer obtained by combining them can be provided.

The dye which can be used for the yellow filter layer and the antihalation layer is preferably a dye which is decolored or removed at the time of development and does not contribute to the density after processing.
When the dye of the yellow filter layer and the antihalation layer is erased or removed at the time of development, the amount of the dye remaining after the processing is １ ／ or less, preferably 1/10 or less immediately before coating, During development, the components of the dye may be transferred from the silver halide color photographic light-sensitive material to the processing member,
It may be converted to a colorless compound by reacting during development.

Specifically, European Patent Application EP549,4
No. 89A and the dye described in JP-A-7-152129.
xF2 to 6 dyes. JP-A-8-10148
No. 7, a solid-dispersed dye can also be used. Further, the mordant and the binder may be dyed with a mordant. In this case, as the mordant and the dye, those known in the field of photography can be used.
No. 4,500,626, columns 58 to 59;
No. 88256, pp. 32-41, JP-A-62-244043.
And mordants described in JP-A-62-244036. Further, by using a compound that reacts with a reducing agent to release a diffusible dye and a reducing agent, the mobile dye can be released with an alkali at the time of development, and transferred to and removed from a processing material. These are specifically described in U.S. Pat.
59,290, 4,783,396, EP 220,746A2, and JP-A-87-6119, and paragraphs 0080 to 0081 of JP-A-8-101487. ing.

A decolorizable leuco dye or the like can also be used. Specifically, JP-A-1-150132 discloses a halogenated solution containing a leuco dye which has been colored in advance with a developer of a metal salt of an organic acid. A silver color photographic light-sensitive material is disclosed. The leuco dye and the developer complex are decolorized by heat or by reaction with an alkaline agent.

Known leuco dyes can be used, and Moriga and Yoshida, "Dyes and Chemicals", pp. 9, 84 (Chemical Products Industry Association), "New Edition Dye Handbook", p. 242 (Maruzen, 197)
0), R. Garner "Reports on the Progress of Appl. C
hem "56, p. 199 (1971)," Dyes and chemicals "1
9, 230 pages (Chemical Products Industry Association, 1974), "Colorants"
62, 288 (1989), "Dyeing Industry", 32, 20
8 and the like.

As the developer, an acid clay-based developer,
In addition to phenol formaldehyde resin, metal salts of organic acids are preferably used. As metal salts of organic acids, metal salts of salicylic acids, metal salts of phenol-salicylic acid-formaldehyde resin, rhodan salts, metal salts of xanthogenates, and the like are useful, and zinc is particularly preferable as the metal. Among the above developers, oil-soluble zinc salicylate salts are described in U.S. Pat.
Nos. 6,941, and Japanese Patent Publication No. 52-1327 can be used.

The coating layer in the silver halide color photographic light-sensitive material of the present invention is preferably hardened with a hardener. Examples of the hardener include U.S. Pat.
8,739, column 41, 4,791,042, JP-A-59-116,655, 62-245,261
No. 61-18,942, JP-A-4-218,04
No. 4 and the like. More specifically,
Aldehyde hardener (such as formaldehyde), aziridine hardener, epoxy hardener, vinyl sulfone hardener (N, N'-ethylene-bis (vinylsulfonylacetamide) ethane, etc.), N- Examples include a methylol-based hardening agent (such as dimethylol urea), boric acid, metaboric acid, and a polymer hardening agent (compounds described in JP-A-62-234157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.1 to 1 g per 1 g of the hydrophilic binder.
005 to 0.5 g are used.

In the silver halide color photographic light-sensitive material of the present invention, various antifogging agents or photographic stabilizers and precursors thereof can be used. Specific examples thereof include the above-mentioned Research Disclosure, U.S. Pat. Pages (9), (57)-(71) and (81)-(97), U.S. Pat. Nos. 4,775,610 and 4,626,500
No. 4,983,494, JP-A-62-174,7
No. 47, 62-239, 148, JP-A No. 1-15
No. 0, 135, 2-110, 557, 2-17
8,650, RD17,643 (1978) (24)
To (25) and the like. These compounds are preferably used in an amount of 5 × 10 ^-6 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, per mol of silver.

The silver halide color photographic light-sensitive material of the present invention comprises a coating aid, an improvement in peelability, an improvement in slipperiness, an antistatic property,
Various surfactants can be used for the purpose of accelerating development and the like. Specific examples of the surfactant include known technology No. 5 (March 22, 1991, published by Aztec Co., Ltd.), pp. 136-138, JP-A-62-173,463.
No. 62-183,457.

The silver halide color photographic light-sensitive material of the present invention may contain an organic fluoro compound for the purpose of preventing slippage, preventing static charge, improving releasability and the like. Representative examples of the organic fluoro compound include Japanese Patent Publication No. 57-9053.
Nos. 8-17, JP-A-61-20944, 62-62
Fluorine surfactants described in JP-B-135826, oily fluorine compounds such as fluorine oil, and hydrophobic fluorine compounds such as solid fluorine compound resins such as fluorinated ethylene resin. For the purpose of achieving both wettability and antistatic of the photosensitive material, a fluorine-based surfactant having a hydrophilic group is also preferably used.

The silver halide color photographic light-sensitive material of the present invention preferably has a sliding property. It is preferable to use the slip agent on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents a value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25 ° C., 6 ° C.
0% RH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level.

Examples of the slipping agents usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and the like. As the polyorganosiloxane, polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. As the layer to which the slip agent is added, the outermost layer of the emulsion layer and the back layer are preferable.
Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable. Silicon oil and chlorinated paraffin are preferably used in order to prevent pressure-sensitive and desensitization of silver halide.

In the present invention, an antistatic agent is preferably used. As those antistatic agents, carboxylic acid and carboxylate, polymers including sulfonate,
Examples include cationic polymers and ionic surfactant compounds. Most preferred as the antistatic agent is Zn
O, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , S
Particles having at least one volume resistivity selected from iO ₂ , MgO, BaO, MoO ₃ , and V ₂ O ₅ of at most 10 ⁷ Ω · cm, more preferably at most 10 ⁵ Ω · cm. Fine particles of crystalline metal oxides or composite oxides thereof (SbP, B, InS, Si, C, etc.) having a size of 0.001 to 1.0 μm, and sol-like metal oxides or composite oxides thereof Fine particles. The content of the silver halide color photographic light-sensitive material is preferably 5 to 500 mg / m ^2, particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5. On the back side of the support of the silver halide color photographic light-sensitive material, JP-A-8-2
It is also preferable to apply a water-resistant polymer described in No. 92514.

The constitution (including the back layer) of the silver halide color photographic light-sensitive material or the processing material described later includes a film for stabilizing dimensions, preventing curling, preventing adhesion, preventing cracking of the film, and preventing pressure fluctuation. Various polymer latexes can be contained for the purpose of improving physical properties. More specifically,
2-245258, 62-136648, 62
Any of the polymer latexes described in JP-A-110066 can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or lower) is used for the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, the curl prevention effect is reduced. can get.

The silver halide color photographic light-sensitive material of the present invention preferably contains a matting agent. Either the emulsion surface or the back surface may be used as the matting agent,
It is particularly preferred to add it to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. As the particle size of the matting agent,
The particle size distribution is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow. It is preferable that 90% or more of the total number of particles is contained between 0.9 and 1.1 times the average particle size.

It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property.
Polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio),
0.3 μm)), polystyrene particles (0.25 μm),
Colloidal silica (0.03 μm) is exemplified. Specifically, it is described in JP-A-61-88256 (page 29). In addition, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, etc.
There are compounds described in JP-A-3-274944 and JP-A-63-274952. In addition, the compounds described in Research Disclosure can be used. These matting agents can be dispersed as necessary with various binders described in the section of the binder, and used as a dispersion. In particular, various kinds of gelatin, for example, an acid-treated gelatin dispersion are easy to prepare a stable coating solution. At this time, it is preferable to optimize pH, ionic strength and binder concentration as necessary.

In the present invention, the following compounds can be used. It is a dispersion medium of an oil-soluble organic compound, for example, P-3,5,16,19,25,30, JP-A-62-215272.
42, 49, 54, 55, 66, 81, 85, 86, 93 (pages 140 to 144). Latex for impregnation of an oil-soluble organic compound, such as the latex described in US Pat. No. 4,199,363. Oxidized developer scavenger, US 4,9
Compounds of formula (I) in columns 54-62 of column 2, 78,606 (especially I-, (1), (2), (6), (12) (columns 4-5), US 4,9
23,787, column 5, lines 5 to 10 (especially those described in compound 1 (column 3)).

Antistain agents, for example, EP 298321A
Formulas (I) to (III) on page 4, lines 30 to 33, especially I-47, 72, III-1, 27
(Pages 24 to 48). It is an anti-fading agent, for example, A-6, 7, 20, 21, 23, 24, 25, 26, 3 of EP 298321A
0,37,40,42,48,63,90,92,94,164 (pp.69-118), US5,12
2,444 columns 25-38 II-1 to III-23, especially III-10, EP
I-1 to III-4 on pages 8 to 12 of 471347A, especially II-2, US 5,139,
931 columns 32 to 40, A-1 to 48, especially A-39, 42. It is a material for reducing the amount of a color-enhancing agent or a color-mixing inhibitor, and is described in EP 411324A on page 5 to page I-1.
To II-15, especially I-46. Formalin scavenger, for example, SCV-1 to 2 on page 24 to 29 of EP 477932A
8, especially SCV-8. Compounds represented by formulas (VII) to (XII) in columns 13 to 23 of H-1,4,6,8,14, US 4,618,573 on page 17 of JP-A-1-148845, for example. H-1 ~
54), the compounds (H-1 to 76) represented by the formula (6) at the lower right of page 8 of JP-A-2-214852, particularly the compounds described in claim 1 of H-14, US 3,325,287.

A development inhibitor precursor is described in
-168139 P-24,37,39 (pages 6-7); compounds described in claim 1 of US 5,019,492, especially 28,29 of column 7; preservatives, fungicides: columns 3-15 of US 4,923,790 I-1 to III-
43, especially II-1,9,10,18, III-25; stabilizers, antifoggants, for example, I-1 to (14) of columns 6 to 16 of US 4,923,793,
In particular, compounds 1 to 65, especially 36, of columns 25 to 32 of I-1,60, (2), (13), US Pat. Chemical sensitizers such as triphenylphosphine selenide,
5-40324, compound 50.

Dyes, for example, 15 to 15 of JP-A-3-156450
A-1 to b-20 on page 18, especially a-1,12,18,27,35,36, b-5,27 to
V-1 to 23 on page 29, especially F-1, F- on page 33 to 55 of EP 445627A
I-1 to F-II-43, especially FI-11, F-II-8, 17 to 2 of EP 457153A
III-1 to 36 on page 8, especially III-1,3, 8 to 26 in WO 88/04794
A microcrystalline dispersion of Dye-1 to 124, Compounds 1 to 22 on pages 6 to 11 of EP 319999A, in particular Compounds D-1 to 87 represented by Formulas (1) to (3) of Compound 1, EP 519306A (Pages 3-28), US 4,26
8,622 compounds represented by the formula (I) (columns 3 to 1)
0), compounds (1) to (3) represented by formula (I) of US 4,923,788.
1) (columns 2 to 9). Compounds (18b) to (18r), 10 represented by the formula (1) of JP-A-46-3335 which are UV absorbers
1 to 427 (pages 6 to 9), compounds (3) to (66) (pages 10 to 44) represented by the formula (I) and compounds HBT-1 to 10 represented by the formula (III) in EP 520938A. (P. 14), compounds (1) to (31) (columns 2 to 9) represented by the formula (1) in EP 521823A.

The various additives described above, specifically, a hardening agent, an anti-fogging agent, a surfactant, a slipping agent, an antistatic agent, a latex, a matting agent, and the like may be added to the processing material as necessary. Or a silver halide color photographic light-sensitive material and a processing material.

In the present invention, as the support of the silver halide color photographic light-sensitive material, a support which is transparent and can withstand the processing temperature is used. In general, papers and synthetic polymers (films) described in the Photographic Society of Japan, "Basics of photographic engineering-silver halide photography-", published by Corona Co., Ltd. (1979), pp. 223-240. And photographic supports. Specific examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, and celluloses (for example, triacetyl cellulose). In the present invention, among these, a polyester containing polyethylene naphthalate as a main component is particularly preferable.
The “polyethylene-naphthalate-based” polyester as used herein means that the content of naphthalenedicarboxylic acid contained in all dicarboxylic acid residues is preferably 50 mol% or more, more preferably 60 mol% or more, and furthermore It is preferably at least 70 mol%. It may be a copolymer or a polymer blend.

In the case of a copolymer, those obtained by copolymerizing units such as terephthalic acid, bisphenol A, and cyclohexanedimethanol in addition to the naphthalenedicarboxylic acid unit and the ethylene glycol unit are also preferable. Among these, the most preferred is a copolymer of a terephthalic acid unit from the viewpoint of mechanical strength and cost. Preferred partners for the polymer blend include polyesters such as polyethylene terephthalate (PET), polyarylate (PAr), polycarbonate (PC), and polycyclohexane dimethanol terephthalate (PCT) from the viewpoint of compatibility. In view of the above, a polymer blend with PET is preferred.

Specific examples of preferred polyesters are shown below. Examples of polyester copolymers (numbers in parentheses indicate molar ratio) 2,6-naphthalenedicarboxylic acid /
Terephthalic acid / ethylene glycol (70/30/10
0) Tg = 98 ° C., 2,6-naphthalenedicarboxylic acid /
Terephthalic acid / ethylene glycol (80/20/10
0) Tg = 105 ° C., polyester polymer blend example (numbers in parentheses indicate weight ratio) PEN / PET (6
0/40) Tg = 95 ° C., PEN / PET (80/2
0) Tg = 104 ° C.
No. 159 (29) to (31), JP-A-1-161,236
(14)-(17), JP-A-63-316,848, JP-A-2-22,651, JP-A-3-56,955, and U.S. Pat. No. 5,001,033. The body can be used. These supports should 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. Can be.

In particular, when heat resistance and curl characteristics are strictly required, a support for a silver halide color photographic light-sensitive material may be used.
JP-A-6-41281, JP-A-6-43581 and JP-A-6-43581
No. 51426, No. 6-51437, No. 6-51442
JP-A-6-82961, JP-A-6-82960, JP-A-6-123937, JP-A-6-82959, and JP-A-6-67
No. 346, No. 6-118561, No. 6-266050
No. 6-202277, No. 6-175282, No. 6-118561, No. 7-219129, No. 7-2
The supports described in the respective publications of 19144 can be suitably used. Further, a support mainly composed of a styrene polymer having a syndiotactic structure can also be suitably used. The thickness of the support is preferably from 5 to 200 μm, more preferably from 40 to 120 μm.

In order to bond the support and the photographic component layer of the silver halide color photographic light-sensitive material, it is preferable to perform a surface treatment. Chemical treatment,
Mechanical treatment, corona discharge treatment, flame treatment, UV treatment,
Surface activation treatments such as high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and the like can be given. Among these surface treatments, preferred are ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment.

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

Regarding the dye used for film dyeing, the color tone is preferably gray dyeing due to the general properties of a silver halide color photographic light-sensitive material. Those having excellent compatibility are preferred. From that point of view, the dyes include Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.
The purpose can be achieved by mixing a commercially available dye for polyester and the like. In particular, from the viewpoint of heat stability, anthraquinone-based dyes are exemplified. For example, those described in JP-A-8-122970 can be suitably used. Further, in the present invention, as the support, for example, JP-A-4-124
No. 645, No. 5-40321, No. 6-35092,
It is preferable to record photographic information and the like using a support having a magnetic recording layer described in JP-A-6-317875.

The magnetic recording layer is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. The magnetic particles include ferromagnetic iron oxide such as γFe ₂ O ₂ , Co-coated γFe ₂ O ₃ , Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal system Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like can be used. Co-coated ferromagnetic iron oxide, such as Co-coated γFe ₂ O _2, is preferred. The shape may be any of a needle shape, a rice grain shape, a spherical shape, a cubic shape, and a plate shape. The specific surface area is preferably at least 20 m ² / g in S _BET, 30 m ² /
g or more is particularly preferred. Saturation magnetization (σs) of ferromagnetic material
Is preferably 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m
And particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁴
0 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, as described in JP-A-6-160332, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent. In addition, magnetic particles having a surface coated with an inorganic substance or an organic substance described in JP-A-4-259911 and JP-A-5-81652 can also be used.

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

As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. JP-A-5-088
No. 283, and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 to 10 μm
And preferably 0.2 to 5 μm, more preferably 0.3 to 3 μm. The weight ratio between the magnetic particles and the binder is:
0.5: 100 to 60: 100 is preferable, and 1: 100
~ 30: 100 is more preferable. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , and 0.01 to ² g / m ^2.
m ² is preferable, and 0.02 to 0.5 g / m ² is more preferable. The transmission yellow density of the magnetic recording layer is 0.01 to
0.50 is preferable, 0.03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable. The magnetic recording layer can be provided on the entire back surface or in a stripe shape by coating or printing on the back surface of the support. As a method for applying the magnetic recording layer, air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in JP-A-341436 is preferable.

The lubricating property is improved, the curl is adjusted,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. US Pat. No. 5,336,589 discloses a photosensitive material having a magnetic recording layer.
Nos. 5,250,404, 5,229,259, 5,215,874, and EP 466,130.

The polyester support preferably used in the silver halide color photographic light-sensitive material having the above-mentioned magnetic recording layer will be further described. No. 94-6023 (Invention Association; 1994.3.1)
5). The polyester is formed with a diol and an aromatic dicarboxylic acid as essential components, and as the aromatic dicarboxylic acid, 2,6-, 1,5-, 1,1,
4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid and the like can be mentioned. As the diol, diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, bisphenol and the like can be mentioned. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Of these, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight of the polymerized polymer ranges from about 5,000 to 200,000. The Tg of the polyester is 50 ° C. or higher, preferably 90 ° C. or higher.

The heat treatment temperature of the polyester support is preferably 40 ° C. or more and less than Tg, and more preferably Tg−20 ° C. or more and less than Tg in order to make the curl less likely to occur.
The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is preferably 0.1 to 1500 hours, and 0.5 to 200 hours.
Time is more preferred. The heat treatment of the support may be performed in the form of a roll, or may be performed while being transported in the form of a web. The surface is made uneven (for example, SnO ₂ or Sb ₂ O ₅
And the like, for example, may be applied to improve the surface state. In addition, it is preferable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), or after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. In order to prevent light pumping, it is possible to achieve the object by applying a commercially available dye or pigment such as Diaresin manufactured by Mitsubishi Kasei Co., Ltd. and Kayaset manufactured by Nippon Kayaku Co., Ltd. for polyester. is there.

Next, a film cartridge which can be loaded with the silver halide color photographic light-sensitive material of the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials include polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Patrone may further contain various antistatic agents,
Carbon black, metal oxide particles, nonionics, anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in Japanese Patent Laid-Open Publication No.
No. 3,12,538. Especially 25 ° C,
Those having a resistance at 25% RH of 10 ¹² Ω or less are preferred. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light-shielding properties. The size of the patrone is
It is also possible to keep the current 135 size, and to reduce the size of the camera, it is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less. The volume of the patrone case is 30 cm ³ or less, preferably 25 cm ^3
3 or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 to 15 g.

[0177] A cartridge that rotates the spool to feed the film may be used. Further, a structure in which the leading end of the film is housed in the patrone main body and the leading end of the film is sent out from the port portion of the patrone by rotating the spool shaft in the film sending direction may be employed. These are described in US Pat. No. 4,834,306 and US Pat.
No. 613.

The above-mentioned silver halide color photographic light-sensitive material can also be preferably used for a film unit with a lens described in JP-B-2-32615 and JP-B-3-39784. The film unit with a lens is a film unit in which an unexposed color or monochrome photographic photosensitive material is preliminarily light-tightly loaded in a manufacturing process of a unit body including a photographing lens and a shutter in, for example, an injection-molded plastic housing. is there. After the user takes a picture of this unit, the unit is sent to a photo lab for development. In the photo lab, the photographic film is taken out of the unit and developed and a photographic print is created. The exterior of the film unit with a lens includes, for example, Japanese Utility Model Publication No. 3-6910, Japanese Utility Model Publication No. 5-31647, and
As described in JP-A-225454 and Japanese Utility Model Publication No. 6-43798, optical parts necessary for photographing, such as a photographing lens unit and a finder unit, and photographing operation parts such as a shutter button and a winding knob are further exposed. It is covered with a paper box or a plastic package on which a description and a design showing the method of use are printed before use.

As described in JP-B-4-1546 and JP-B-7-1380, a film unit with a lens coated with paper or plastic may be made of a moisture-impermeable material or, for example, an ASTM test method. D-570
Of a non-hygroscopic material of 0.1% or less, such as an aluminum foil laminated sheet, a transparent or moisture-permeable plastic package on which aluminum foil or metal is deposited. In view of the storability of the photographic film built in the film unit with a lens, the humidity of the film unit with a lens in the above moisture-proof package is 25 ° C.
, The humidity is adjusted to be 40 to 70% relative humidity, preferably 50 to 65%. Furthermore, actual fairness 6
No.-6346, Japanese Utility Model Publication No. 6-8589 and U.S. Pat.
As described in the specification of JP-A-239-324, there is also a type in which a film unit with a lens covered with paper or plastic is housed in a shutter and a transparent waterproof case that can be rolled up to add an underwater or waterproof function.

The unit main body from which the photographic film has been removed at the developing station is collected at the unit manufacturing plant, and after inspection, reusable parts are reused, and some non-reusable plastic parts are melted and repelleted. The photographic lenses used for recycling are described in JP-B-7-56363, JP-A-63-199351, JP-B-3-22746, JP-B-3-39784, JP-B5-38353 and JP-B-7-35. As described in Japanese Patent No. 33237 and Japanese Utility Model Publication No. 7-50746, a plastic lens composed of one or two spherical or aspherical lenses is used. It is desirable that the film receiving surface of the exposure unit has a curved surface so as to be concave with respect to the photographing lens in the film running direction. There.

Further, the finder is based on Japanese Utility Model 2-4162.
No. 1, Jitsuhei 3-69910 and Jitsuhei 3-39784
As described in the specification, a transparent fine that only defines a finder opening in the housing may be used, or, for example, as described in Japanese Utility Model Publication No. 7-10345, an eyepiece and an objective finder lens are provided. An inverted Galileo or Albada finder may be used.

Further, JP-A-7-64177 and JP-A-6-64177
As described in JP-A-250282 and JP-A-7-128732, the finder is provided with a screen switching function,
In conjunction with this, the shooting aperture is switched so that normal size and panorama size exposure can be performed, or the standard panorama or high vision size shot on the film is optically or magnetically linked with the above finder switching. It may be recorded. Others change the focal length of the photographing lens and specify the finder field of view to perform approaching and telephoto photographing.

As the photographic film used in the film unit with a lens, a sheet-like or roll-like film can be used, and the photographic film can be stored directly as described in Dutch Patent No. 6,708,489. Alternatively, as shown in Japanese Patent Publication No. 2-32615, the film is housed in a container and loaded into a film unit with a lens. After taking a picture, to remove the photographed photo film from the film unit with lens for development,
As described in JP-B-6-16158 and JP-B-7-15545, a cover for taking out a photo film is provided at the bottom of a film unit housing with a lens, and the photo film is taken out by opening the cover. May be
As described in Dutch Patent 6,708,489, the photographic film may be taken out by opening or breaking the back cover. As described in U.S. Pat. No. 5,202,713, an opening which is usually in a light-shielded state is formed in a part of a film unit housing with a lens, and one end of the film is grasped and pulled out from the opening. It may be.

When a roll-shaped photographic film is used for the lens-fitted film unit, it is desirable that the roll-shaped photographic film be housed in a container and then housed in the lens-fitted film unit. Containers used are described, for example, in JP-A-54-111822 and JP-A-63-1.
No. 94255, U.S. Pat.
834,306, JP-A-2-124564 and 3-
Nos. 155544, 2-264248, JP-B-5-40508, JP-B2-32615 and JP-B-7
A cartridge for 135 film specified by the ISO standard described in the specification of JP-A-117707, or a photographic film that can be loaded with a photographic film of the ISO standard but has a smaller diameter than the above standard, or JP-A-8-21509, 8
-262645 and AP described in 8-26239
A single-axis cartridge or a cartridge having a spool to which one end of a film is fixed, such as a cartridge for S (Advanced Photo System), is advantageously used. Further, a two-axis cartridge using a 110-size standard film described in Japanese Utility Model Publication Nos. 4-14748 and 3-22746 can also be used. If necessary,
A photo film with a backing paper can also be used.

When a one-axis cartridge or cartridge having a spool to which one end of the film is fixed is used, the cartridge or cartridge is stored in one storage chamber of the film unit with the lens, and the cartridge is stored in the other storage chamber. Alternatively, most of the photographic film is pulled out from the patrone, and pre-winding (factory pre-winding) is performed in the manufacturing stage of the film unit with a lens for storing the rolled film, and the photographic film pulled out at each photographing is taken. The spool of the cartridge or patrone may be rotated by an external winding member and wound around the cartridge or patrone, or conversely, the leading end of the photographic film may be stored in one of the storage compartments of the film unit with a lens. A cartridge or patrone other than the cartridge or patrone connected to is loaded, and a cartridge or patrone in which most of the photographic film is stored in the other storage chamber is loaded. Alternatively, the cartridge or the cartridge may be drawn out and wound on a spool other than the cartridge or the cartridge.

In the factory pre-wind system, a photographic film drawn from a cartridge or a cartridge may be wound in a spool separate from the cartridge or the cartridge, and stored in the other storage room. As described in JP-A-32615, it may be stored in the other storage chamber in a hollow state. Also,
The above factory pre-wind is the Japanese Patent Publication 7-565
As described in No. 64, a photographic film is drawn in advance from a cartridge or a patrone in a dark room and wound into a roll, and the cartridge or the patrone and the photographic film in a roll are loaded into a film unit with a lens, and then the film unit with a lens is mounted. The back cover may be closed to shield light, or as described in JP-B-2-32615, a cartridge or a cartridge containing most of the photographic film is loaded in one storage chamber. At the same time, a cartridge other than the cartridge or patrone connected to the leading end of the photo film is loaded in the other storage room, the back cover is closed and light is shielded, and then the other spool is rotated from outside the film unit with the lens. You may make it wind up on the said spool.

The film unit with a lens is
As described in JP-A-1546 and JP-A-7-20667, a shutter mechanism for kicking shutter blades is charged by driving a driven sprocket engaged with a perforation of a film by an operation of rolling up a photographic film for each photographing. A self-cocking mechanism that prevents further winding is advantageously used. The charged shutter mechanism is released from the charged position by pressing the shutter button, kicks the shutter blades to perform exposure for photographing, and allows rewinding. Further, as described in Japanese Utility Model Publication Nos. 2-34688, 6-41227, JP-A-7-122389 and JP-B-6-12371, a film unit with a lens is provided with an external strobe charging device. A strobe board provided with a switch may be built-in.In this case, by turning on a synchro switch in conjunction with the photographing exposure operation by the shutter blade, the strobe light is emitted in conjunction with the photographing operation. Good.

On the other hand, a film unit with a lens includes:
As described in Japanese Utility Model Publication No. 4-1546, a counter is provided for displaying the number of shots or the number of remaining shots. A mechanism is provided for inhibiting the winding of the photo film, whereby the photographic film can be continuously wound up to the final winding position by a subsequent winding operation.

The processing layer of the processing material used in the present invention contains at least a base and / or a base precursor.
As the base, an inorganic or organic base can be used. As the inorganic base, JP-A-62-2094
No. 48, hydroxides, phosphates, carbonates, borates, organic acid salts of alkali metals or alkaline earth metals;
And acetylides of alkali metals or alkaline earth metals described in JP-A-3-25208.

As the organic base, ammonia,
Aliphatic or aromatic amines (eg, primary amines, secondary amines, tertiary amines, polyamines, hydroxylamines, heterocyclic amines), amidines,
Bis or tris or tetraamidine, guanidines, water-insoluble mono or bis or tris or tetraguanidines, quaternary ammonium hydroxides and the like can be mentioned.

As the base precursor, decarboxylation type, decomposition type, reaction type and complex salt forming type can be used. In the present invention, European Patent Publication 210,6
No. 60, U.S. Pat. No. 4,740,445, as a base precursor, a basic metal compound which is hardly soluble in water and a metal ion constituting this basic metal compound undergoes complex formation reaction with water as a medium. It is effective to adopt a method of generating a base by a combination of the obtained compounds (referred to as complex forming compounds). In this case, the basic metal compound which is hardly soluble in water is preferably added to the silver halide color photographic light-sensitive material, and the complex-forming compound is preferably added to the processing material, and vice versa.

The amount of the base or base precursor used is 0.1 to 20 g / m ^2, preferably 1 to 10 g / m ² . As the binder of the processing layer, the same hydrophilic polymer as that of the silver halide color photographic light-sensitive material can be used. The processing material is preferably hardened with a hardening material as in the case of a silver halide color photographic light-sensitive material. As the hardener, the same hardeners as those used in silver halide color photographic light-sensitive materials can be used.

The processing material may contain a mordant for the purpose of transferring and removing the dye used in the yellow filter layer and antihalation layer of the silver halide color photographic light-sensitive material as described above. As the mordant, a polymer mordant is preferable. Examples thereof include polymers containing secondary and tertiary amino groups, polymers having a nitrogen-containing heterocyclic moiety, and polymers containing these quaternary cation groups and having a molecular weight of 5,000 to 200,000, especially 10,000 to 20,000.
50,000. Specifically, US Pat.
48,564, 2,484,430, 3,14
8,061 and 3,756,814, 3,62
5,694, 3,859,096, 4,12
8,538, 3,958,995, 2,72
1,852, 2,798,063, 4,16
8,976, 3,709,690, 3,78
8,855, 3,642,482, 3,48
8,706, 3,557,066, 3,27
1,147, 3,271,148, 2,67
5,316, 2,882,156, British Patent 12
No. 77453, JP-A-54-115228 and JP-A-54-115228.
No. 145529, No. 54-126027, No. 50-7
1332, 53-30328, 52-15552
No. 8, No. 53-125, No. 53-1024, and the like. As the addition amount of the mordant,
^{0.1g / m 2 ~10g / m 2} , and preferably from ^{0.5g / m 2 ~5g / m 2} .

In the present invention, the processing material may contain a development terminator or a precursor of the development terminator, and the development terminator may be activated at the same time as the development or at a delayed timing. As used herein, the term "development terminator" refers to a compound that neutralizes a base immediately after appropriate development or reacts with the base to reduce the base concentration in the film and stop the development, or to interact with silver or a silver salt for development. Is a compound that suppresses Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that undergoes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For details, see
No. 190529, pages (31) to (32).

Similarly, a silver halide printout inhibitor may be included in the processing material, and its function may be developed simultaneously with the development. Examples of the printout inhibitor include JP-B-54-164 and JP-A-53-46.
No. 020, No. 48-45228, JP-B-57-845
No. 4, etc .;
Examples thereof include compounds of 1-phenyl-5-mercaptotetrazole described in 5,144, and viologen compounds described in JP-A-8-184936. The amount of the printout inhibitor used is 10 ^-4 to 1 mol / Ag mol, preferably 10 ^-3 to 10 ^-2 mol / Ag mol.

Further, the processing material contains a physical development nucleus and a silver halide solvent, solubilizes a part of the silver halide of the halogenated color photographic light-sensitive material simultaneously with the development, and fixes the silver halide on the processing layer. However, if the amount of the silver halide solvent is excessively increased, desensitization and a decrease in density are likely to occur. As the reducing agent required for physical development, those known in the field of halogenated color photographic light-sensitive materials can be used. In addition, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat in the process can be used. As the reducing agent, a developing agent that has not been used for development in the photosensitive material diffused from the silver halide color photographic photosensitive material can be used, and the reducing agent is previously contained in the processing material. You may keep it. In the latter case, the reducing agent contained in the processing material may be the same as or different from the reducing agent contained in the halogenated color photographic light-sensitive material.

Examples of the reducing agent used in the present invention include:
U.S. Pat. Nos. 4,500,626, columns 49-50, 4,483,914, columns 30-31 and 4,33.
0,617, 4,590,152, JP-A-60-1985.
140335, pages (17) to (18), 57-4
No. 0245, No. 56-138736, No. 59-178
No. 458, No. 59-53831, No. 59-18244
No. 9, No. 59-182450, No. 60-119555
Nos. 60-128436 to 60-128439
No. 60-198540, 60-18174
No. 2, 61-259253, 62-244444
No. 62-131256 to No. 62-131256
Until now, reducing agents and reducing agent precursors described in EP 220746A2, pages 78 to 96 can be used. Combinations of various reducing agents disclosed in U.S. Pat. No. 3,039,869 can also be used.

When a diffusion-resistant developing agent is used,
If necessary, an electron transfer agent and / or a precursor of the electron transfer agent may be used in combination. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. When the reducing agent is added to the processing material, the addition amount is 0.01 to 10
g / m ² , preferably 1/10 to 5 times the number of moles of silver in the silver halide color photographic light-sensitive material.

The physical development nucleus is for reducing soluble silver salt diffused from a silver halide color photographic light-sensitive material to convert it into physically developed silver, which is fixed to a processing layer. As the physical development nucleus, zinc, mercury, lead, cadmium,
Heavy metals such as iron, chromium, nickel, tin, cobalt, copper and ruthenium, or precious metals such as palladium, platinum, gold and silver, or these heavy metals, precious metal sulfur and selenium,
All known materials such as colloid particles of chalcogen compounds such as tellurium can be used. The physical development nuclei preferably have a particle size of about 2 to 200 nm. These physical development nuclei are added to the processing layer in an amount of 10 ⁻³ mg to 10 mg.
g / m ² .

As the silver halide solvent, known solvents can be used. For example, thiosulfates, sulfites, thiocyanates, thioether compounds described in JP-B-47-11386, uracils described in JP-A-8-179458, compounds having 5- to 6-membered imide groups such as hydantoin,
A compound having a carbon-sulfur double bond described in JP-A-53-144319, Analytical Chemika Acta (Analy
Mesoionic thiolate compounds such as trimethyltriazolium thiolate described in Tica Chinica Acta, 248, pp. 604-614 (1991) are preferably used. The compounds described in JP-A-8-69097 which can fix and stabilize silver halide can also be used as the silver halide solvent. The silver halide solvent may be used alone, or a plurality of silver halide solvents may be used in combination. The use of a halogenated solvent tends to cause a decrease in sensitivity, an increase in fogging, and a decrease in the maximum density. .

The total silver halide solvent content in the processing layer is 5 mmol / m ² or less, preferably ² mmol / m ² or less.
1 / m ² or less. The molar ratio is not more than 1/5, preferably not more than 1/10, more preferably not more than 1/20, relative to the amount of silver applied to the light-sensitive material. The silver halide solvent may be added as a solvent such as water, methanol, ethanol, acetone, dimethylformaldehyde, or methylpropyl glycol, or as an alkali or acidic aqueous solution, or may be added to the coating solution after dispersing solid fine particles.

The processing material includes a protective layer,
There may be an undercoat layer, a back layer, and other various auxiliary layers. The processing material is preferably provided with a processing layer on a continuous web. The term "continuous web" as used herein means that the length of the processing material is sufficiently longer than the long side of the corresponding silver halide color photographic light-sensitive material during processing, and a part thereof is cut when used for processing. And has a length enough to process a plurality of silver halide color photographic materials. Generally, it means that the length of the processing material is not less than 5 times and not more than 10000 times the width. The width of the processing material is arbitrary, but is preferably not less than the width of the corresponding silver halide color photographic light-sensitive material.

It is also preferable that a plurality of silver halide color photographic materials be processed in parallel, that is, a plurality of silver halide color photographic materials be processed side by side. in this case,
The width of the silver halide color photographic light-sensitive material is preferably equal to or more than the width of the silver halide color photographic light-sensitive material x the number of simultaneous processing. Such continuous web processing is preferably supplied from a delivery roll, wound up on a take-up roll and discarded. In particular, in the case of a silver halide color photographic light-sensitive material having a large size, disposal is easy. As described above, the handling property of the continuous web processing material is significantly improved as compared with the conventional sheet member.

The thickness of the support used in the processing material of the present invention is arbitrary, but is preferably thinner, particularly preferably 4 μm or more and 120 μm or less. Support thickness is 4
It is particularly preferable to use a processing material of 0 μm or less. In this case, the amount of the processing material per unit volume increases, so that the processing material roll can be made compact. The material of the support is not particularly limited, and a material that can withstand the processing temperature is used. In general,
The Photographic Society of Japan, "Basics of Photographic Engineering-Silver Halide Photography-",
Published by Corona Co., Ltd. (1979) (pp. 223-240)
A photographic support such as the paper or synthetic polymer (film) described above may be used.

The material for the support can be used alone or as a support coated or laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, JP-A-62-2531,1
No. 59, pages 29-31, JP-A-1-161,23
No. 6, pages 14 to 17; JP-A-63-31684.
8, JP-A-2-22,651, JP-A-3-56,955
And the supports described in U.S. Pat. No. 5,001,033. In addition, a support mainly composed of a styrene polymer having a syndiotactic structure can also be preferably used.

The surface of these supports may be coated with a hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black or another antistatic agent. A support on which aluminum is deposited can also be preferably used.

In the present invention, as a method for developing a silver halide color photographic light-sensitive material photographed by a camera or the like,
The silver halide color photographic light-sensitive material is used 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 silver halide color photographic light-sensitive material and the processing material. The material and the processing material are overlapped with the photosensitive layer and the processing layer facing each other.
Heat at a temperature of ° C for 5 to 60 seconds. The water here may be any water that is generally used. Specifically, distilled water, ion exchange water, tap water, well water, mineral water, and the like can be used. A method in which a small amount of a preservative is added to these waters for the purpose of preventing generation of scale and decay, and circulating and filtering the water with an activated carbon filter, an ion exchange resin filter or the like is also preferably used.

In the present invention, a silver halide color photographic light-sensitive material and / or a processing material are bonded together in a state of being swollen with water and heated. The state of the film at the time of swelling is unstable, and it is important to limit the amount of water to the above range in order to prevent local uneven coloring. The amount of water required for maximum swelling is determined by immersing a silver halide color photographic light-sensitive material or a processing material having a coating film to be measured in water to be used and measuring the film thickness when sufficiently swelled. After the calculation, the weight can be obtained by reducing the weight of the coating film. An example of a method for measuring the degree of swelling is described in Photographic Science Engineering, Vol. 16, p. 449 (197).
2 years).

As a method for applying water, there is a method in which a silver halide color photographic light-sensitive material or a processing material is immersed in water and excess water is removed with a squeeze roller. However,
It is preferable to apply a certain amount of water to the silver halide color photographic light-sensitive material or the processing material by coating. Further, a plurality of nozzle holes for injecting water are arranged at a certain interval in a straight line along a direction intersecting the transport direction of the silver halide color photographic light-sensitive material or the processing material, and the nozzles on the transport path. A method in which water is sprayed by a water coating device having an actuator for displacing the silver halide color photographic light-sensitive material or the processing material toward the processing material is particularly preferable. In addition, a method of applying water with a sponge or the like is also preferable because the apparatus is simple. The temperature of the water to be applied is 30 ° C to 60 ° C.
C is preferred.

An example of a method of superposing a silver halide color photographic light-sensitive material and a processing material is described in JP-A-62-2.
53, 159 and JP-A-61-147,244.

As a heating method in the development step, a heating block, a plate, a hot plate, a hot presser, a heating roller, a heating drum, a halogen lamp heater, an infrared and far-infrared lamp heater, or the like is used. Or through a high-temperature atmosphere. In the heat development process of the present invention, any of various heat development devices can be used. For example, JP-A-59-75,247, JP-A-59-177,547, JP-A-59-181,353,
No. 60-18,951, Japanese Utility Model Showa 62-25,944
No., Japanese Patent Application No. 4-277,517 and No. 4-243,07
No. 2, 4-244, 693, 6-164, 421
No. 6,164,422, etc. are preferably used.

Examples of commercially available devices include a Pictrostat 100, a Pictrostat 200, a Pictrostat 300, a Pictrostat 330, a Pictrostat 50, a Pictrograph 3000, a Pictograph 2000 and a Pictrostat 200 manufactured by Fuji Photo Film Co., Ltd. Can be used.

The silver halide color photographic light-sensitive material and / or the processing material used in the present invention may have a form having a conductive heating element layer as a heating means for heat development. The heat generating element of the present invention includes Japanese Patent Application Laid-Open No. 61-145,5.
No. 44 etc. can be used.

[0214]

Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.

[0215] Example 1 (1) Preparation of Emulsion - tabular silver bromide emulsion 1-A (comparative emulsion) - deionized average molecular weight of 15,000 treated gelatin 1g and H ₂ in an aqueous solution 1,000cc including KBr0.4g S
O ₄ was added to adjust the pH to 2 and the mixture was stirred while maintaining the temperature at 40 ° C., and 20 cc of 0.3 M AgNO ₃ aqueous solution (A) was added.
20 cc of a 3M aqueous KBr solution (B) was simultaneously added by a double jet for 40 seconds. Thereafter, the pH was adjusted to 5.0 by adding NaOH, and the temperature was raised to 75 ° C. in 35 minutes.
After adding 35 g of oxidized gelatin, 1.2 M Ag was added.
948 cc of the NO ₃ aqueous solution (C) and 850 cc of the 1.4 M KBr aqueous solution (D) were added for 33 minutes while accelerating the flow rate while maintaining the pAg at 8.3 (the flow rate at the end was 7.2 times that at the start). . 1.8 M AgNO ₃ aqueous solution (E) 115
cc and 131 cc of a 1.8 M aqueous KBr solution (F)
Ag was added at a constant rate while keeping it at 8.3. Thereafter, this emulsion was cooled to 35 ° C., washed with water by a conventional flocculation method using Demol made by Kao as a precipitant, 75 g of gelatin and 10 cc of phenoxyethanol were added, and PH = 5.5, pA
g was adjusted to 8.2.

In the obtained grains, tabular grains accounted for more than 99% of the total projected area of all grains, the average equivalent sphere diameter was 0.76 μm, the average thickness was 0.15 μm, and the average equivalent circle equivalent diameter. Is 1.4 μm and the aspect ratio is 9.3.
It was a hexagonal silver bromide tabular grain emulsion. The values of the average particle thickness and the average equivalent circle equivalent diameter were determined by taking transmission electron micrographs by the replica method.

-Tabular silver bromide emulsion 1-B (Emulsion of the present invention)-Except for the following, it was prepared in the same manner as emulsion 1-A. To the solution (F), 6 × 10 ⁻⁵ mol of yellow blood salt corresponding to iron was added. In the obtained grains, tabular grains accounted for more than 99% of the total projected area of all grains, had an average equivalent sphere diameter of 0.76 μm, an average thickness of 0.15 μm, and an average equivalent circle equivalent diameter of 1.4 μm. And a hexagonal silver bromide tabular grain emulsion having an aspect ratio of 9.3.

-Normal Crystalline Silver Bromide Emulsion 1-C (Comparative Emulsion)-H ₂ SO ₄ was added to 1,000 cc of an aqueous solution containing 36 g of demineralized gelatin and 0.6 g of KBr, and the pH was adjusted to 2 to 70 ° C. 80 cc of 0.3 M AgNO ₃ aqueous solution (A) and 0.3 M KBr aqueous solution (B) 8
0 cc were added simultaneously by a double jet for 2 minutes. Then, after adjusting the pH to 5.0 by adding NaOH,
933cc of 1.2M AgNO ₃ aqueous solution (C) and 1.4
M KBr aqueous solution (D) (850 cc) and pAg of 8.4
The addition was performed for 33 minutes while accelerating the flow rate while maintaining the flow rate (the flow rate at the end was 7.2 times that at the start). 115 cc of 1.8 M AgNO ₃ aqueous solution (E) and 1.8 M of KBr aqueous solution (F)
131 cc was added at a constant rate while maintaining the pAg at 8.4. Washing and dispersion were performed in the same manner as in the emulsion 1-A. The average equivalent sphere diameter was 0.76 μm and the emulsion was a silver bromide octahedral grain emulsion.

-Normal Crystalline Silver Bromide Emulsion 1-D (Comparative Emulsion)-Except for the following, it was prepared in the same manner as in Emulsion 1-C. To the solution (F), 6 × 10 ⁻⁵ mol of yellow blood salt corresponding to iron was added. The obtained grains were silver bromide octahedral grain emulsions having an average equivalent sphere diameter of 0.76 μm.

-Normal Crystalline Silver Bromide Emulsion 1-E (Comparative Emulsion)-H ₂ SO ₄ was added to 1,000 cc of an aqueous solution containing 36 g of demineralized gelatin and 0.45 g of KBr, and the pH was adjusted to 2 to 50 ° C. With stirring, and 1.2M AgNO ₃
850 cc of the aqueous solution (A) and 900 cc of a 1.4 M KBr aqueous solution (B) were added at a constant speed while maintaining the pAg at 8.0.
Added for 0 minutes. Five minutes later, 115 cc of a 1.8 M AgNO ₃ aqueous solution (C) and a 1.8 M KBr aqueous solution (D)
131 cc was added at a constant rate while maintaining the pAg at 8.4. Washing and dispersion were performed in the same manner as in the emulsion 1-A. The resulting grains were silver bromide octahedral grain emulsions having an average equivalent spherical diameter of 0.15 μm.

-Normal Crystalline Silver Bromide Emulsion 1-F (Comparative Emulsion)-Except for the following, it was prepared in the same manner as in Emulsion 1-E. To the solution (D), 6 × 10 ⁻⁵ mol of yellow blood salt corresponding to iron was added. The resulting grains were silver bromide octahedral grain emulsions having an average equivalent spherical diameter of 0.15 μm.

-Tabular silver bromide emulsion 1-G (comparative emulsion)-The same preparation as in the above emulsion 1-A, except that demineralized gelatin having an average molecular weight of 100,000 was used. In the resulting grains, tabular grains account for more than 99% of the total projected area of all grains, have an average equivalent sphere diameter of 0.76 μm, an average thickness of 0.25 μm, and an average equivalent circle equivalent diameter of 1.08 μm. so,
It was a hexagonal silver bromide tabular grain emulsion having an aspect ratio of 4.3.

-Tabular silver bromide emulsion 1-H (comparative emulsion)-Except for the following, the emulsion was prepared in the same manner as the emulsion 1-G. To the solution (F), 6 × 10 ⁻⁵ mol of yellow blood salt corresponding to iron was added. In the obtained grains, tabular grains account for more than 99% of the total projected area of all grains, have an average sphere equivalent diameter of 0.76 μm, an average thickness of 0.25 μm, an average equivalent circle equivalent diameter of 1.08 μm, and an aspect ratio of This was a hexagonal silver bromide tabular grain emulsion having a ratio of 4.3.

-Tabular silver bromide emulsion 1-I (emulsion of the present invention)-A silver bromide emulsion 1-I was prepared in the same manner as the emulsion 1-B, except for the following. To 1000 cc of an aqueous solution containing 0.5 g of oxidized gelatin and 0.37 g of KBr, add H ₂ SO ₄ to adjust pH = 2, stir while maintaining at 40, and add 20 cc of 0.3 M AgNO ₃ aqueous solution (A) to 0.1 cc. 3M KBr aqueous solution (B) 2
0 cc were added simultaneously by a double jet for 40 seconds.
Then, the pH was adjusted to 5.0 by adding NaOH to 35.
After raising the temperature to 75 ° C. for 35 minutes and adding 35 g of oxidized gelatin, a 1.2 M AgNO ₃ aqueous solution (C) 948 c
c and 850 cc of a 1.4 M aqueous KBr solution (D)
g was maintained at 8.58 while the flow was accelerated (final flow was 7.2 times the start) and added for 33 minutes. afterwards,
1.8 M KBr containing 115 cc of 1.8 M AgNO ₃ aqueous solution (E) and 6 × 10 ^-5 mol of yellow blood salt corresponding to iron
131 cc of aqueous solution (F) was added. The resulting particles are
Tabular grains account for more than 99% of the total projected area of all grains, have an average equivalent spherical diameter of 0.76 μm, and have an average thickness of
It was a hexagonal tabular grain emulsion having an aspect ratio of 23.9 and an average equivalent circle diameter of 1.91 μm, which was 0.08 μm.

-Tabular silver bromide emulsion 1-J (comparative emulsion)-Except for the following, it was prepared in the same manner as in emulsion 1-A. (F) Rhodium III bromide potassium is added to the solution at a concentration of rhodium equivalent 6 × 10 ⁻⁵
Mole was added. In the obtained grains, tabular grains accounted for more than 99% of the total projected area of all grains, had an average sphere equivalent diameter of 0.76 μM, an average thickness of 0.15 μm, and an average equivalent circle equivalent diameter of 1.4 μm. Was obtained as a hexagonal silver bromide tabular grain emulsion.

-Tabular silver bromide emulsion 1-K (comparative emulsion)-A silver bromide emulsion 1-K was prepared in the same manner as the emulsion 1-A, except for the following. (F) 6
Iridium potassium bromide was added in an amount of 6 × 10 ⁻⁵ mol of iridium. In the obtained grains, tabular grains accounted for more than 99% of the total projected area of all grains, had an average equivalent sphere diameter of 0.76 μm, an average thickness of 0.15 μm, and an average equivalent circle equivalent diameter of 1.4 μm. Was obtained as a hexagonal silver bromide tabular grain emulsion.

(2) Chemical sensitization The emulsions 1-A to 1-K were prepared at 60 ° C. and PH = 6.
2. Under the condition of pAg = 8.4, the following spectral sensitizing dye (sensitizing dye I for green-sensitive emulsion), compound 1, potassium thiocyanate, chloroauric acid, sodium thiosulfate and selenium sensitizer were added. Spectral sensitization and chemical sensitization were performed. A chemical sensitizer was used to stop the chemical sensitization. The amount of chemical sensitizer was adjusted to maximize the sensitivity of each emulsion for 1/100 second exposure.

[0228]

Embedded image

[0229]

Embedded image

(3) Preparation and Evaluation of Dispersion and Coated Sample 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.

Further, an emulsified dispersion of a magenta coupler was prepared. 7.80 g of magenta coupler (a), 5.45 g of developing agent (b), 8.21 g of high-boiling organic solvent (d)
And 24.0 ml of ethyl acetate were dissolved at 60 ° C. The above solution was mixed with 150 g of an aqueous solution in which 12.0 g of lime-processed gelatin and 0.6 g of surfactant (e) were dissolved, and emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver stirrer. After the dispersion, distilled water was added so that the total amount became 300 g, and the mixture was mixed at 2,000 rpm for 10 minutes.

[0232]

Embedded image

These dispersions and Emulsions 1-A to 1-K were combined and coated on a support with the composition shown in Table 1.
A silver halide color photographic light-sensitive material having a single layer of No. 01 to 111 was prepared.

[0234]

[Table 1]

Further, treatment materials P-1 as shown in Tables 2 and 3 were prepared.

[0236]

[Table 2]

[0237]

[Table 3]

[0238]

Embedded image

[0239]

Embedded image

Silver halide color photographic light-sensitive materials 101 to
111 was exposed for 1/100 second through an optical wedge and a green filter. 15 ml / m ^{2 of} 40 ° C. warm water was applied to the surface of the exposed silver halide color photographic light-sensitive material, and the processing material P-1 and the respective film surfaces were overlapped with each other. For 20 seconds. After this heat development, the silver halide color photographic light-sensitive material was peeled off to obtain a magenta-colored wedge-shaped image. For reading the image, the transmission densities of these color samples were measured to obtain a so-called characteristic curve. The reciprocal of the exposure corresponding to the density 0.15 higher than the fog density was defined as the relative sensitivity, and the sample 101
Is expressed as a relative value with the value of 100 as 100. In order to evaluate the image storability of the processed silver halide color photographic light-sensitive material, the following evaluation was performed. The specimen was placed in a fluorescent lamp fading tester equivalent to 500 Lux for 5 hours to evaluate a decrease in contrast with an increase in stain. Evaluation criteria were evaluated as follows. Dmax-Dmin decrease within 25%: ○, 2
5% or more and 50% or less were evaluated as Δ, and 50% or more as X. Table 4 summarizes the sensitivity and the results of the fluorescent lamp fading test.

[0241]

[Table 4]

From the results shown in Table 4, it can be seen that the use of a tabular photosensitive silver halide emulsion having a thickness of 0.2 μm or less using a shallow electron trap has effects of increasing the sensitivity and preventing an increase in stain after processing. . The image of the wedge-shaped image after the heat development processing was captured by a digital lab system frontier manufactured by Fuji Photo Film Co., Ltd., and output by Pictography 3000 manufactured by the company. As a result, in the comparative example using tabular emulsion grains, when image capture was repeated four times, the printout due to light exposure during scanner reading increased stain, lost contrast, and was no longer possible to read with a scanner. Met. On the other hand, the product of the present invention
Even when image capturing was repeated 12 times, the stain increase was small, and no deterioration of the captured image information was observed. The printout of the silver halide color photographic light-sensitive material before unprocessing was poor for all 101 to 111. It is considered that the heat development treatment makes it difficult to print out a photosensitive silver halide having a thickness of 0.2 μm or less containing a metal complex ion which is a shallow electron trap.

Example 2-(100) Tabular silver chlorobromide emulsion 2-A (comparative emulsion)-25 g of deionized alkali-treated bone gelatin having a methionine content of about 40 µmol / g, 1 g of sodium chloride and 1 N nitric acid 4 1,200 ml of an aqueous gelatin solution having a pH of 4.3 containing 0.5 ml was placed in a reaction vessel, and the temperature was raised to 40 ° C. While vigorously stirring this solution, a mixture of 100 ml of an aqueous solution containing 20 g of silver nitrate (A) and a solution of 100 ml of an aqueous solution containing 0.71 g of potassium bromide and 6.67 g of sodium chloride (B) were simultaneously mixed in 36 ml portions for 45 seconds. Was added. After stirring for 3 minutes after completion of the addition, potassium bromide 1.1 was added.
g of an aqueous solution containing 100 g of solution (C) 43.4 ml,
The addition took 30 seconds. After that, the temperature was lowered to 30 ° C. for 3 minutes and the temperature was kept constant. Then, the solution (A) and the solution (D) of 100 ml of an aqueous solution containing 7.02 g of sodium chloride were added to the solution (108).
The mixture was added simultaneously for 2 minutes and 15 seconds by ml. Then one
After stirring for 20 minutes, 20 ml of a 10% sodium chloride solution,
Add 7 ml of 1N aqueous sodium hydroxide solution and add PH
6.5 After the silver potential was set to 80 mV to the saturated calomel electrode, 2 ml of aqueous hydrogen peroxide (35%) was added. Thereafter, the temperature was raised to 75 ° C., and the mixture was aged for 5 minutes. Then
857.1 ml of solution (A) and 900 ml of solution (B) were added at an initial flow rate of 12 ml / min and finally doubled for 45 minutes while maintaining the silver potential (vs. SCE) at 120 mV. The temperature was lowered to 35 ° C., and desalting was performed according to a conventional method.

The resulting silver halide emulsion had an average grain size of 0.79 μm expressed in terms of sphere equivalent diameter, an average grain equivalent diameter of 1.48 μm, and an average grain thickness of 0.15 μm.
m, and an emulsion composed of silver chlorobromide (100) tabular grains having a silver bromide content of 5 mol% and an aspect ratio of 9.9. The same applies to the following emulsion 2-B. This emulsion 2-A was chemically sensitized in the same manner as in emulsion 1-A, except that a ribonucleic acid decomposition product was added after the addition of the sensitizing dye. I chose the amount that gives the highest feeling.

-(100) Tabular silver chlorobromide emulsion 2-B (Emulsion of the present invention)-The solution (D), which is 270 ml of an aqueous solution containing 0.14 g of yellow blood salt, is added to the second stage (A) Liquid, addition of liquid (B) 10
Minutes before, except that milk was added at a flow rate of 27 ml / min, the preparation was the same as for emulsion 2-A except for milk. The obtained silver halide emulsion has an average grain size of 0.3 as a diameter equivalent to a sphere.
Silver chlorobromide (100) tabular with 79 μm, average equivalent circle diameter of 1.48 μm, average grain thickness of 0.15 μm, aspect ratio of 9.9, and 5 mol% silver bromide content The emulsion was composed of grains. Chemical sensitization was performed in the same manner as for emulsion 2-A.

-(111) Tabular high silver chloride emulsion 2-C (comparative emulsion)-1,200 ml of an aqueous gelatin solution containing 2.4 g of deionized alkali-treated bone gelatin and 2 g of sodium chloride was placed in a reaction vessel, and heated to 35 ° C. While maintaining the solution and stirring the solution vigorously, an aqueous solution containing 100 g of an aqueous solution containing 165 g of silver nitrate (A) solution and an aqueous solution containing 59.1 g of sodium chloride were added.
100 ml of the solution (B) was simultaneously mixed and added in 60 ml portions for 1 minute. One minute after the completion of the addition, Compound (3) 0.1.
50 ml of solution (C), which is an aqueous solution containing 285 g,
1 minute, and after 1 minute, 10% aqueous sodium chloride solution 4
5 ml was added. Thereafter, the temperature was raised to 60 ° C. over 25 minutes. After 16 minutes, 260 ml of an aqueous gelatin solution containing 29 g of phthalated gelatin was added. After 3 minutes, 10 ml of the solution (C) was added.
Was added. One minute later, the solution (A) and the solution (B)
68 ml each, initial velocity 2.85 ml / min, acceleration 0.8
It was added simultaneously at 18 ml / (min) 2. From 10 minutes before the completion of the addition of the solution (A) and the solution (B), 3.9 g of sodium chloride was further added. Added in 3 seconds. (A) liquid
(B) 3 minutes after the addition of the solution, potassium thiocyanate 1%
After adding 27 ml, 260 ml of a 0.15% methanol solution of sensitizing dye I for green-sensitive emulsion was added, and one minute later, the temperature was raised to 75 ° C. and maintained for 10 minutes. The temperature was lowered to 40 ° C., and desalting was carried out using the precipitant (1) according to a standard method. The dispersion was carried out using 67 g of deionized alkali-treated bone gelatin, zinc nitrate and phenoxyethanol. pH 6.3, pA
g was adjusted to 7.7.

The obtained silver halide emulsion had an average grain size of 0.79 μm expressed as a sphere-equivalent diameter, an aspect ratio of 9, and a thickness of 0.16 μm, and a silver bromide content of 5 mol%. Of silver chlorobromide (111) tabular grains. Chemical sensitization was carried out at 60 ° C., and the sedimentation agent (1), 4-human peroxy-6-methyl-1,3,3a, 7-tetra-as-a-diene-tin, sodium thiosulfate, selenium sensitizer, gold chloride An acid and sodium benzenethiosulfonate were sequentially added to perform chemical sensitization to obtain the highest sensitivity. Termination of chemical sensitization was carried out using compound (4)
This was performed using

[0248]

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-(111) Tabular silver chlorobromide emulsion 2-D (emulsion of the present invention)-In silver halide emulsion 2-C, yellow blood salt was newly added to the emulsion.
Solution (D), which is 270 ml of an aqueous solution containing 1 g, was added at a rate of 27 m / min from 10 minutes before the completion of the addition of solution (A) and solution (B) in the second stage.
Except for adding at a flow rate of l,
Emulsion 2-D was prepared. The resulting silver halide emulsion is
0.79 μm average particle size expressed as sphere equivalent diameter
The emulsion was an emulsion composed of silver chlorobromide (111) tabular grains having an aspect ratio of 9 and a thickness of 0.16 μm and a silver bromide content of 5 mol%.

In the same manner as in Example 1, coating samples 201 to 204 were prepared for emulsions 2-A to 2-D, processed, and
Exposure and heat development were performed. The reading of the image was performed in the same manner as in Example 1. The results are shown in Table 5. Note that the sensitivity of the sample 201 was set to 100.

[0251]

[Table 5]

As shown in Table 5, by introducing metal ions and metal complex ions, which are shallow electron traps, in the high silver chloride tabular grain emulsion, the high silver chloride emulsion has high sensitivity. It can be seen that the increase in stain after the treatment is small. Further, as described in Example 1, when a repeated experiment of image reading was performed using a digital lab system frontier manufactured by Fuji Photo Film Co., Ltd., the comparative product showed a marked increase in stain after 3 times of image capturing. Although the contrast was lost, the product of the present invention did not print out and did not degrade the image information even when image capturing was repeated 10 times.

Example 3 Emulsion 3-A (Comparative Emulsion) H ₂ SO ₄ was added to 1000 cc of an aqueous solution containing 0.5 g of oxidized gelatin and 0.37 g of KBr, and the mixture was adjusted to PH = 2 and stirred at 40 ° C. And 0.3M AgNO ₃
Aqueous solution (A) 20cc and 0.3M KBr aqueous solution (B)
20 cc were added simultaneously with a double jet for 40 seconds. Thereafter, the pH was adjusted to 8.0 by adding NaOH (1N).
Was adjusted to pAg9.9 by adding a KBR solution, and the temperature was raised to 75 in 35 minutes. Five minutes after the addition of NaOH (1N), an aqueous solution containing 30 mg of sodium ethylthiosulfonate was added. After raising the temperature to 75 ° C., 35 g of oxidized gelatin was added, and then a 1.2 M AgNO ₃ aqueous solution (C) 921 was added.
cc and 800 cc of 1.4 M KBr aqueous solution (D)
The addition was performed for 33 minutes while maintaining the Ag at 8.58 and accelerating the flow rate (the flow rate at the end was 7.2 times that at the start). afterwards,
The temperature was lowered to 55 C and a 0.4 M AgNO ₃ aqueous solution (E) 8
0 cc and 223 cc of a 0.12 M KI aqueous solution (F) were added in a fixed amount for 3 minutes, followed by addition of a KBr aqueous solution to adjust the pAg to 8.8, and 115 cc of a 1.8 M AgNO ₃ aqueous solution (G). 1.8M KBr aqueous solution (H)
131 cc. Thereafter, the emulsion was cooled to 35 ° C., washed with water by a conventional flocculation method using Demol made by Kao, and 75 g of gelatin and 10 cc of phenoxyethanol were added to adjust the pH to 5.5 and the pAg to 8.2. It was adjusted.

In the obtained silver halide emulsion, tabular grains accounted for more than 99% of the total projected area of all grains, had an average equivalent sphere diameter of 0.76 μm, and had an average thickness of 0.08 μm.
The average equivalent circle equivalent diameter is 1.91μm and the aspect ratio is
It was a hexagonal tabular grain emulsion of 23.9.

-Emulsion 3-B (Emulsion of the present invention)-Emulsion 3-A was prepared in the same manner as Emulsion 3-A, except for the following. To the solution (H), 6 × 10 ⁻⁵ mol of yellow blood salt corresponding to iron was added. The resulting silver halide emulsion had tabular grains of 9% of the total projected area of all grains.
Occupies more than 9% and has an average equivalent spherical diameter of 0.76μ
m, an average thickness of 0.08 μm, an average equivalent circle diameter of 1.91 μm, and a hexagonal tabular grain emulsion having an aspect ratio of 23.9.

-Emulsion 3-C (Comparative emulsion)-Next, 930 ml of distilled water containing 0.74 g of gelatin having an average molecular weight of 12,000 and 0.3 g of potassium bromide was placed in a reaction vessel, and the temperature was raised to 35 ° C. did. To this solution, 30 ml of an aqueous solution (A) containing 1.2 g of silver nitrate and 30 ml of an aqueous solution (B) containing 0.82 g of potassium bromide were added over 20 seconds with vigorous stirring. After maintaining the temperature at 40 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was raised to 75 ° C. After adding 27.0 g of oxidized gelatin together with 200 ml of distilled water, 100 ml of an aqueous solution (C) containing 22.5 g of silver nitrate and 80 ml of an aqueous solution (D) containing 15.43 g of potassium bromide.
Was added over 11 minutes while accelerating the addition flow rate. Thereafter, the pH was adjusted to 8.2 by adding NaOH (1N), and then an aqueous solution (E) 250 containing 75.1 g of silver nitrate was added.
ml of potassium iodide and potassium bromide in a molar ratio of 3:97
(F) (potassium bromide concentration: 26%) was added over 20 minutes while accelerating the addition flow rate so that the silver potential of the reaction solution became -20 mV with respect to the saturated calomel electrode. (E) Three minutes after the addition of the solution, an aqueous solution containing 50 mg of sodium ethylthiosulfonate was added. Further, 75 ml of an aqueous solution (G) containing 18.7 g of silver nitrate and a 21.9% aqueous solution (H) of potassium bromide were added over 3 minutes.
And the silver potential of the reaction solution is 0 mV with respect to the saturated calomel electrode.
Was added so that After maintaining the temperature at 75 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was lowered to 55 ° C. Next, 120 ml of an aqueous solution (I) containing 8.1 g of silver nitrate and 320 ml of an aqueous solution (J) containing 7.26 g of potassium iodide were added over 5 minutes. After completion of the addition, potassium bromide 5.5
g, and kept at 55 ° C. for 1 minute.
180 ml of an aqueous solution (K) containing 4.3 g and 160 ml of an aqueous solution (L) containing 34.0 g of potassium bromide were added over 8 minutes. The temperature was lowered and desalting was performed according to a standard method.

In the emulsion obtained, tabular grains accounted for more than 99% of the total projected area of all grains, had an average equivalent spherical diameter of 0.66 μm, an average thickness of 0.095 μm, and an equivalent circular diameter of 1%. It was .42 μm and the aspect ratio was 15.

-Emulsion 3-D (Emulsion of the present invention)-The emulsion was prepared in the same manner as in Emulsion 3-C, except for the following. To the solution (K), yellow blood salt was added in an amount of 3 × 10 ⁻⁵ mol corresponding to iron. The resulting silver halide emulsion had tabular grains of 9% of the total projected area of all grains.
Occupies over 8% and has an average equivalent spherical diameter of 0.66μ
m, the average thickness is 0.095 μm, and the equivalent circular diameter is 1.
The aspect ratio was 15 at 42 μm.

-Emulsion 3-E (comparative emulsion)-950 ml of distilled water containing 12.5 g of gelatin having an average molecular weight of 15,000, 4.35 g of potassium bromide and 0.32 g of potassium iodide was placed in a reaction vessel, and the mixture was placed in a reaction vessel. The temperature was raised to ° C. While the solution was vigorously stirred, 50 ml of an aqueous solution containing 8.3 g of silver nitrate (A) and 50 ml of an aqueous solution containing 2.67 g of potassium bromide (B) were added over 45 seconds. After maintaining at 45 ° C. for 4 minutes, the temperature of the reaction solution was raised to 63 ° C. After adding 17.0 g of gelatin together with 130 ml of distilled water, 150 ml of an aqueous solution containing 51.2 g of silver nitrate (C)
And a 24.8% aqueous solution of potassium bromide (D) were added over a period of 13 minutes while accelerating the addition flow rate so that the silver potential of the reaction solution became 0 mV with respect to the saturated calomel electrode. After completion of the addition, the mixture was kept at 63 ° C. for 2 minutes, and then NaOH
(1N) was added to adjust the pH to 8.4. Thereafter, the temperature of the reaction solution was lowered to 45 ° C., and an aqueous solution containing 65 mg of sodium ethylthiosulfonate was added. Then, 5.9 silver nitrate.
g of an aqueous solution containing 50 g (E) and potassium iodide 5.82
g of an aqueous solution containing 320 g (F) were added over 5 minutes. Further, an aqueous solution 35 containing 104.3 g of silver nitrate
0 ml (G) and a 25% aqueous solution of potassium bromide (H) were added over 45 minutes so that the silver potential of the reaction solution became 10 mV with respect to the saturated calomel electrode. After completion of the addition, 1.4 g of potassium bromide and 4 mg of sodium ethylthiosulfonate were added, and the mixture was kept at 45 ° C. for 5 minutes.

The obtained emulsion had an average particle size of 0.37 μm expressed by a sphere-equivalent diameter and an average circle equivalent diameter of 0.58 μm.
m, average thickness 0.1 μm, average aspect ratio 5.
And 8 hexagonal tabular grains.

-Emulsion 3-F (Emulsion of the present invention)-Emulsion 3-F was prepared in the same manner as Emulsion 3-A, except for the following. To the solution (H), 8 × 10 ⁻⁵ mol of yellow blood salt corresponding to iron was added. The resulting emulsion had an average grain size of 0.37 μm, expressed as a diameter equivalent to a sphere.
m, the average equivalent circle diameter is 0.58 μm, and the average thickness is 0.1 μm.
It was a hexagonal tabular grain having a size of 1 μm and an aspect ratio of 5.8.

The chemical sensitization of these emulsions was carried out in the same manner as in Emulsion 1 except that the sensitizing dye used was sensitizing dye II for blue-sensitive emulsion.
Performed in the same manner as in -A. The amounts of chloroauric acid, sodium thiosulfate, and selenium sensitizer were adjusted so that the exposure was increased by 1/100 second exposure. The spectral sensitizing dye and the chemical sensitizer were changed in proportion to the grain surface area of each emulsion.

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Emulsions 3-A, 3-B, 3-C, 3-
In D, 3-E and 3-F, the pH during grain formation was adjusted to 5.0, and sensitizing dyes were used as sensitizing dyes III to V for red-sensitive emulsions.
3-A (r), 3-B (r), 3-C
(R), 3-D (r), 3-E (r) and 3-F (r)
Was prepared. Further, the emulsions 3-A, 3-B, 3-C,
In 3-D, 3-E and 3-F, pH during particle formation
Is 5.0 and the sensitizing dyes are sensitizing dyes VI to VI for green-sensitive emulsions.
3-A (g), 3-B (g), 3-C changed to I
(G), 3-D (g), 3-E (g) and 3-F (g)
Was prepared.

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[0266]

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Further, according to the method for preparing a coupler dispersion of Example 1, cyan and yellow coupler dispersions were also prepared. The compounds used are shown below.

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-Preparation of Dye Composition for Yellow Filter and Antihalation Layer- The dye composition was prepared and added as an emulsified dispersion as follows. The leuco dye, the developer and, if necessary, the high-boiling organic solvent are weighed, and ethyl acetate is added, and the mixture is heated and dissolved at about 60 ° C. to form a homogeneous solution. 100 cc of this solution is mixed with 1 part of sodium dodecylbenzenesulfonate. 0.0g, about 6
6.6% aqueous solution of lime-processed gelatin heated to 0 ° C 19
Add 0cc and 10,000 r for 10 minutes with a homogenizer.
Dispersed at pm. Two types of dye dispersions shown in Table 6 were prepared.

[0270]

[Table 6]

[0271]

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The emulsions 3-A, 3-C and 3-E were used for a high-speed emulsion layer, a medium-speed emulsion layer and a low-speed emulsion layer of a blue-sensitive yellow-color-forming layer, respectively.
(R), 3-C (r) and 3-F (r) were used in a high-speed emulsion layer, a medium-speed emulsion layer and a low-speed emulsion layer of a red-sensitive cyan coloring layer, respectively. (G), 3-C
(G) and 3-E (g) were used for the high-speed emulsion layer, the medium-speed emulsion layer, and the low-speed emulsion layer of the green-sensitive magenta color-forming layer, respectively, to prepare the above dispersions. 10 to 10 (Table 7
Tables 10 to 10 describe one table divided into four for convenience. 2), a multilayer silver halide color photographic light-sensitive material 301 was prepared.

[0273]

[Table 7]

[0274]

[Table 8]

[0275]

[Table 9]

[0276]

[Table 10]

[0277]

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A silver halide color photographic light-sensitive material 302 was constructed in the same manner as the silver halide color photographic light-sensitive material 301 except that the emulsion was changed as follows. Emulsions 3-B, 3-D and 3-
F was used for a high-speed emulsion layer, a medium-speed emulsion layer, and a low-speed emulsion layer of a blue-sensitive yellow-color-forming layer, respectively.
(R), 3-D (r) and 3-F (r) were used in a high-speed emulsion layer, a medium-speed emulsion layer and a low-speed emulsion layer of a red-sensitive cyan color-forming layer, respectively. (G), 3-D
(G) and 3-F (g) were used in a green-sensitive magenta color-forming layer, a high-speed emulsion layer, a medium-speed emulsion layer, and a low-speed emulsion layer, respectively.

The photographic characteristics of these silver halide color photographic light-sensitive materials were tested in the same manner as in Example 1 except that the filter at the time of exposure was removed. First, each silver halide color photographic light-sensitive material was exposed to light for 1/100 second through an optical wedge. Processing solution P-2 was applied to the surface of the silver halide color photographic light-sensitive material after exposure by applying 20 ml / m ² of warm water at 40 ° C.
After laminating the film surfaces with each other, heat development was performed at 83 ° C. for 30 seconds using a heat drum. The image of the silver halide color photographic light-sensitive material thus processed is displayed in blue,
Using green and red filters, measure the transmission density of the wedge-shaped image of yellow, magenta, and cyan to obtain a characteristic curve,
As in Example 1, the reciprocal of the exposure amount corresponding to the density 0.15 higher than the fog density was defined as the relative sensitivity, and the sensitivity of each color sensitivity was expressed as a relative value with the value of Sample 301 being 100. Processing material P-2 is the same processing material as P-1 except that the amount of guanidine picolinate was changed to 4500 mg / m ² . Exposure was performed and the above processing was performed. Quantify the decrease in contrast with increasing sensitivity and stain,
The image was captured in the same manner as in Example 1, and the results are summarized in Table 11.

[0280]

[Table 11]

From the above results, even in a multilayer silver halide color photographic light-sensitive material, tabular light-sensitive silver halide emulsion grains containing metal ions and metal complex ions, which are shallow electron traps, were used as in the present invention. The silver halide color photographic light-sensitive material for thermal development used was found to have the effects of high sensitivity and little increase in stain after processing.

Example 4-4-A (Comparative emulsion)-21 g of deionized alkali-treated bone gelatin having a methionine content of about 40 µmol / g and 0.8 g of sodium chloride and 1 g
1,000 ml of an aqueous gelatin solution having a pH of 4.6 containing 3.8 ml of normal sulfuric acid was placed in a reaction vessel, and the temperature was raised to 40 ° C. A solution (A) of 30 ml of an aqueous solution containing 11 g of silver nitrate and a solution (B) of 30 ml of an aqueous solution containing 0.4 g of potassium bromide and 3.7 g of sodium chloride were simultaneously added to this solution with stirring for 45 seconds. After stirring for 10 minutes after the addition was completed, the temperature was lowered to 30 ° C. over 3 minutes. 37 ml of aqueous solution (C) containing 1.1 g of potassium bromide was added for 14 seconds at the beginning of the temperature drop. After the temperature was kept constant at 30 ° C., 92 ml of solution (A) and 11.68 g of sodium chloride were added.
Was added simultaneously for 2 minutes and 15 seconds. After stirring for 1 minute, 17 ml of 10% sodium chloride solution and 5 ml of 1N aqueous sodium hydroxide solution were added to adjust the pH to 6.5, and then 2 ml of hydrogen peroxide (35%) was added. Thereafter, the temperature was raised to 65 ° C., and the mixture was aged for 3 minutes. Next, 675 ml of the (E) solution containing 135 g of silver nitrate and 675 ml of the aqueous solution containing 4.73 g of potassium bromide and 44.1 g of sodium chloride were added while maintaining the silver potential (vs. SCE) at 120 mV.
For 2 minutes and 42 seconds, it was added at an initial flow rate of 11.7 ml / min, finally accelerating 1.7 times. After aging for 25 minutes, 102 ml of an aqueous solution containing 9 g of demineralized gelatin was added. After 10 minutes, the temperature was lowered to 35 ° C. and desalting was performed according to a conventional method.

The resulting emulsion had an average particle size of 0.58 μm expressed as a sphere-equivalent diameter, and an average particle circle-equivalent diameter of 0.5.
Silver chlorobromide (1 mol, 87 μm, average grain thickness 0.17 μm, aspect ratio 5.2, 5 mol% silver bromide content)
00) Emulsion consisting of tabular grains. Chemical sensitization
Performed in the same manner as in 2-A.

-Emulsion 4-B (Emulsion of the present invention)-Solution (G), which is 270 ml of an aqueous solution containing 0.3 g of yellow blood salt, is newly added with solution (E) and solution (F) in the second stage. End 1
It was prepared in the same manner as in Emulsion 4-A except that it was added at a flow rate of 27 ml / min from 0 minutes before. The resulting silver halide emulsion had an average grain size of 0.58 μm expressed as a diameter equivalent to a sphere.
m, an average grain equivalent circle diameter of 0.87 μm, an average grain thickness of 0.17 μm, an aspect ratio of 5.2, and an emulsion composed of silver chlorobromide (100) tabular grains having a silver bromide content of 5 mol%. Met. Chemical sensitization was performed in the same manner as in the emulsion 4-A.

The above silver halide color photographic light-sensitive material 30
In 1, the middle-speed emulsion layer of each of the green, red and blue light-sensitive layers was removed, and the emulsion 2 was added to the green-sensitive high-speed emulsion layer.
-A, the emulsion 2-A was added to the red-sensitive high-sensitivity emulsion layer.
The same emulsion 2-A (r) was used except that a sensitizing dye for a red-sensitive emulsion was used, and a sensitizing dye for a blue-sensitive emulsion in Emulsion 2-A was used in a blue-sensitive high-sensitivity emulsion layer. The same emulsion 3-A (b) was used except that
Emulsion 4-A is the same except that emulsion 4-A is used for the green light-sensitive low-sensitivity emulsion layer and sensitizing dye for red-sensitive emulsion is used for emulsion 4-A for the red light-sensitive low-sensitivity emulsion layer.
Using (r), the emulsion 4-
A comparative silver halide color photographic light-sensitive material 401 having a multilayer structure was prepared using the same emulsion 4-A (b) except that a sensitizing dye for a blue-sensitive emulsion was used in A.
In silver halide color photographic light-sensitive material 401, emulsions 2-A, 2-A (r), 2-A (b), 4-A, 4-A
(R) and 4-A (b) were converted to 2-B and 2-B, respectively.
(R), 2-B (b), 4-B, 4-B (r) and 4-
A silver halide color photographic light-sensitive material 402 of the present invention was prepared in the same manner except that B (b) was changed.

The emulsions 2-B (r) and 4-B (r)
Each of the emulsions 2-B and 4-B is the same silver halide emulsion except that a sensitizing dye for a red-sensitive emulsion is used. The emulsions 2-B (b) and 4-B (b) are the same silver halide emulsions except that a sensitizing dye for a blue-sensitive emulsion was used in each of the emulsions 2-B and 4-B. When processing and tests were performed in the same manner as in Example 3 except that the development time was changed to 20 seconds, the silver halide color photographic light-sensitive material 402 of the present invention was compared with the comparative silver halide color photographic light-sensitive material 401. It was found that the sensitivity became high and the image stability after the processing was improved, and the effect of the present invention was shown.

Example 5 Emulsion 5-A (Comparative Emulsion) In Emulsion 2-C, the amount of solution (A) and solution (B) was changed to 1.2 g with deionized alkali-treated bone gelatin.
Emulsion 2 except that 0 ml was added simultaneously for 3 minutes.
Emulsion 5-A was prepared in the same manner as in -C. The resulting silver halide emulsion has an average grain size expressed as a sphere-equivalent diameter of 0.53 μm, an aspect ratio of 4.5, and a thickness of 0.1 mm.
Silver chlorobromide (1 mol.
11) Emulsion consisting of tabular grains.

-Emulsion 5-B (Emulsion of the present invention)-In the emulsion 5-A, a solution (D), which is 270 ml of an aqueous solution containing 0.3 g of yellow blood salt, is newly added to the solution (A) in the second stage.
(B) Emulsion 5-B was prepared in the same manner as Emulsion 5-A, except that it was added at a flow rate of 27 ml / min from 10 minutes before the completion of the addition of the solution.
Was prepared. The obtained silver halide emulsion had an average grain size expressed by a diameter equivalent to a sphere of 0.53 μm, an aspect ratio of 4.5, a thickness of 0.17 μm, and a silver bromide content of 5 mol%. The emulsion was composed of silver chlorobromide (111) tabular grains.

In the photosensitive material 401, the emulsion 2-
A, 2-A (r), 2-A (b), 4-A, 4-A
(R) and 4-A (b) were converted to 2-C and 2-C, respectively.
(R), 2-C (b) 5-A, 5-A (r) and 5-A
A photosensitive material 501 was prepared in the same manner except that (b) was changed.

Emulsions 2-C (r) and 5-A (r) are the same emulsions except that a sensitizing dye for a red-sensitive emulsion was used in each of the emulsions 2-C and 5-A. Emulsion 2-C (b)
And 5-A (b) are the same emulsions except that a sensitizing dye for a blue-sensitive emulsion was used in each of the emulsions 2-C and 5-A. In the photosensitive material 401, emulsions 2-A,
-A (r), 2-A (b), 4-A, 4-A (r) and 4-A (b) are converted to 2-D, 2-D (r), 2-D, respectively.
A light-sensitive material 502 of the present invention was prepared in the same manner except that (b), 5-B, 5-B (r) and 5-B (b) were changed.

Emulsions 2-D (r) and 5-B (r) are the same emulsions except that a sensitizing dye for a red-sensitive emulsion was used in each of emulsions 2-D and 5-B. Emulsion 2-D (b)
And 5-B (b) are the same emulsions except that a sensitizing dye for a blue-sensitive emulsion was used in each of the emulsions 2-D and 5-B.

When processing and tests were carried out in the same manner as in Example 4, the light-sensitive material 502 of the present invention was compared with the light-sensitive material 501 of the comparative example.
It was found that the sensitivity was higher and the image stability after the processing was improved as compared with that of the above, and the effect of the present invention was shown.

Example 6 In the multi-layer coated samples prepared in Examples 3, 4 and 5,
The support was changed to a support prepared by the following manufacturing method, a sample was placed in a cartridge, a sample was loaded into a camera, and a photographing test was performed. A good image was obtained, and the product was manufactured by Fuji Photo Film Co., Ltd. Images were captured by Digital Lab System Frontier and output by Pictography 3000.
When the image capturing was repeated twice, the comparative product showed a large increase in stain, the contrast disappeared, and a good hard copy image could not be obtained. On the other hand, according to the product of the present invention, even when image reading was repeated eight times, the increase in stain was small, and a good hard copy image was obtained even when the image information captured at that time was used. The effects of the present invention having high feeling and image stability after processing were confirmed.

1) Support The support used in this example was prepared by the following method. <Preparation of Support> A support used in the present invention was prepared by the following method. 100% by weight of polyethylene-2,6-naphthalate (PEN) polymer and Tinuvin P. After drying 2 parts by weight of 326 (manufactured by Ciba-Geigy Corporation), the mixture was melted at 300 ° C., extruded from a T-die, stretched by a factor of 3.3 at 140 °, and then stretched at 130 ° by 3.times. Perform 3 times lateral stretching, and then 6
This was heat-set for 2 seconds to obtain a PEN film having a thickness of 92 μm.
The PEN film has a blue dye, a magenta dye, and a yellow dye (public technical report: official technical report No. 94-6023).
-1, -4, -6, -24, -26, -2
7, -5) were converted to yellow density 0.01 and magenta density 0.
08 and a cyan concentration of 0.09. Furthermore,
Wrap it around a 20 cm diameter stainless steel core
The substrate was given a heat history of 30 hours and was hardly curled.

<Coating of Undercoat Layer> The support was subjected to a corona discharge treatment, a UV irradiation treatment and a glow discharge treatment on both surfaces, and then gelatin (0.1 g / m 2) was applied to each surface.
² ), sodium α-sulfodi-2-ethylhexyl succinate (0.01 g / m ² ), salicylic acid (0.02
5 g / m ² ), PQ-1 (0.005 g / m ² ), PQ
-2 (0.006 g / m ² ) was applied (10 cc / m ² , using a bar coater) to provide an undercoat layer 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 set at 115 ° C.).

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<Coating of Back Layer> 1) Coating of Antistatic Layer A tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm. about 0.08μ; 0.027g / m ^2), gelatin (0.03g / m ^2),
(CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ (0.02 g / m ² ), poly (degree of polymerization 10) oxyethylene-p-nonylphenol (0.005 g /
m ² ), PQ-3 (0.008 g / m ² ) and resorcin.

[0298]

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2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g) , Major axis 0.14μm,
Short axis 0.03 μm, saturation magnetization 89 emu / g, Fe ^{+ 2} / Fe + ⁺³ = 6/94,
The surface was treated with 2 wt% of iron oxide by aluminum oxide silicon) 0.06 g / m ² of diacetyl cellulose 1.15 g / m
² (Iron oxide dispersion was carried out with an open kneader and a sand mill), PQ-4 (0.075 g / m ² ), PQ-
5 (0.004 g / m ² ) was applied with a bar coater using acetone, methyl ethyl ketone, cyclohexanone, and dibutyl phthalate as a solvent to obtain a 1.2 μm-thick magnetic recording layer. C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (50g /
m ² ), silica particles as a matting agent (average particle size 1.0 μm)
And abrasive aluminum oxide (Reynolds Metal Reynolds Me
tal ERC-DBM; average particle size 0.44 μm)
g / m ² and 15 mg / m ² . 11 for drying
The test was carried out at 5 ° C for 6 minutes (115 ° C for all rollers and conveyors in the drying zone). The increase in the DB color density 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 ×
104 A / m and the squareness ratio were 65%.

[0300]

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3) Preparation of Sliding Layer Hydroxyethylcellulose (25 mg / m ² ), PQ-6 (7.
5mg / m ^2), was applied to ^{PQ-7 (1.5mg / m 2} ) polydimethylsiloxane (B-3) 1.5mg / m 2. This mixture was melted at 105 ° C in xylene / propylene glycol monomethyl ether (1/1), poured into propylene monomethyl ether (10 times the volume) at room temperature, dispersed, and then dispersed in acetone. (Average particle size: 0.01 μm). Drying was carried out at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were at 115 ° C.). The sliding layer has a dynamic friction coefficient of 0.10 (5mm φ stainless steel hard ball, weight of 100g, speed
6 cm / min), the coefficient of static friction was 0.09 (clip method), and the coefficient of kinetic friction between the emulsion surface and the sliding layer described later was 0.18, which were excellent characteristics.

[0302]

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[0303]

According to the present invention, the above-mentioned conventional problems can be solved. Further, according to the present invention, a silver halide color photographic light-sensitive material for high-sensitivity photography, which does not require a bleaching / fixing step, has a low impact on the environment, and can easily and quickly form a stable image against light, and The color image forming method used can be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 7/392 G03C 7/392 Z 7/407 7/407

Claims (6)

[Claims] 1. A photosensitive silver halide emulsion on a support,
A photographic component layer containing at least one photosensitive layer containing a developing agent, a compound that forms a dye by a coupling reaction with an oxidized form of the developing agent, and a binder; In a silver halide color photographic material in which an image in which part or all of the silver halide in the reaction remains is read and the image is read, at least one of the photosensitive silver halide emulsions has a depth of at least one. Containing at least one selected from metal ions and metal complex ions that are electron traps of 0.2 eV or less,
A silver halide color photographic light-sensitive material comprising tabular light-sensitive silver halide grains having an average thickness of 0.2 [mu] m or less and an average aspect ratio of 3 to 100. 2. The method according to claim 1, wherein the metal ions and the metal complex ions, which are electron traps having a depth of 0.2 eV or less, include Pb ions, cyan ligands, and Re, Os, Ru, Fe,
2. The silver halide color photographic light-sensitive material according to claim 1, which is an ion containing Ir or Co. 3. The silver halide color photographic material according to claim 1, wherein said photosensitive silver halide emulsion contains silver chloride in an amount of 50 mol% or more. 4. The developing agent is represented by any one of the following general formulas (1), (2), (3), (4) and (5). 4. The silver halide color photographic light-sensitive material as described in any one of 1. to 3. above. Embedded image Embedded image Embedded image Embedded image Embedded image In the general formulas (1) to (5), R _{1 to} R ₄ 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, Alkoxy, aryloxy, alkylthio, arylthio, alkylcarbamoyl, arylcarbamoyl, carbamoyl, alkylsulfamoyl, arylsulfamoyl, sulfamoyl, cyano,
Represents an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group or an acyloxy group. R ₅ represents a substituted or unsubstituted alkyl group, aryl group or 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 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.
R ₇ and R ₈ may be bonded to each other to form a double bond or a ring. 5. After the silver halide color photographic material is exposed, 1/10 to 1/10 of the total amount of water required for the maximum swelling of all the coating films in the silver halide color photographic material.
A double amount of water is interposed between the silver halide color photographic light-sensitive material and a processing material containing a base and / or a base precursor on a support, and heat development is performed in a state where both are bonded to each other, A color image is formed on the silver halide color photographic light-sensitive material, and a part or all of the unreacted silver halide remains in the silver halide color photographic light-sensitive material. 5. A color image forming method for reading a color image above and forming a color image based on the read image information, wherein the silver halide color photographic light-sensitive material is the silver halide color photographic material according to any one of claims 1 to 4. A color image forming method, which is a photographic light-sensitive material. 6. After exposing a silver halide color photographic light-sensitive material, 1/10 to 1/10 of the total amount of water required for maximum swelling of all coating films in the silver halide color photographic light-sensitive material.
The same amount of water was interposed between the silver halide color photographic light-sensitive material and the processing material containing a base and / or a base precursor on a support, and heat development was performed in a state where both were adhered. A color image is formed on the silver halide color photographic light-sensitive material, and a part or all of the unreacted silver halide is left on the silver halide color photographic light-sensitive material. 5. A color image forming method for reading a color image by a scanner and printing out based on the image information, wherein the silver halide color photographic light-sensitive material is
5. A color image forming method, which is the silver halide color photographic light-sensitive material according to any one of the above.