JPH10161263A - Silver halide color photographic sensitive material and color image forming method by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the head-developable silver halide color photographic sensitive material high in sensitivity and small in uneven development and adapted to image formation by simple rapid and easy processing small in load on the environment. SOLUTION: At least one of the photographic constituent layers formed by coating on a support is a photosensitive layer containing a photosensitive silver halide emulsion, a developing agent, a compound to the allowed to release a dye by coupling with a oxidation product of a developing agent, and a binder and this emulsion contains at least one kinds selected from metal ions and metal complex ions functions as an electron trap having a depth of <=0.6eV and at least one kind of flat silver halide grains having an average aspect ratio of 4-100.

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, and more particularly, to a method for forming an image by a simple and rapid processing with less environmental load. The use of silver halide color photographic light-sensitive materials for high-quality photography with high sensitivity and no image unevenness during the development process, and the use of the silver halide color photographic light-sensitive materials reduces the burden on the environment. The present invention also relates to a color image forming method capable of easily and quickly forming a high-quality image without unevenness.

[0002]

2. Description of the Related Art In recent years, photosensitive materials for color photography using silver halide have been increasingly developed, and it is now possible to easily obtain high-quality color images.
For example, in a system usually called a color photograph, a color negative film is used to take a picture, and image information recorded on the developed color negative film is optically printed on color photographic paper to obtain a color print. In recent years, this process has advanced to a high degree, and with the spread of the color lab, which is a large-scale centralized base that produces large amounts of color prints with high efficiency, or the so-called mini-lab, which is a small and simple printer processor installed in stores, But you can easily enjoy color photos.

[0003] In the currently popular color photography system,
The principle of color reproduction by the subtractive color method is adopted. In a general color negative film, a light-sensitive layer using a silver halide emulsion, which is a light-sensitive element having photosensitivity in the blue, green, and red regions, is provided on a transmission support. So-called color couplers forming respective dyes of yellow, magenta and cyan, each of which is a complementary color, are contained in combination. The color negative film that has been imagewise exposed by photography is developed in a color developer containing an aromatic primary amine developing agent. At this time, the exposed silver halide grains are reduced (developed) by a developing agent.
The respective dyes are formed (colored) by a coupling reaction between the oxidized form of the developing agent and the color coupler, which are simultaneously formed. A color image is formed by removing metallic silver (developed silver) and unreacted silver halide generated by the color development and development by bleaching and fixing, respectively. On a color photographic paper, which is a photosensitive material obtained by coating a photosensitive layer having a similar combination of a photosensitive wavelength region and a coloring hue on a reflective support, optical exposure is performed through a color negative film after development processing, By performing the same color development and development, and bleaching and fixing, a color print reproducing the scene at the time of photographing can be obtained.

[0004] Although systems for obtaining such color prints are now widespread, demands for improving their simplicity 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. . Against this background, there is a demand for a color image forming system that does not use the color developing agents and bleaching agents used in existing systems, reduces the burden on the environment, and is excellent in simplicity and speed. Is increasing more and more.

Recently, many improved techniques have been proposed to meet the above demand. For example, IS &T's 48t
h Annual Conference Process
On page 180 of edings, the dye produced by the development reaction was transferred to the mordant layer, and then removed to remove developed silver and unreacted silver halide, which was essential for conventional color photographic processing. A system is disclosed that eliminates the need for a bleach-fix bath. However, in the technology proposed here, development processing with a processing solution containing a color developing agent is still necessary, and it cannot be said that environmental problems have been solved.

As a system that does not require a processing solution containing a color developing agent, Fuji Photo Film Co., Ltd. has provided a pictocolor system. The Pictrocolor system is applied to an application in which a formed dye is fixed to a dye fixing layer and the dye is viewed as a dye image. In this Pictrocolor system, a small amount of water is supplied to a photosensitive material containing a base precursor, which is bonded to an image receiving material, and a development reaction is caused by heating. This is extremely advantageous. Therefore, it is conceivable to solve the above-mentioned problem by applying the Pictocolor system to processing of a recording material for photography.

[0007]

In the above-mentioned pictocolor system, a photosensitive material contains a dye formed in advance and the dye is transferred to the image receiving material side to form a color image on the image receiving material side. However, such a method does not achieve the resolution required for the photographic material. From such a viewpoint, it is advantageous to form the photosensitive material on the photosensitive material side, not on the image receiving material side. Further, since a dye formed in advance is contained in the photosensitive material, the sensitivity is disadvantageous due to a filter effect, and the high sensitivity required as a photographic material cannot be achieved. From this viewpoint, it is more advantageous to use a method in which a coupler that forms a dye at the time of development by performing a coupling reaction with an oxidized form of a developing agent is contained in a photosensitive material, rather than forming a dye in advance.

However, in a system in which an image is formed on the light-sensitive material side and a small amount of water is supplied using a high-sensitivity emulsion for photography in a system utilizing a coupling reaction, rapid image formation by heat development is performed. Was found to cause a serious problem of image unevenness. This phenomenon did not occur in the above-mentioned Pictrocolor system. Even if you try to reproduce the original scene on a photosensitive material for printing from a photosensitive material for photography that caused image unevenness, you can only obtain an image that is unappreciable for viewing, and correct processing unevenness from image information read by a scanner etc. Although it is possible in principle to reproduce a hard copy, it takes a lot of time and is not practical. As described above, the image unevenness has been a serious obstacle in processing the photosensitive material for photography quickly and with a method having a low environmental load.

An object of the present invention is to solve the above conventional problems and achieve the following objects. The present invention is a silver halide color photographic light-sensitive material suitable for image formation by simple and quick processing, which has a low impact on the environment, and which is high in sensitivity and free from image unevenness during development processing. The purpose is to provide. Also,
The present invention provides a color image forming method capable of forming a high-quality image easily and quickly without unevenness by reducing the burden on the environment by using such a silver halide color photographic light-sensitive material. The purpose is to:

[0010]

The above object has been achieved by the following means. (1) At least one photosensitive layer containing a photosensitive silver halide emulsion, a developing agent, a compound forming a dye by a coupling reaction with an oxidized form of the developing agent, and a binder is provided on the support. A photographic component layer is coated, and after exposure, a coating film and a coating material containing a base layer and / or a base precursor are coated on a support. Water is supplied to the photosensitive layer surface or the processing layer surface of the processing material, and the photosensitive layer surface and the processing layer surface are bonded together. A silver halide color photographic light-sensitive material in which a color image is formed by heating and developing, wherein the photosensitive silver halide emulsion contains metal ions as electron traps having a depth of 0.6 eV or less; And also contains at least one selected from metal complex ion, an average aspect ratio of 4 to 100
Is a silver halide color photographic light-sensitive material characterized by containing at least one kind of tabular grains.

(2) The metal ions and metal complex ions, which are electron traps having a depth of 0.6 eV or less, are Pb
Ion, cyanide ligand and Re, Os, Ru, Fe, I
The silver halide color photographic light-sensitive material according to the above (1), which is an ion containing r or Co, and an ion containing a halogen ion ligand or a thiocyanate ion ligand and Ir or Pd.

(3) The developing agent has the following general formula I:
The silver halide color photographic material according to the above (1) or (2), which is represented by any one of the general formulas II, III and IV.

[0013]

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[0014]

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[0015]

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[0016]

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In the general formulas I to IV, 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, Group, aryloxy group, alkylthio group, arylthio group, alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group,
Arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group,
Represents an alkylcarbonyl group, an arylcarbonyl group or an acyloxy group. R ₅ represents an alkyl group, an aryl group or a heterocyclic group. Z represents a group of atoms forming a (hetero) aromatic ring. When Z is a benzene ring, the total value of Hammett constant (σ) of the substituent is 1 or more. R ₆ is
Represents an alkyl group. X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom. R ₇ and R ₈ represent a hydrogen atom or a substituent. R ₇ and R ₈ may be bonded to each other to form a double bond or a ring. Further, each of the general formulas I to IV has at least one ballast group having 8 or more carbon atoms in order to impart oil solubility to the molecule. (4) After exposing the silver halide color photographic light-sensitive material, the above-described silver halide color photographic light-sensitive material and a constituent layer including a processing layer containing a base and / or a base precursor are coated on a support. Water is supplied to the photosensitive layer surface of the silver halide color photographic light-sensitive material or the processing layer surface of the processing material, the amount of water being 1/10 to 1 times the total amount of water required for the maximum swelling of all coating films in the processing material. A color image forming method for forming a color image by laminating the photosensitive layer surface and the processing layer surface and performing heat development, wherein the silver halide color photographic light-sensitive material is any of the above (1) to (3). A color image forming method, characterized by being the silver halide color photographic light-sensitive material described in (1) or (2).

[0018]

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. The photosensitive silver halide emulsion contains at least one (one or more) selected from metal ions and metal complex ions that are electron traps having a small depth.

Conventionally, a technique for incorporating metal ions and / or metal complex ions (hereinafter sometimes referred to as “metal ions or the like”) into silver halide emulsion grains is as follows.
It is well known among such traders. 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 high-sensitivity photosensitive silver halide emulsions for photography taking heat development, by adjusting the depth as electron traps for metal ions, etc., the temperature dependence during development processing is reduced, and high sensitivity is achieved. The effect of the present invention that a high-quality image without image unevenness can be obtained has not been known until now, and was found for the first time as a result of intensive studies by the inventor of the present invention.

In the present invention, the depth of the shallow electron trap is 0.6 eV or less (at most 0.6 eV).
V) is preferable, and 0.4 eV or less (at most 0.4 eV).
V) is more preferable, and 0.2 eV or less (at most, 0.
2 eV) is particularly preferred. For example, [Rh] is a metal ion having an electron trap depth of more than 0.6 eV.
_{Cl 5 (H 2 O)]} 2-, [RhCl 4 (H 2 O) 2] -,
^{_{[RuCl 5 (NO)] 2-}} , [Cr (CN) 6] 3-,
When [RhCl ₆ ] ³⁻ and [RhBr ₆ ] ³⁻ are used,
The temperature dependency during development is not sufficiently improved,
It is not preferable because desensitization is large and image unevenness is likely to occur during high-temperature development processing. On the other hand, when metal ions or the like, which is a shallow electron trap having a depth of 0.6 eV or less, are used, such a phenomenon does not occur. This is preferable in that a large latent image can be formed. This is presumed to be due to the difficulty in dispersing the latent image due to metal ions or the like, which are electron traps having an appropriate depth, and as a result, the size of the latent image has increased. Further, it is preferable in that a high-quality image with high sensitivity and no image unevenness can be obtained. When the pressure is 0.4 eV or less, and more preferably 0.2 eV or less, the effect is remarkable, which is preferable.

The metal ions and metal complex ions which can serve as the shallow electron trap are as follows. For example, metal ions and metal complex ions that can be a shallow electron trap of 0.2 eV or less include Pb ²⁺ , [M
_{(CN) x L y N z} ] and the like. In the above formula, M is R
e ⁺ , Os ²⁺ , Ru ²⁺ , Fe ²⁺ , Ir ³⁺ or Co ³⁺ . X represents 4, 5 or 6. L and N are fluorine ion, chlorine ion, bromine ion, a halogen ion such as iodide ion, SCN ^-, NCS ^-, such as an inorganic ligand, or, pyridine, phenanthroline, imidazole, pyrazole, such as H ₂ O Represents an organic ligand.
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. For example, as a metal ion and a metal complex ion that can serve as a shallow electron trap of more than 0.2 eV and 0.6 eV or less, an ion containing a halogen ion ligand or a thiocyanate ion ligand and Ir or Pd can be given. Among these, for example,
[IrCl ₆ ] ^3- , [IrBr ₆ ] ^-3 , [Ir (SCN)
₆ ] ^3- , [IrI ₆ ] ^{3- and the} like are preferably used.

The value of the depth of the electron trap due to the metal ions and 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, for example, by performing 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 tabular grains of the photosensitive silver halide emulsion which can be used in the present invention is silver chloride, silver iodochloride, silver chlorobromide, silver iodochlorobromide or silver iodobromide. Can be preferably used. Also, other silver salts, for example, silver thiocyanate, silver sulfide, silver selenide,
Organic silver, such as silver carbonate, silver phosphate, or benzotriazole silver, may be fixed in the halide grains or bonded thereto. 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 materials, a photosensitive 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, silver iodide may be contained. In this 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 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 or more parallel twin planes are included. When twins are formed and the outer surface consists of (100) planes, no twin planes exist. Twin plane spacing is disclosed in US Pat.
0.01720, as described in US Pat.
2 μm or less.
As described in JP-A-249585, a value obtained by dividing the distance between the (111) main planes by the twin plane spacing can 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 elliptical. Even if the main plane is (111),
The side surface connecting the principal planes may be a (111) plane, a (100) plane, a mixture of both, or a plane having a higher index. Good. When the outer surface is the (100) plane, the photosensitive silver halide emulsion grains have a rectangular shape when viewed from above.

In the photosensitive silver halide emulsion used in the present invention, tabular grains preferably occupy 80 to 100%, more preferably 90 to 100%, and 95 to 100% of the total projected area. It is particularly preferred that they occupy.

The average grain thickness of the tabular grains in the photosensitive silver halide emulsion used in the present invention is from 0.005 to 0.005.
0.2 μm is preferred, and 0.01 to 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 circle equivalent diameter of the average projected area of the tabular grains in the photosensitive silver halide emulsion is preferably 0.2 to 8 μm, more preferably 0.3 to 5 μm, and 0.4 to 4 μm.
μm is particularly preferred.

The ratio of the circle equivalent diameter to the average thickness of the tabular grains in the photosensitive silver halide emulsion is called an aspect ratio. The average aspect ratio of the tabular photosensitive silver halide emulsion grains in the present invention is from 4 to 10
0 is preferable, and 6 to 80 is more preferable. When the average aspect ratio is less than 4, it is disadvantageous in terms of sensitivity,
If it exceeds 100, the pressure properties are poor and the particle size distribution tends to be polydisperse, which is not preferable. 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 grains in the photosensitive silver halide emulsion has a hexagonal shape, all tabular grains having a ratio of a maximum length side length to a minimum length side length of 1 to 2 are obtained. It preferably occupies 50 to 100% of the projected area of the grain, more preferably 70 to 100%. The ratio is preferably hexagonal tabular grains close to 1. When the projection surface of the tabular grains in the photosensitive silver halide emulsion is rectangular, tabular grains having a maximum length side length ratio of 1 to 2 with respect to a minimum length side length are projected from all grains. It preferably occupies 50 to 100% of the area, more 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 photosensitive 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) silver bromide having 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 amount of sensitizing dye adsorbed 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 grains in the photosensitive silver halide emulsion used in the present invention may have dislocation lines. The dislocation line is a linear lattice defect at a boundary between a region that has already slipped and a region that has not yet slipped on the slip surface of the crystal.

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 directly observing the dislocation lines 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 emulsion grains are placed on a mesh for observation with an electron microscope, and the sample can be observed by a transmission method in a cooled state 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 therethrough.
The use of an electron microscope (200 kV or more with respect to a thickness of m) enables more clear observation.

JP-A-63-220238 discloses 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 for each grain as viewed from the direction perpendicular to the main plane are determined from the photographs of the grains taken with an electron microscope as described above. Can be.

When the tabular grains in the photosensitive 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 selected as appropriate, and it is optional. However, 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 side 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, or 50 or more per grain. .

The photosensitive silver halide emulsion containing tabular grains and the silver halide emulsion other than that of 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. Glafkides, Chimie et P.).
hysique Photographique Paul Montel, 1967) "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF
Duffin, Photographic Emulsion Chemistry (Focal Pr
ess, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VL Zelikman et a
l. Making and Coating Photographic 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.

Gelatin is preferably used as the protective colloid used in the preparation of the emulsion in the present invention, 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.

It is also preferable to use a silver halide solvent when forming the silver halide emulsion grains. 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 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 rate. 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 the photosensitive silver halide emulsion in the present invention, it is preferable to carry out a desalting step for removing excess salts. 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 chemical sensitization. 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, a thiosulfate (eg, 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. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.) ), Selenoketones, selenoamides, aliphatic isoselenocyanates (eg, allyl isoselenocyanate), selenocarboxylic acids and esters, selenophosphates, diethyl selenides, diethyl diselenides, and other selenides. 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, besides the above-described chalcogen sensitization, sensitization with a noble metal can also 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, and amides, 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. The coating amount of the photosensitive silver halide emulsion is 1 mg / m ^{2 to} 10 g / m ² in terms of silver.

It is preferable to use an oxidizing agent for silver during the production process of the photosensitive silver halide emulsion of the present invention. The oxidizing agent for silver refers to a compound having an action of converting metallic silver into silver ions. In particular, a compound that converts extremely fine silver particles by-produced in the process of forming the photosensitive silver halide emulsion grains and the chemical sensitization process into silver ions is effective. The silver ion generated here may form a silver salt which is hardly soluble in water such as silver halide, silver sulfide, silver selenide, or a silver salt which is easily soluble in water such as silver nitrate. Is also good. The oxidizing agent for silver may be an inorganic substance or an organic substance.

Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (eg, NaBO _{2.
H 2 O 2 · 3H 2 O} , 2NaCO 3 · 3H 2 O 2, Na
_{4 P 2 O 7 · 2H 2} O 2, 2Na 2 SO 4 · H 2 O 2 ·
2H ₂ O), peroxy acid salts (eg, K ₂ S ₂ O ₈ ,
_{K 2 C 2 O 6, K} 2 P 2 O 8), peroxy complex compounds _{(e.g., K 2 [Ti (O 2} ) C 2 O 4] · 3H 2 O,
4K ₂ SO ₄ .Ti (O ₂ ) OH.SO ₄ .2H ₂ O,
Na ₃ [VO (O ₂ ) (C ₂ H ₄ ) ₂ ] · 6H ₂ O),
Oxygenates such as permanganate (eg, KMnO ₄ ) and chromate (eg, K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine, and perhalates (eg, potassium periodate) , High valent metal salts (eg, potassium hexacyanoferrate) and thiosulfonates.

As the organic oxidizing agent, for example, p-
Quinones such as quinones, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N
-Bromosuccinimide, chloramine T, chloramine B)
Is given as an example.

In the present invention, preferred examples of the oxidizing agent for silver include ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents of thiosulfonates, and organic oxidizing agents of quinones. European Patent No. 06276
The disulfide compound described in 57A2 is also a preferred compound. It is a preferred embodiment to use the above-described reduction sensitization in combination with an oxidizing agent for silver. After the use of the oxidizing agent, the method can be selected from a method of performing reduction sensitization, a reverse method thereof, or a method of coexisting both of them. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The light-sensitive silver halide emulsion for photography used in the present invention can prevent fogging during the production process, storage or processing of a silver halide color photographic light-sensitive material, or stabilize photographic performance. For this purpose, various compounds can be contained. That is, thiazoles,
For example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzo Triazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as triazain Dens, tetraazaindenes (especially 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers, such as 3,3a, 7) tetraazaindenes, pentaazaindenes and the like can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,984.
2,947 and JP-B-52-28660 can be used. One of the preferred compounds is a compound described in JP-A-63-212932. Anti-fogging agents and stabilizers are used before particle formation,
During particle formation, after particle formation, water washing step, at the time of dispersion after water washing,
It can be added according to the purpose at various times before, during, after chemical sensitization and before coating. In addition to exhibiting the original anti-fogging and stabilizing effect by adding during emulsion preparation, control the crystal habit of the grains, reduce the grain size, reduce the solubility of the grains, control the chemical sensitization,
It can be used for various purposes such as controlling the arrangement of dyes.

The photosensitive silver halide emulsion for photography used in the present invention is preferably spectrally sensitized by a methine dye or the like in order to exhibit the effects of the present invention.
Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used as basic heterocyclic nuclei in cyanine dyes can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; Nucleus fused with an aromatic hydrocarbon ring, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzene An imidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or composite merocyanine dye includes, as nuclei having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, and a thiazolidine-2,4-nucleus.
A 5- to 6-membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,9.
No. 77,229, No. 3,397,060, No. 3,
No. 522,052, No. 3,527,641, No. 3,617,293, No. 3,628,964, No. 3,666,480, No. 3,672,898,
No. 3,679,428, No. 3,703,377
No. 3,769,301, No. 3,814,60
No. 9, No. 3,837,862, No. 4,026,7
No. 07, British Patent Nos. 1,344,281 and 1,5
No. 07,803, JP-B-43-4936,
No. 53-12375, JP-A-52-110618,
No. 52-109925.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful. Most commonly, this is done after completion of chemical sensitization but before coating, but US Pat. No. 3,628,969.
As described in JP-A-58-1139 and JP-A-4225666, spectral sensitization can be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in JP-A-28, or it can be added before the completion of precipitation of silver halide grains to start spectral sensitization. Furthermore, as taught in U.S. Pat. No. 4,225,666, these compounds may be added separately, ie, some of these compounds may be added prior to chemical sensitization and the remainder Can be added after chemical sensitization, and at any time during the formation of photosensitive silver halide emulsion grains, including the method disclosed in U.S. Pat. No. 4,183,756. Is also good.

The addition amount was 4 × / mol of silver halide.
It can be used in an amount of from 10 ^-6 to 8 × 10 ^-3 mol. In the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ^-5 to 2 × 10 ^-3 mol is more effective. It is.

The above-mentioned various additives are used in the photosensitive silver halide emulsion according to the present invention, but other various additives can be used according to the purpose. These additives are described in more detail in Research Disclosure (RD) Item 17643 (December 1978), Item 18716 (November 1979) and Item 17643 (November 1979).
m308119 (December 1989), and the relevant locations are summarized below.

Additive Type RD17643 RD18716 RD308119 Chemical sensitizer page 23 648 page right column page 996 2. Sensitivity increasing agent Same as above 3. 3. Spectral sensitizer, page 23-24, page 648, right column-996 right-998 right Supersensitizer, page 649, right column Brightener 24 pages 998 Right 5. 5. Antifoggant page 24 to 25 page 649 right column 998 right to 1000 right and stabilizer 6. Light absorber, pages 25 to 26, page 649, right column to page 1003, left to 1003 right, filter dye, page 650, left column, UV absorber 7. Stain inhibitor 25 pages right column 650 left to right column 1002 right Dye image stabilizer page 25 1002 right 9. Hardening agent Page 26 651 Left column 1004 right to 1005 left 10. Binder page 26 Same as above 1003 right to 1004 right 11. Plasticizers and lubricants 27 pages 650 pages right column 1006 left to 1006 right 12. Coating aid, pages 26 to 27 Same as above 1005 left to 1006 left Surfactant 13. Static page 27 Same as above 1006 right to 1007 left Inhibitor 14. Matting agent 1008 left to 1009 left

The photosensitive silver halide emulsion according to the present invention and techniques such as layer arrangement which can be used for a silver halide color photographic light-sensitive material using the photosensitive silver halide emulsion, photosensitive silver halide emulsion and dye Forming coupler, DI
Functional couplers such as R couplers, various additives, and development processing are also described in European Patent No. 056596A1 (published on October 13, 1993) and the patents cited therein. The following is a list of each item and the corresponding places.

1. 1. Layer structure: page 61, lines 23 to 35, page 61, line 41 to page 62, line 14 2. Intermediate layer: page 61, lines 36-40, 3. Multilayer effect imparting layer: page 62, lines 15-18, 4. Silver halide composition: page 62, lines 21-25, 5. Silver halide crystal habit: page 62, line 26-30, 6. Silver halide grain size: page 62, lines 31-34, 7. Emulsion manufacturing method: page 62, line 35-40, Silver halide grain size distribution: page 62, 41-42
Row, 9. 9. Tabular grains: page 62, lines 43-46, 10. Internal structure of particle: page 62, line 47 to line 53, Emulsion latent image formation type: page 62, line 54-page 63, 5
Line, 12. 12. Physical ripening and chemical ripening of emulsion: page 63, line 6-9, 13. Mixed use of emulsion: page 63, lines 10-13, 14. Overlaid emulsion: page 63, lines 14-31, Non-light-sensitive emulsion: page 63, lines 32-43, 16. 16. Silver coating amount: page 63, lines 49-50, Photographic additives: Research Disclosure (R
D),

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.
Range. In the silver halide color photographic light-sensitive material of the present invention, by incorporating a color developing agent capable of forming a dye by coupling an oxidant generated by silver development with a coupler described below, a process including a color developing agent The use of a liquid was unnecessary, the reduction of environmental load was achieved, and a simple and quick processing became possible.

In order to exhibit the effect of the built-in developing agent in the present invention, a processing material containing a base precursor and / or a base described below, a silver halide color photographic light-sensitive material, and a whole coating film constituting the processing material Is supplied to a coating film of the silver halide color photographic light-sensitive material and / or the processing material, and then bonded and heated to form a color / development. It is preferable to heat only the silver halide color photographic light-sensitive material, or it may be heat-developed by bonding to a processing material without using water at all. The present invention can reduce the load on the environment due to liquid development, but of course, an activator method using an alkaline processing liquid is also possible, and an image can be formed by developing with a processing liquid containing a developing agent and a base. It is possible.

As a method of adding the developing agent, a high-boiling organic solvent (for example, alkyl phosphate, alkyl phthalate, etc.) is mixed with a low-boiling solvent (for example,
Ethyl acetate, methyl ethyl ketone, etc.), dispersed in water using an emulsification dispersion method known in the art, and then added. Further, addition by the solid dispersion method described in JP-A-63-271339 is also possible. It is also preferable to co-emulsify with a coupler described later (a compound that forms a dye by a coupling reaction with an oxidized developing agent). In the present invention, the amount of the developing agent to be added is preferably 0.01 to 20 mol, more preferably 0.1 to 10 mol, per mol of silver.
Molar is more preferred. In addition, for the coupler, 0.0
The addition is preferably 1 to 100 mole times, more preferably 0.1 to 10 mole times. The developing agent is preferably contained in the photosensitive layer containing the photosensitive silver halide emulsion, but may be contained in the intermediate layer.

In the present invention, it is preferable to use a compound represented by the general formula I, the general formula II, the general formula III or the general formula IV as a developing agent. Among these, the compounds represented by the general formula I or the general formula II are particularly preferably used.

Hereinafter, these developing agents will be described in detail. The compound represented by the general formula I is a compound generally referred to as sulfonamidophenol, and is a compound known in the art. When used in the present invention, it is preferable that at least one of the substituents R _{1 to} R ₅ has a ballast group having 8 or more carbon atoms.

In the above general formulas I to IV, R _{1 to} R ₄ represent a hydrogen atom, a halogen atom (for example, chloro or bromo),
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 is an alkyl group (for example, methyl group, ethyl group, butyl group, octyl group, lauryl group, cetyl group, stearyl group), an aryl group (for example, phenyl group, tolyl group, xylyl group, 4-methoxyphenyl group) , Dodecylphenyl, chlorophenyl, trichlorophenyl, nitrochlorophenyl, triisopropylphenyl, 4-dodecyloxyphenyl, 3,5-di-
(Methoxycarbonyl) group) or a heterocyclic group (for example,
Pyridyl group).

The compound represented by the general formula II is a compound generally called carbamoylhydrazine. Both are compounds known in the art. When used in the present invention, those having a ballast group having 8 or more carbon atoms in R ₅ or a substituent of the ring are preferred.

In the above formula, Z represents an atom group forming an aromatic ring. The aromatic ring formed by Z needs to be sufficiently electron-attracting in order to impart silver developing activity to the present compound. For this reason, an aromatic ring which forms a nitrogen-containing aromatic ring or has an electron-withdrawing group introduced into a benzene ring is preferably used. As such an aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinoxaline ring and the like are preferable. In the case of a benzene ring, examples of the substituent include an alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), a halogen atom (eg, chloro group, bromo group), an alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group) , Ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, piperidinecarbamoyl, morpholinocarbamoyl), arylcarbamoyl (for example, phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl), carbamoyl An alkylsulfamoyl group (for example, a methylsulfamoyl group, a dimethylsulfamoyl group, an ethylsulfamoyl group, a diethylsulfamoyl group, a dibutylsulfamoyl group) Amoiru group, piperidyl sulfamoyl group, Mori Hori Rusuru sulfamoyl group), an aryl sulfamoyl group (e.g., phenyl sulfamoyl group, methylphenyl sulfamoyl group, ethylphenyl sulfamoyl group,
Benzylphenylsulfamoyl group), sulfamoyl group, cyano group, alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group) ), Alkoxycarbonyl groups (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group),
Examples include an aryloxycarbonyl group (for example, a phenoxycarbonyl group), an alkylcarbonyl group (for example, an acetyl group, a propionyl group, a butyroyl group), and an arylcarbonyl group (for example, a benzoyl group, an alkylbenzoyl group). Group Hammett constant σ
The sum of the values is preferably 1 or more. R ₅ is the same as in general formula I.

The compound represented by the general formula III is a compound generically called carbamoylhydrazone. The compound represented by the general formula IV is a compound generically called sulfonylhydrazine. Both are compounds known in the art. When used in the present invention, it is preferable that at least one of R _{5 to} R ₈ has a ballast group having 8 or more carbon atoms.

In the above general formulas III and IV, R ₆ represents an 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 represents a hydrogen atom or a substituent (those mentioned as substituents of the benzene ring of the Z are mentioned as examples), R ₇ and R
₈ may combine with each other to form a double bond or a ring.
R ₅ is the same as in general formula I. In addition, among the compounds represented by the general formulas I to IV, the compounds represented by the general formulas I and II are preferable in the present invention, particularly from the viewpoint of raw storability.

Each of the groups R _{1 to} R ₈ includes those having a possible substituent, and examples of the substituent include those described above as the substituent for the benzene ring of Z. Hereinafter, specific examples of the compounds represented by the general formulas I to IV are shown.
The compounds of the present invention are of course not limited thereby.

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These compounds can be synthesized by a generally known method. An example of a simple synthesis route is listed below.

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Combinations of a p-phenylenediamine developing agent with a phenol or an active methylene coupler described in US Pat. No. 3,531,256;
No. 1,270, a combination of a p-aminophenol-based developing agent and an active methylene coupler, and the like can be used. The combination of a sulfonamide phenol and a 4-equivalent coupler as described in U.S. Pat. is there. When a developing agent is incorporated, a precursor of the developing agent may be used. For example, US 3,342,59
No. 7, the indoaniline compound described in US Pat.
No. 342,599, Schiff base compounds described in Research Disclosure Nos. 14,850 and 15,159, aldol compounds described in 13, 924, and US Pat. No. 3,719,492. Examples thereof include metal salt complexes and urethane compounds described in JP-A-53-135628.

Further, a sulfonamide phenol-based active compound described in Japanese Patent Application No. 7-180,568, and Japanese Patent Application No. 7-4
Combinations of hydrazine-based developing agents and couplers described in JP-A Nos. 9287 and 7-63572 can also be suitably used in the silver halide color photographic light-sensitive material of the present invention.

When a diffusion-resistant developing agent is used,
If necessary, an electron transfer agent and / or an electron transfer agent precursor can be used in combination to promote electron transfer between the diffusion-resistant developing agent and the developable silver halide. Particularly preferably, said US Patent No. 5,139,
No. 919 and European Patent Publication No. 418,743 are used. Japanese Patent Application Laid-Open No. Hei 2-230, 1
As described in JP-A-43-43 and JP-A-2-235,044, a method of stably introducing a compound into a layer is preferably used.

The electron transfer agent or its precursor can be selected from the above-mentioned developing agents and its precursors. It is desirable that the electron transfer agent or its precursor has a higher mobility than the diffusion-resistant developing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. An electron donor precursor as described in JP-A-3-160,443 is also preferably used. Further, various reducing agents can be used in the intermediate layer and the protective layer for various purposes such as preventing color mixing and improving color reproduction. Specifically, European Patent Publication Nos. 524,649 and 357,040, JP-A-4-249,245, JP-A-2-46,450, and JP-A-63-186,240. The reducing agents described in the above publications are preferably used. In addition, Japanese Patent Publication No. 3-63,733,
JP-A-1-150,135, JP-A-2-46,450,
Development inhibitor releasing reducing compounds as described in JP-A-2-64,634 and JP-A-3-43,735 and European Patent Publication No. 451,833 are also used.

It is also possible to use a developing agent precursor which does not itself have a reducing property but develops a reducing property by the action of a nucleophilic reagent or heat in the developing process. In addition, the following reducing agents may be incorporated in the silver halide color photographic light-sensitive material. Examples of the reducing agent used in the present invention include columns 49 to 50, 4,839,272, 4,330,617, and 4,590 of U.S. Pat. Nos. 5,152,454, 5,139,919, and JP-A-60-14.
No. 0,335, pp. (17)-(18), pp. 57-40, 2;
No. 45, No. 56-138, 736, No. 59-178,
No. 458, No. 59-53, 831, No. 59-182,
No. 449, No. 59-182, No. 450, No. 60-11
9,555, 60-128,436, 60-1
No. 28,439, No. 60-198,540, No. 60-
Nos. 181,742, 61-259,253, 62
-244,044, 62-131,253, 6
Nos. 2-131, 256, 64-13, 546
Pp. (40)-(57), JP-A-1-120,553, and EP-A-220,746 A2, No. 78.
On page 96 and the like. Also, combinations of various reducing agents such as those disclosed in U.S. Pat. No. 3,039,869 can be used.

In the present invention, it is necessary to use a compound (coupler) which forms a dye by a coupling reaction with an oxidized form of the developing agent. The coupler that can be used in the present invention may be a 4-equivalent coupler or a 2-equivalent coupler.
Further, the diffusion-resistant group may form a polymer chain. A specific example of a coupler is THJames "The Theory of the Ph
otographic Process, 4th edition, pages 291-334 and 35
4-361 pages, JP-A-58-123533, 58-123.
No. 149046, No. 58-149047, No. 59-1
Nos. 11148, 59-124399, 59-17
No. 4835, No. 59-231439, No. 59-231
No. 540, No. 60-2950, No. 60-2951,
Nos. 60-14242, 60-23474, 60
-66249, Japanese Patent Application No. 6-270700, 6-3
These are described in detail in, for example, JP-A Nos. 07049 and 6-321380.

It is preferable to use the following couplers. As a yellow coupler, for example, EP
Couplers represented by the formulas (I) and (II) described in JP-A-502,424A: couplers represented by the formulas (1) and (2) described in EP-513,496A, Japanese Patent Application No.
A coupler represented by the general formula (I) in claim 1 of JP-A-134523: a coupler represented by the general formula D in column 1, lines 45 and 55 of US Pat. No. 5,066,576; No. 498,381 A1.
Couplers described in claim 1 on page 40 of the specification, EP
Couplers represented by formula (Y) on page 4 of 447,969A1 and couplers represented by formulas (I) to (IV) on line 36 and 58 in column 7 of U.S. Pat. No. 4,476,219. No. Examples of the magenta coupler include couplers described in JP-A-3-39737, JP-A-6-43611, JP-A-5-204106, and JP-A-4-3626. Examples of the cyan coupler include, for example, JP-A-4-208443,
And the couplers described in JP-A-43345 and JP-A-4-23633. Examples of the polymer coupler include the couplers described in JP-A-2-44345.

Examples of couplers in which a coloring dye has an appropriate diffusivity include US Pat. No. 4,366,237 and GB 2,12.
5,570, EP 96,570, DE 3,234
No. 533 are preferred.

The silver halide color photographic light-sensitive material of the present invention may contain the following functional coupler. Examples of a coupler for correcting unnecessary absorption of a coloring dye include a yellow colored cyan coupler described in EP 456,257A1, a yellow colored magenta coupler described in the EP, and US Pat. No. 4,833,06.
No. 9, magenta colored cyan coupler, US
No. 4,837,136, (2), WO92 / 115
75. A colorless masking coupler represented by the formula (A) of claim 1 (especially an exemplified compound on pages 36 to 45). In the present invention, it is preferable to use a coupler or another compound which releases a photographically useful compound by reacting with an oxidized form of the developing agent. Compounds (including couplers) that react with the oxidized form of the developing agent to release photographically useful compound residues
Examples include the following. That is, as a development inhibitor releasing compound, EP 378,236A1
Compounds represented by formulas (I) to (IV) described on page 1;
Formula (I) described on page 7 of P436,938A2
A compound represented by the formula (1) in JP-A-5-307248, and a compound represented by the formula (I), (II) or (III) described on pages 5 and 6 of EP440,195A2. A compound, a compound-ligand releasing compound represented by the formula (I) of claim 1 of JP-A-6-59411, a compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478, and the like. No.

In the present invention, as a coupler, a 4-equivalent coupler and a 2-equivalent coupler can be selectively used depending on the type of the developing agent. First, a 4-equivalent coupler is used for the developing agent represented by the general formula (I). In the developing agent of the general formula (I), the coupling site is substituted by a sulfonyl group, and at the time of coupling, the sulfonyl group is released as sulfinic acid, so that the leaving group on the coupler side must be released as a cation. . Therefore, it reacts with a 4-equivalent coupler capable of releasing a proton as a leaving group during coupling, but does not react with a 2-equivalent coupler whose leaving group is an anion. vice versa,
2 for the developing agents represented by formulas (II) and (III)
Use an equivalent coupler. In the developing agents represented by the general formulas (II) and (III), the coupling site is substituted by a carbamoyl group, and the hydrogen atom on the nitrogen atom is released as a proton during the coupling. Must be eliminated as an anion. Therefore, it reacts with a 2-equivalent coupler capable of releasing an anion as a leaving group during coupling, but does not react with a 4-equivalent coupler whose leaving group is a proton. By using this combination, it is possible to prevent color turbidity due to interlayer movement of the oxidized form of the developing agent. Specific examples of the coupler include a four-equivalent coupler and a two-equivalent coupler both in the theory of the photographic process (edited by 4th Ed. THJames, Macmillan, 1977), pages 291 to 334 and 354 to 361. JP-A-58-12
No. 353, No. 58-149046, No. 58-1490
No. 47, No. 59-11114, No. 59-124399
Nos. 59-174835 and 59-231439
No. 59-231540, No. 60-2951, No. 60-14242, No. 60-23474, No. 60-
This is described in detail in each of the publications of US Pat.

In the silver halide color photographic light-sensitive material of the present invention, it is necessary to use a base or a base precursor for the purpose of accelerating the silver development and the dye-forming reaction. As in the present invention, in a system in which heat development is carried out in the presence of a small amount of water, the specifications of European Patent Publication No. 210,660 and U.S. Pat. -12
No. 9848, a combination of a basic metal compound which is hardly soluble in water, and a compound capable of forming a complex with metal ions constituting the basic metal compound using water as a medium (referred to as a complex-forming compound). And JP-A-61-2324.
Compounds that generate a base by electrolysis described in JP-A-51-51 can also be used as a base precursor. In particular, the former has a high base generation efficiency. The sparingly soluble metal compound and the complex-forming compound are preferably separately added to a silver halide color photographic light-sensitive material and a processing material, respectively, as described in the above-mentioned patent publication, from the viewpoint of storage stability and the like. The amount of the base or base precursor used is usually 0.1 to 20 g / m ² ,
-10 g / m ² are preferred.

Preferred examples of the hardly soluble base metal compound include:
Examples include zinc or aluminum oxides, hydroxides, and basic carbonates. Of these, zinc oxide, zinc hydroxide, and basic zinc carbonate are particularly preferable. The water-insoluble metal compound is used after being dispersed in fine particles in a hydrophilic binder as described in JP-A-59-174830. As the average particle size of the metal compound hardly soluble in water,
It is 0.001-5 μm, preferably 0.01-2 μm. The content of the water-insoluble metal compound in the silver halide color photographic light-sensitive material is 0.01 to 8 g / m ^2.
And 0.05 to 5 g / m ² is preferable.

The complex forming compound of the basic metal compound which is hardly soluble in water with respect to the metal ion is known as a chelating agent in analytical chemistry and a water softener in photographic chemistry. The details thereof are described in A.I. Ringbomb, Translated by Nobuyuki Tanaka and Haruko Sugi “Complexation Reaction” (Sangyo Tosho)
It is also described in The complex-forming compound preferred in the present invention is a water-soluble compound. Specifically, for example, aminopolycarboxylic acids (including salts) such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, and aminotris ( Aminophosphonic acid (salt) such as ethylenediaminetetramethylenephosphonic acid) and pyridinecarboxylic acid (salt) such as 2-picolinic acid, pyridine-2,6-dicarboxylic acid and 5-ethyl-2-picolinic acid. No. Among these, pyridinecarboxylic acid (salt) is particularly preferred.

In the present invention, the complex-forming compound is preferably used as a salt neutralized with a base. In particular, salts with organic bases such as guanidines, amidines and tetraalkylammonium hydroxide and salts with alkali metals such as sodium, potassium and lithium are preferred. These mixtures may be used. Specific examples of preferred complex-forming compounds are described in the above-mentioned JP-A-62-129848, European Patent Publication 210,660A2, and the like. The content in the complex-forming compound is 0.1 to 20 g / m ^2.
And 0.1 to 10 g / m ² is preferable.

As the binder for the constituent layers of the silver halide color photographic light-sensitive material, hydrophilic binders are preferably used. Examples thereof include the above-mentioned Research Disclosure and pages (71) to (7) of JP-A-64-13546.
5) Those described on page 5 are mentioned. Specifically, transparent or translucent hydrophilic binders are preferred, for example, natural compounds such as gelatin, proteins such as gelatin derivatives or cellulose derivatives, starch, gum arabic, dextran, pullulan and other polysaccharides, and polyvinyl alcohol. ,
Synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymer are exemplified. Also, U.S. Pat.
0,681 Pat superabsorbent polymers described in JP-A-62-245,260 Publication, i.e., -COOM or -SO ₃ M (M represents a hydrogen atom or an alkali metal)
Homopolymers of vinyl monomers having the above or copolymers of these vinyl monomers with each other or with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumitagel L-5H manufactured by Sumitomo Chemical Co., Ltd.)
Is also used. These binders may be used alone or in combination of two or more. Particularly, a combination of gelatin and the 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 is preferably used in combination. In the present invention, the coating amount of the binder is preferably 20 g / m ² or less, and more preferably 10 g / m ^2.
The following are particularly preferred.

The above-mentioned hydrophobic additives such as couplers, developing agents, and diffusion-resistant reducing agents are described in US Pat. No. 2,322,02.
It can be introduced into a layer of a silver halide color photographic light-sensitive material by a known method such as the method described in the specification of JP-A No. 7. In this case, US Pat. No. 4,555,470
Nos. 4,536,466 and 4,536,467
Nos. 4,587,206 and 4,555,476
Nos., 4,599,296, JP-B 3-6
A high-boiling organic solvent as described in JP-A-2,256 or the like can be used, if necessary, in combination with a low-boiling organic solvent having a boiling point of 50 to 160 ° C. These dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, etc.
More than one species can be used in combination. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 0.1 to 1 g, per 1 g of the hydrophobic additive used. Also, for 1 g of binder,
1 cc or less, preferably 0.5 cc or less, and 0.3 cc or less.
cc or less is particularly preferred.

JP-B-51-39,853, JP-A-51-3985
A dispersion method using a polymer described in each of JP-A-59,943 and a method of adding as a fine particle dispersion described in JP-A-62-30,242 can also be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example,
JP-A-59-157,636, Nos. (37) to (3)
8) The surfactants described as the surfactants described in Research Disclosure described above can be used. Also,
Phosphate ester surfactants described in Japanese Patent Application Nos. 5-204325 and 6-19247 and West German Patent No. 1,932,299A can also be used.

In the present invention, the scene at the time of shooting is recorded,
In order to construct a silver halide color photographic light-sensitive material used for reproducing a color image, the principle of color reproduction by a subtractive color method can be basically used. That is, at least three types of photosensitive layers having photosensitivity are provided in the blue, green, and red regions, and yellow, magenta, and cyan dyes are formed in each of the photosensitive layers, which are complementary colors to the photosensitive wavelength region. The color information of the original scene can be recorded by including a color coupler which can be used. By exposing a color printing paper having a similar relationship between the photosensitive wavelength and the color hue through the dye image obtained in this way, the scene at the time of shooting can be reproduced. Further, information of a dye image based on a scene at the time of shooting can be read by a scanner or the like, and an image for viewing can be reproduced based on this information.

As the silver halide color photographic light-sensitive material of the present invention, a light-sensitive layer having photosensitivity in three or more wavelength ranges can be provided. It is also possible to provide a relationship other than the above-described complementary colors between the photosensitive wavelength region and the color hue. In such a case, after fetching the image information as described above, by performing image processing such as hue conversion, it is possible to reproduce the color information of the scene at the time of shooting.

In the present invention, it is preferable to include at least two types of photosensitive silver halide emulsions having sensitivity to the same wavelength region and different average grain projected areas. Having photosensitive in the same wavelength region in the present invention means having photosensitive in the same wavelength region effectively. Therefore, even when the photosensitive silver halide emulsions whose spectral sensitivity distributions are slightly different from each other are used, if the main photosensitive regions overlap, it means that the photosensitive silver halide emulsions having sensitivity in the same wavelength region are regarded as photosensitive silver halide emulsions. .

In the present invention, in order to include a plurality of photosensitive silver halide emulsions having sensitivity to these same wavelength regions and different average grain projected areas, separate photosensitive silver halide emulsions are required for each of the photosensitive silver halide emulsions. A photosensitive layer may be provided, or one photosensitive layer may contain a mixture of a plurality of the above-described photosensitive silver halide emulsions. When these light-sensitive silver halide emulsions are contained in separate light-sensitive layers, it is preferable to use color couplers having the same hue, but it is preferable to use couplers having different hues. It is also possible to use different coloring hues for the respective photosensitive layers, and to use couplers having different absorption profiles of the coloring hues for the respective photosensitive layers.

In the present invention, when coating a photosensitive silver halide emulsion having photosensitivity in these same wavelength regions, these photosensitive silver halide emulsions are coated in a unit area of a silver halide color photographic light-sensitive material. The ratio of the number of silver halide grains of the emulsion having a larger average grain projected area is such that the coated silver amount of the photosensitive silver halide emulsion is 3 / (the average grain projected area of the photosensitive silver halide emulsion grains contained in the emulsion). It is necessary to configure so as to be larger than the ratio of the value divided by the square. By adopting such a configuration, an image having good granularity can be obtained even under development conditions heated to a high temperature. In addition, high developability and a wide exposure latitude can be satisfied at the same time.

Conventionally, in a color negative film which has been used for photography, not only the improvement of the photosensitive silver halide emulsion to achieve the desired granularity, but also the coupling reaction with the oxidized form of the developing agent is required. Techniques such as using a so-called DIR coupler that releases a development inhibiting compound have been used. In the silver halide color photographic light-sensitive material of the present invention, excellent granularity can be obtained even when no DIR coupler is used. In addition, the combination of DIR compounds results in increasingly better granularity.

In a silver halide color photographic light-sensitive material, a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, etc. Various non-photosensitive layers may be provided, and various auxiliary layers such as a back layer may be provided on the side opposite to the support. Specifically, the layer constitution as described in the above patent publication, the undercoat layer as described in U.S. Pat. No. 5,051,335, JP-A-1-16783.
8, an intermediate layer having a solid pigment as described in JP-A-61-20,943, and JP-A-1-120,55.
No. 3, No. 5-34,884 and No. 2-64,634, an intermediate layer having a reducing agent or a DIR compound, U.S. Pat. Nos. 5,017,454 and 5,13.
No. 9,919, an intermediate layer having an electron transfer agent as described in JP-A-2-235,044, and a protection having a reducing agent as described in JP-A-4-249,245. A layer or a combination thereof can be provided.

Dyes which can be used in the yellow filter layer and the antihalation layer are preferably those which are decolored or eluted during development and do not contribute to the density after processing. The fact that the dye in the yellow filter layer and the antihalation layer is erased or removed at the time of development means that the amount of the dye remaining after the processing is 1/3 or less, preferably 1 /
The dye component may be eluted from the light-sensitive material at the time of development or may be transferred to the processing material during development, or may be converted to a colorless compound upon reaction during development.

As the dye that can be used in the silver halide color photographic light-sensitive material of the present invention, known dyes can be used. For example, a dye that dissolves in the alkali of the developer, a component in the developer, a sulfite ion, a developing agent, or a dye that reacts with the alkali to erase the color can be used. Specific examples include dyes described in European Patent Publication EP549,489A and ExF2 to Ex6 dyes described in JP-A-7-152129. Japanese Patent Application No. 6-2598
A solid-dispersed dye as described in JP-A-05-2005 can also be used. This dye can be used when the silver halide color photographic light-sensitive material is developed with a processing solution, but is particularly preferable when the silver halide color photographic light-sensitive material is heated and developed using the method described below.

Further, the mordant and the binder may be mordanted with a dye. In this case, the mordant and the dye
Known materials in the field of photography can be used.
JP-A-00,626, columns 58 to 59, and
-88256, pages 32 to 41, JP-A-62-24
And mordants described in JP-A-4043 and 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, eluted in a processing solution, or transferred and removed. Specifically, U.S. Patent Nos. 4,559,290 and 4,783,
No. 369, European Patent No. 220,746A2, JP-A-87-6119, and paragraph No. 0080-00 of Japanese Patent Application No. 6-259805.
81.

A decolorizable leuco dye or the like can also be used. Specifically, JP-A-1-150132 discloses a halogenated compound containing a leuco dye which has been colored in advance with a developer of a metal salt of an organic acid. A silver light-sensitive material is disclosed. Since the leuco dye and the developer complex react with heat or an alkali agent to decolor, when the silver halide color photographic light-sensitive material is heat-developed in the present invention, the leuco dye and the developer are mixed with each other. Are preferred. As the leuco dye, known ones can be used, and Moriga and Yoshida “Dyes and Chemicals”
9, 84 (Chemicals Industry Association), "New Edition Dye Handbook" 24
2 pages (Maruzen, 1970), R. Garner "Reports on the P
Rogress of Appl. Chem "56, 199 (1971),
"Dyes and Chemicals," p. 19, 230 (Japan Chemical Industry Association, 19
74), "Coloring Materials", 62, p. 288 (1989), and "Dye Industry", 32, 208. As the color developer, a metal salt of an organic acid is preferably used in addition to the acid clay color developer and phenol formaldehyde resin. 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 advantageous, and zinc is particularly preferable as the metal. Among these developers, oil-soluble zinc salicylates are described in U.S. Pat. Nos. 3,864,146 and 4,046,941 and Japanese Patent Publication No. 52-1327. What was done can be used.

In the present invention, a compound capable of activating development and simultaneously stabilizing an image can be used in a silver halide color photographic light-sensitive material. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide emulsion. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the oxidizing agent for the organic silver salts include US Pat.
There are benzotriazoles, fatty acids and other compounds described in, for example, columns 52 to 53 of JP-A-00,626. Further, silver acetylene described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above organic silver salt is a photosensitive silver halide 1
0.01 to 10 mol, preferably 0.01 to 10 mol per mol
１1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is 0.05 to 10 in terms of silver.
a g / m ^2, preferably 0.1-4 g / m ^2.

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. No. 4,678,739, column 41, 4,791,042, JP-A-59-116,655, and JP-A-62-245, No. 261,
Hardening agents described in JP-A-61-18,942 and JP-A-4-218,044 are exemplified. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), N-methylol-based hardeners (such as dimethylol urea), boric acid, metaboric acid and polymer hardeners (compounds described in JP-A-62-234157). These hardeners are used in an amount of 0.001 to 1 per gram of the hydrophilic binder.
g, preferably 0.005 to 0.5 g.

In the silver halide color photographic light-sensitive material, various antifogging agents or photographic stabilizers and precursors thereof can be used. Specific examples thereof include the aforementioned Research Disclosure, US Pat.
9,378, 4,500,627, 4,61
No. 4,702, JP-A-64-13564, pages (7) to (9), (57) to (71) and (81) to (97),
U.S. Pat. Nos. 4,775,610 and 4,626,50
Nos. 0, 4,983,494, and
Nos. 174,747 and 62-239,148, JP-A-1-150,135, 2-110,557, 2-178,650 and RD17,643 (1978) Compounds described on pages (24) to (25) are exemplified. The amount of these compounds used is 5 × per mole of silver.
It is preferably 10 ^-6 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-5 mol.
１1 × 10 ⁻² mol is more preferred.

The general heat treatment of a silver halide color photographic light-sensitive material is known in the art, and the heat-developable light-sensitive material and its process are described in, for example, Fundamentals of Photographic Engineering (1970, published by Corona Co., Ltd.). 553-555
Page, published in April 1978, 40 pages of video information, Nabletts Han
dbook of Photography and Reprography 7th Ed. (VnaNos
trand and Reinhold Company), pages 32-33, U.S. Pat. Nos. 3,152,904 and 3,301,678.
No. 3,392,020 and 3,457,07
No. 5, British Patent Nos. 1,131,108 and 1,16
7,777, and Research Disclosure Magazine, June 1978, pages 9 to 15 (RD-1702).
9).

The present invention relates to an activator treatment, a developing agent /
Development with a processing solution containing a base is possible, but can be performed by the following method.

The activator processing refers to a processing method in which a developing agent is incorporated in a photosensitive material and a developing process is performed using a processing solution containing no developing agent. The processing solution in this case is characterized in that it does not contain a developing agent contained in a normal developing solution component, and other components (for example,
Alkalis, auxiliary developing agents, etc.). Regarding the activator treatment, European Patent No. 545,
This is exemplified in publicly known documents such as 491A1 and 565,165A1.

The method of developing with a processing solution containing a developing agent / base is described in RD. No. 17643, pp. 28-29, No. 1
No. 307105, left column to right column, 651 of 8716
On pages 880-881. Next, a processing material and a processing method used for heat development in the present invention will be described in detail.

A thermal solvent may be added to the silver halide color photographic light-sensitive material of the present invention for the purpose of promoting heat development. Examples thereof include polar organic compounds as described in U.S. Pat. Nos. 3,347,675 and 3,667,959. Specifically, amide derivatives (benzamide etc.), urea derivatives (methyl urea, ethylene urea etc.), sulfonamide derivatives (Japanese Patent Publication No. 1-40974 and Japanese Patent Publication No. 4-13701)
Etc.), polyol compounds sorbitols) and polyethylene glycols. When the thermal solvent is insoluble in water, it is preferably used as a solid dispersion. The layer to be added depends on the purpose.
Either a photosensitive layer or a non-photosensitive layer may be used. The amount of the thermal solvent to be added is 10 to 500% by weight, preferably 20 to 300% by weight of the binder of the layer to be added. When heat development is performed without using water, the use of a thermal solvent is preferred. The temperature during heat development is generally about 50 to 250.
Although it is 60 ° C in the present invention, it is preferably 60 ° C or more,
150 ° C. is more preferred.

In addition to the processing materials other than the base, processing materials other than bases may be used to block air during heat development, to prevent volatilization of the materials from the silver halide color photographic light-sensitive material, and to use other materials for processing. It may be provided with a function of supplying the material to the photographic material, removing materials (YF dye, AH dye, etc.) in the silver halide color photographic material which become unnecessary after development or removing unnecessary components generated during development. As the support and the binder of the processing material, the same materials as those of the silver halide color photographic light-sensitive material can be used. A mordant may be added to the processing material for the purpose of removing the dye or for other purposes. As the mordant, those known in the field of photography can be used, and US Pat. No. 4,50,626, No. 58
To 59 column, and No. 32 to of JP-A-61-88256.
41 pages, JP-A-62-244043, JP-A-62-244043
And mordants described in JP-A-244036.
Further, a dye-accepting polymer compound described in US Pat. No. 4,463,079 may be used, and the above-mentioned thermal solvent may be contained.

The treatment layer of the treatment material contains a base or a base precursor. As the base,
Any of an organic base and an inorganic base may be used, and as the base precursor, those described above can be used. The amount of the base or base precursor used is 0.1 to 20.
a ^{g / m 2, 1~10g / m} 2 is preferred.

In the heat development using the processing material, it is preferable to use a small amount of water for the purpose of accelerating the development, facilitating the transfer of the processing material, and promoting the diffusion of unnecessary substances. Specifically, U.S. Patent Nos. 4,704,245 and 4,47
0,445, and JP-A-61-238056. Water may contain inorganic alkali metal salts or organic bases, low-boiling solvents, surfactants, antifoggants, complex-forming compounds with poorly soluble metal salts, fungicides, germicides, etc. Good. The water is not particularly limited as long as it is commonly used water. Specifically, ion-exchanged water, distilled water, tap water, well water, mineral water, and the like can be used. Further, in the heat developing apparatus using the silver halide color photographic light-sensitive material and the processing material of the present invention, water may be used up, or water may be circulated and used repeatedly. In the latter case, water containing components eluted from the material will be used. Further, Japanese Patent Application Laid-Open No. 63-1
44,354, 63-144,355, 62-
No. 38,460, JP-A-3-210,555 and the like, and the apparatus and water described in each publication may be used. Water may be applied to a silver halide color photographic light-sensitive material, a processing material, or both. The amount of water used is 1/1/3 of the total amount of water required to swell all coated films (excluding the back layer) of the silver halide color photographic light-sensitive material and the processing material.
The amount is preferably 10 to 1 times. As a method for applying the water, for example, a method described in page (5) of JP-A-62-253,159, JP-A-63-85,544 or the like is preferably used. Further, the solvent can be used by being encapsulated in a microcapsule or incorporated in advance in a silver halide color photographic light-sensitive material or a processing material, or both in the form of a hydrate. The temperature of the water to be applied is
The temperature may be 30 to 60 ° C. as described in JP-A-63-85,544.

When heat development is performed in the presence of a small amount of water,
EP 210,660, U.S. Pat. No. 4,74
As described in the specifications of Japanese Patent No. 0,445, a basic metal compound which is hardly soluble in water and a compound capable of forming a complex with a metal ion constituting the basic metal compound using water as a medium (complex formation) It is effective to employ a method of generating a base by a combination of the compounds. In this case, it is preferable that a basic metal compound which is hardly soluble in water is added to a silver halide color photographic light-sensitive material, and a complex-forming compound is added to a processing material from the viewpoint of raw storage stability.

As a heating method in the heating and developing 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 may be used. There are methods such as contacting and passing through a high temperature atmosphere. A method of superposing a silver halide color photographic light-sensitive material and a processing material in such a manner that the light-sensitive layer and the processing layer face each other is disclosed in JP-A-62-253,159 and JP-A-61-147,244. (27) can be applied.

In the processing of the silver halide color photographic light-sensitive material of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-75247 and JP-A-59-1
Nos. 77,547, 59-181,353, 60-
Nos. 18,951, 62-25,944, Japanese Patent Application Nos. 4-277,517, 4-243,072, and 4
-244, 693, 6-164,421, 6-
Apparatus described in each gazette such as 164,422 is preferably used. Examples of commercially available devices include the Pictrostat 100, the Pictrostat 200, the Pictrostat 300, the Pictrostat 330, the Pictrostat 50, the Pictrograph 3000, the Pictrograph 20 manufactured by Fuji Photo Film Co., Ltd.
00 or the like can be used.

The silver halide color photographic light-sensitive material of the present invention may have a form having a conductive heating layer as a heating means for heat development. As the heat-generating elements, those described in JP-A-61-145544 can be used.

In the present invention, image information can be taken in without removing developed silver and undeveloped photosensitive silver halide generated by development, but an image can be taken after removal. In the latter case, a means for removing them at the same time as or after the development can be applied. In order to remove the developed silver in the silver halide color photographic light-sensitive material at the same time as the development and to complex or solubilize the photosensitive silver halide, an oxidizing agent for silver, which acts as a bleaching agent for the processing material, or rehalogenation. An agent or a silver halide solvent acting as a fixing agent may be contained so as to cause these reactions during thermal development. After the development of the image is completed, a second material containing a silver oxidizing agent, a rehalogenating agent or a silver halide solvent is attached to a silver halide color photographic light-sensitive material to remove developed silver or to remove photosensitive silver. It can also cause complexation or solubilization of silver halide. In the present invention, it is preferable to carry out these processes to the extent that image information is not obstructed after photographing and subsequent image formation and development. In particular, undeveloped photosensitive silver halide causes a high haze in the gelatin film and increases the background density of the image. It is preferable to remove all or part of the film from the film. It is also preferable to use tabular grains having a high average aspect ratio or tabular grains having a high silver chloride content for the purpose of reducing the haze of the photosensitive silver halide itself. Tabular grains having a high average aspect ratio have a large decrease in haze due to a reduction in the amount of coated silver.

As the bleaching agent that can be used in the processing material of the present invention, any commonly used silver bleaching agent can be used. Such bleaches are disclosed in U.S. Pat. No. 1,315,46.
No. 4, No. 1,946,640, and Ph.
otographic Chemistry, vol2, chapter30, Foundation Pre
ss, London, England. These bleaches effectively oxidize and solubilize photographic silver images. Examples of useful silver bleaches include alkali metal dichromates, alkali metal ferricyanides. Preferred bleaches are those which are soluble in water and are ninhydrin, indandione, hexaketocyclohexane, 2,4-dinitrobenzoic acid, benzoquinone, benzenesulfonic acid, 2,2
Includes 5-dinitrobenzoic acid. Also, there are metal organic complexes, for example, ferric salts of cyclohexyldialkylaminotetraacetic acid, ferric salts of ethylenediaminetetraacetic acid, and ferric salts of citric acid. As the fixing agent, a silver halide solvent that can be included in a processing material (first processing material) for developing the silver halide color photographic light-sensitive material can be used. The same binder, support, and other additives that can be used in the second processing material can be used as in the first processing material. The amount of bleach applied
The amount of silver to be applied per unit area of the silver halide color photographic light-sensitive material should be changed depending on the silver content of the silver halide color photographic light-sensitive material to be laminated.
01 to 10 are used at a coverage of silver mole mole / photosensitive material.
The molar ratio is preferably 0.1 to 3 mol / mol of silver applied to the light-sensitive material, and more preferably 0.1 to 2 mol / mol of silver applied to the light-sensitive material.

As the silver halide solvent, known solvents can be used. For example, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, sulfites such as sodium sulfite and sodium bisulfite, thiocyanates such as potassium thiocyanate and ammonium thiocyanate, described in JP-B-47-11386. 1,8-
Thioether compounds such as di-3,6-dithiaoctane, 2,2'-thiodiethanol, 6,9-dioxa-3,12-dithiatetradecane-1,14-diol;
Use of a compound having a 5- or 6-membered imide ring such as uracil and hydantoin described in Japanese Patent Application No. 6-325350 and a compound of the following general formula (I) described in JP-A-53-144319. Can be. Analytica Chemica Acta 248 604
To 614 (1991) are also preferred as meso-ion thiolate compounds of trimethyltriazolium thiolate. The compounds described in Japanese Patent Application No. 6-206331 which can fix and stabilize silver halide can also be used as a silver halide solvent.

General formula (I): N (R ¹ ) (R ² ) -C (=
S) —X—R ^{3 In the} general formula (I), X represents a sulfur atom or an oxygen atom. R ¹ and R ² may be the same or different,
Each represents an aliphatic group, an aryl group, a heterocyclic residue or an amino group. R ³ represents an aliphatic group or an aryl group. R
¹ and R ² , or R ² and R ³ may combine with each other to form a 5- or 6-membered heterocycle. The above-mentioned silver halide solvents may be used in combination. Among the above compounds,
Particularly preferred are compounds having a 5- to 6-membered imide ring, such as sulfites, uracil and hydantoin.

The total content of the silver halide solvent in the processing layer is 0.01 to 100 mmol / m ² .
Preferably from 1 to 50 mmol / m ^2, more preferably 10 to 50 mmol / m ^2. The molar ratio is 1/20 to 20 times, preferably 1/10 to 10 times, more preferably 1/3 to 3 times, based on the amount of silver applied to the silver halide color photographic light-sensitive material. The silver halide solvent may be added to a solvent such as water, methanol, ethanol, acetone, dimethylformamide, methylpropyl glycol, or an alkali or acidic aqueous solution, or may be added to a coating solution by dispersing solid fine particles. Good.

Further, a physical development nucleus and a silver halide solvent are contained in the processing material, so that the photosensitive silver halide emulsion of the silver halide color photographic light-sensitive material is solubilized simultaneously with the development.
And may be fixed to the treatment layer. The physical development nucleus is for reducing a soluble silver salt diffused from a silver halide color photographic light-sensitive material to convert it into physically developed silver and fixing it to a processing layer. Physical development nuclei include heavy metals such as zinc, mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt, copper, ruthenium, or palladium, platinum, silver,
Any of known noble metals such as gold or colloidal particles of chalcogen compounds such as sulfuric acid, selenium, tellurium and the like can be used as physical development nuclei. These physical development nuclei substances are prepared by reducing the corresponding metal ions with a reducing agent such as ascorbic acid, sodium borohydride, or hydroquinone to form a metal colloidal dispersion or a soluble sulfide, selenide or telluride solution. To form a colloidal dispersion of a water-insoluble metal sulfide, metal selenide or metal telluride. These dispersions are preferably formed in a hydrophilic binder such as gelatin. The method of preparing colloidal silver particles is described in U.S. Pat. No. 2,688,601. If necessary, a desalting method for removing an excess salt known in the method for preparing a silver halide emulsion may be performed. The physical development nuclei preferably have a particle diameter of 2 to 200 nm. These physical development nuclei are usually added to the processing layer in an amount of 10 ^{−3 to} 100 mg / m ² , preferably 10 to 100 mg / m ² .
^{-2 to} 10 mg / m ² . Physical development nuclei can be separately prepared and added to a coating solution, but in a coating solution containing a hydrophilic binder, for example, silver nitrate and sodium sulfide, or chloroauric acid and a reducing agent, etc. It may be made by reacting. As the physical development nucleus, silver, silver sulfide, palladium sulfide and the like are preferably used. When physical developed silver transferred to the complexing agent sheet is used as an image, palladium sulfide, silver sulfide, and the like are preferably used because Dmin is cut off and Dmax is high.

Both the first processing material and the second processing material can have at least one polymerizable timing layer. The polymerizable timing layer can temporarily delay the bleaching / fixing reaction until the desired reaction between the silver halide and the dye-providing compound or the developing agent is substantially completed. The timing layer can be made of gelatin, polyvinyl alcohol, or polyvinyl alcohol-polyvinyl acetate. This layer also
For example, US Patent Nos. 4,056,394 and 4,06
It may be a barrier timing layer as described in the specifications of US Pat. Nos. 1,496 and 4,229,516. When applying this timing layer, usually 5 to 5
It is applied to a thickness of 0 μm, preferably 10 to 30 μm.

In the present invention, as a method for bleaching / fixing a halogenated color photographic light-sensitive material after development using a second processing material, a back layer of both the halogenated color photographic light-sensitive material and the second processing material is used. After supplying the halogenated color photographic light-sensitive material or the second processing material with water in an amount of 0.1 to 1 times the total amount of water required for maximally swelling the entire coating film except for the halogenated color photographic light-sensitive material and the second processing material, Are superposed on each other so that the photosensitive layer and the processing layer face each other, and heated at 40 to 100 ° C. for 5 to 60 seconds. The amount of water,
With respect to the type of water, the method of applying water, and the method of overlapping the halogenated color photographic light-sensitive material with the processing material, the same materials as those for the first processing material can be used.

More specifically, JP-A-59-13673
3, bleaching / fixing sheets described in U.S. Pat. No. 4,124,398 and JP-A-55-28098 can be used.

In the halogenated color photographic light-sensitive material, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of slipperiness, antistatic, development acceleration and the like. As a specific example of the surfactant, known technology No. 5 (1991)
Aztec Co., Ltd., March 22, 2003)
38 pages, JP-A-62-173,463, 62-173
183,457. The halogenated color photographic light-sensitive material may contain an organic fluoro compound for the purpose of preventing slippage, preventing static charge, and improving releasability. Representative examples of the above-mentioned organic fluoro compounds are described in JP-B-57-9053, columns 8-17, and JP-A-61-2.
No. 0944, No. 62-135826, etc., or fluorine-containing surfactants, or hydrophobic fluorine such as oily fluorine-containing compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin Compounds.

Since the halogenated color photographic light-sensitive material preferably has a slip property, the halogenated color photographic light-sensitive material can contain a slipping agent. It is preferable to use the slip agent on both the photosensitive layer surface and the back surface.
Preferred examples of the slip property include a slip agent having a dynamic friction coefficient of 0.01 to 0.25. This dynamic friction coefficient is 60 c for a stainless steel ball having a diameter of 5 mm.
m / min (25 ° C, 60 ° C)
% 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 usable sliding agents include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethylsiloxane, polydiethylsiloxane, and polydiethylsiloxane. Examples include styrylmethylsiloxane and polymethylphenylsiloxane. Among these, polydimethylsiloxane and esters having a long-chain alkyl group are particularly preferred. The layer to which the slip agent is added is preferably the outermost layer of the emulsion layer or the back layer.

In the present invention, an antistatic agent is preferably used. As the antistatic agent, for example,
Examples thereof include polymers containing a carboxylic acid, a carboxylate, and a sulfonate, cationic polymers, and ionic surfactant compounds. The most preferred antistatic _{agents, ZnO, TiO 2, SnO 2} , Al 2 O 3, In
_At least one selected from the group consisting of ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , and V ₂ O _{5 has} a volume resistivity of 10 ⁷ Ω.
Cm or less, more preferably 10 ⁵ Ω · cm or less, a crystalline metal oxide having a particle size of 0.001 to 1.0 μm or a composite oxide thereof (Sb, P, B, I
(n, S, Si, O, etc.), and fine particles of a sol, a metal oxide, or a composite oxide thereof. The content of the antistatic agent in the silver halide color photographic light-sensitive material is preferably 5 to 500 mg / m ² ,
~350mg / m ² is particularly preferred. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is 1
/ 300 to 100/1 is preferred, and 1/100 to 100
/ 5 is more preferred.

The silver halide color photographic light-sensitive material (including the back layer) has dimensional stability, curl prevention, adhesion prevention,
Various polymer latexes can be contained for the purpose of improving film physical properties such as prevention of cracking of the film and prevention of pressure increase / decrease sensation. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, and 62-110066 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. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be either a processing solution soluble or a processing solution insoluble,
Preferably, both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size of the matting agent is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow. 90 to 90% of the total number of particles is 0.9 to 1.1 times the average particle size. It is preferable to include them. 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. )), Polystyrene particles (0.25 μm), colloidal silica (0.
03 μm). Specifically, JP-A-61-8
No. 8256, page (29). In addition, JP-A-63-274944 such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads.
And the compounds described in JP-A-63-274952. In addition, the compounds described in the above research disclosure can be used.

In the present invention, a support capable of withstanding the processing temperature is used as a support for the silver halide color photographic light-sensitive material and the processing material. Generally, The Photographic Society of Japan, "Basics of Photonic Engineering-Silver Halide Photography-", Inc.
Photographic supports such as papers and synthetic polymers (films) described on pages 223 to 240 of Corona (1979). Specific examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, and celluloses (for example, triacetyl cellulose). These can be used alone or as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition, JP-A-62-253,159, pages (29) to (31), JP-A-1-161,236, pages (14) to (17),
-316,848, JP-A-2-22,651, JP-A-3-56,955, U.S. Pat.
The support described in 1,033, etc. can be used.

Particularly when the requirements for heat resistance and curl characteristics are strict, as a support for a silver halide color photographic light-sensitive material, JP-A-6-41281, JP-A-6-43581, JP-A-6-51426, and JP-A-6-51426 can be used. No. 51437, 6-514
No. 42, Japanese Patent Application No. 4-251845, No. 4-23182
No. 5, 4-253545, 4-258828,
4-240122, 4-221538, 5-
No. 21625, No. 5-15926, No. 4-33192
No. 8, No. 5-199704, No. 6-13455, No. 6-1466, and the like can be preferably used. Further, a support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used.

In order to adhere the support and the photographic component layer, it is preferable to perform a surface treatment. The surface treatment includes chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc. Is mentioned. 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. Vinyl chloride, vinylidene chloride,
Butadiene, methacrylic acid, acrylic acid, itaconic acid,
Including copolymers starting from monomers selected from maleic anhydride and the like, polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose,
Gelatin. Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, gelatin hardeners such as chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine) And the like, 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.

As a support, for example, Japanese Patent Application Laid-Open No.
No. 124645, No. 5-40321, No. 6-3509
No. 2, Japanese Patent Application Nos. 5-58221, 5-106979, etc., using a support having a magnetic recording layer described in each gazette,
It is preferable to record shooting information and the like.

The magnetic recording layer is obtained by coating an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder on a support. The magnetic particles include a 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 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. Needle shape, rice grain shape,
Any of spherical, cubic, and plate shapes may be used. The specific surface area is preferably at least 20 m ² / g in S _BET, 30m ² / g
The above is particularly preferred. The saturation magnetization (σs) of a ferromagnetic material is
It is preferably from 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, and particularly preferably from 4.0 × 10 ^{4 to} 2.5 × 100 ^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, etc. 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 magnetic recording layer has lubricating properties, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. 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 a magnetic recording layer described above 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.

[0187] 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.

A method for producing a print on a color paper or a heat-developable photosensitive material using the color photographing material is disclosed in JP-A-5-241251 and JP-A-5-19364.
And the method described in JP-A-5-19363 can be used.

A method for producing a print on a color paper or a heat-developable photosensitive material using the silver halide color photographic light-sensitive material is described in JP-A-5-241251 and JP-A-5-241251.
Nos. 19364 and 5-19363 can be adopted.

[0190]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. Example 1 (1) Preparation of Emulsion - tabular silver iodobromide emulsion 1-A (comparative emulsion) - In addition to H ₂ SO ₄ aqueous solution 1,000cc containing oxidized gelatin 0.5g and KBr0.37G PH = 2, stirring at 40 ° C. and 0.3M AgNO
( ₃ ) 20 cc of the aqueous solution (A) and 20 cc of the 0.3 M aqueous KBr solution (B) were simultaneously added by a double jet for 40 seconds. Thereafter, the pH was adjusted to 5.0 by adding NaOH, and the pAg was adjusted to 9.9. The temperature was raised to 75 ° C. in 35 minutes, and 35 g of oxidized gelatin was added.
921 cc of a 2M aqueous AgNO ₃ solution (C) and 800 cc of a 1.4 M aqueous KBr solution (D) were maintained at a pAg of 8.58 while accelerating the flow rate (the flow rate at the end was 7.
(2x) added for 33 minutes. Then, the temperature was lowered to 55 ° C,
80cc of 0.4M AgNO ₃ aqueous solution (E) and 0.12
223 cc of a KI aqueous solution of M (F) was added in a fixed amount for 3 minutes, and then an aqueous solution of KBr was added to adjust the pAg to 8.8. Then, a 1.8 M aqueous solution of AgNO ₃ (G) 115 was added.
cc and 131 cc of an aqueous KBr solution (H) were added. Thereafter, the emulsion was cooled to 35 ° C., and a sedimentation agent (Kao Corporation)
(Demol), 75 g of gelatin and 10 cc of phenoxyethanol.
And adjusted to PH = 5.5 and pAg = 8.2. The resulting grains had tabular grains of 99% of the total projected area of all grains.
And the average aspect ratio is 23.9,
The average equivalent spherical diameter is 0.76 μm, and the average particle thickness is 0.
It was a hexagonal tabular grain emulsion having a diameter of 08 μm and an average equivalent circle diameter of 1.91 μm. The values of the average particle thickness and the average equivalent circle diameter were determined by taking a transmission electron micrograph by a replica method.

The following tabular silver iodobromide emulsions 1-B to 1-D
Is also a tabular silver iodobromide emulsion 1-A except for the following points.
Prepared in the same manner as The obtained tabular silver iodobromide emulsion 1-B
1-D was almost the same in average aspect ratio and average equivalent sphere diameter as tabular silver iodobromide emulsion 1-A.

[0192] - the (H) outside the 6 iridium tripotassium chloride was added iridium equivalent 1 × 10 ^-7 mol to liquid, - (light-sensitive silver halide emulsion of the present invention) tabular silver iodobromide emulsion 1-B Tabular silver iodobromide emulsion 1
Prepared as in -A.

[0193] - tabular silver iodobromide emulsion 1-C (light-sensitive silver halide emulsion of the present invention) - (H) outside of adding iron corresponding 6 × 10 ^-5 mol of potassium ferrocyanide in solution, plate-shaped Prepared similarly to Silver iodobromide emulsion 1-A.

-Tabular silver iodobromide emulsion 1-D (comparative emulsion)
-(H) Rhodium hexabromide 3 potassium in rhodium solution 2
× 10 ^-8 mol, except that tabular silver iodobromide emulsion 1-A
Prepared in the same manner as

(2) Chemical sensitization The tabular silver iodobromide emulsions 1-A to 1-D were treated at 60 ° C.
Under the conditions of PH = 6.2 and pAg = 8.4, the spectral sensitizing dye shown in Chemical formula 23 (sensitizing dyes I to III for green-sensitive emulsion), the compound 1 shown in Chemical formula 24 and a selenium sensitizer, and thiocyanate Spectral sensitization and chemical sensitization were performed by adding potassium acid, chloroauric acid and sodium thiosulfate. To stop chemical sensitization,
The chemical sensitization terminator shown in Chemical formula 24 was used. The amount of the chemical sensitizer (selenium sensitizer) was set to 1/1 of each tabular silver iodobromide emulsion.
The sensitivity of the 00 second exposure was adjusted to be the highest. In addition,
With respect to the tabular silver iodobromide emulsions 1-C and 1-D, zinc nitrate was added to the tabular silver iodobromide emulsion at the time of redispersion of gelatin after washing with water.

[0196]

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[0197]

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(3) Preparation of dispersion and coated sample and evaluation thereof A dispersion of zinc hydroxide used as a base precursor was prepared as follows. The particle size of the primary particles is 0.
31 g of zinc hydroxide powder of 2 μm, 1.6 g of carboxymethylcellulose and 0.4 g of sodium polyacrylate as a dispersant, and lime-treated ossein gelatin 8.5
g and 158.5 ml of water were mixed, and 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 as follows. Magenta coupler (a) 7.80 g, developing agent (b) 5.45 g shown in Chemical formula 25,
8.21 g of high boiling organic solvent (d) and ethyl acetate
0 ml was dissolved at 60 ° C. to prepare a solution. 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.

[0200]

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The dispersion and the tabular silver iodobromide emulsion 1-A were combined and coated on a support with the composition shown in Table 1 to prepare a single layer photosensitive material containing a developing agent (Sample 101). Also,
"1-A" in Table 1 is replaced with "1-B", "1-C",
The silver halide color photographic light-sensitive materials of the present invention (samples 102 and 103) and the light-sensitive material (sample 104) were prepared by substituting “1-D”, respectively. The antifoggant (c) was added when preparing the coating solution for the magenta coloring layer.

[0202]

[Table 1]

[0203]

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Further, first processing materials P-1 shown in Tables 2 and 3 were produced. Table 2 shows that the processing material P-1
In Table 3, details of the treatment layer applied on the support (transparent support A) are shown, and Table 3 shows details of the support (transparent support A).

[0205]

[Table 2]

[0206]

[Table 3]

[0207]

Embedded image

The samples 101 to 104 were passed through an optical wedge and a green filter through a sensitometer MRRKVI manufactured by EGG.
An exposure of 1 / 10,000 seconds was performed at I. 15 ml / m ² of 40 ° C. warm water was applied to the photosensitive layer surface (magenta coloring layer, intermediate layer and protective layer) of each sample after exposure, and the processing material P-1
And the photosensitive layer surface of each of the above samples was overlapped with each other, and then heated at 78 ° C. for 1 hour using a heat drum.
Heat development was performed for 7 seconds. After the above first processing, when each sample was peeled off from the processing material P-1, a magenta-colored wedge-shaped image was obtained for each sample. Next, these samples 10
1 to 104, the second processing material P-2 shown in Table 4
For a second treatment. In Table 4,
"Compound (2)" is as shown in the above-mentioned Chemical formula 27,
Details of "Transparent support A" are as shown in Table 3.

[0209]

[Table 4]

The second processing was performed as follows.
That is, after applying 10 ml / m ² of water to the surface of the treatment layer (first to fourth layers) of the second treatment material P-2, the surface of the treatment layer and the sample 101 after the first treatment were performed. To 104, and heat-developed at 60 ° C. for 30 seconds. After the second treatment, the transmission density of each sample was measured to obtain a so-called characteristic curve. 0.1 than fog density
5 The relative sensitivity is defined as the reciprocal of the exposure amount corresponding to the higher density.
The sensitivity of 104 was expressed as a relative value of the sensitivity of Sample 101. Further, in order to estimate the density fluctuation due to the fluctuation of the temperature in the photosensitive material during the heat development processing, 78 ° C.
With respect to the exposure amount required to obtain a density of 1 in 17 seconds, the density change ΔD when the temperature of the heat development was 83 ° C. was examined. sensitivity,
Dmin, density change ΔD due to temperature fluctuation, and image unevenness in the intermediate density portion during heating development processing at 80 ° C. were visually evaluated. The results are shown in Table 5. In this case, the evaluation criteria were as follows: ×: NG, Δ: acceptable, ○: OK.

[0211]

[Table 5]

From the results shown in Table 5, it can be seen that the image unevenness corresponds to the change in density with respect to the processing temperature of heat development, and that the photosensitive silver halide emulsion containing tabular grains containing metal ions and the like as shallow electron traps was used. It can be seen that when used, the sensitivity is high, the dependency of the density change on the temperature in the development processing is reduced, and the image unevenness is improved.

Example 2 A method for preparing ultrafine silver chloride emulsion 2- (a) for epitaxial bonding is described below. That is, the solution (I) and the solution (II) shown in Table 7 were simultaneously added to a well-stirred aqueous solution of gelatin having a composition shown in Table 6 over a period of 3 minutes, and 5 minutes later, (III) Liquid and liquid (IV) were added simultaneously over 5 minutes.

[0214]

[Table 6]

[0215]

[Table 7]

After washing with water and desalting (using a sedimenting agent (manufactured by Kao Corporation; Demol)) in a conventional manner, 22 g of lime-treated gelatin was added to adjust the pH to 6.1 and the pAg to 7.1, and then phenoxyethanol was added. added. The grain size was a silver chloride cubic emulsion having an average side length of 0.06 μm. The yield of the ultrafine silver chloride emulsion 2- (a) for epitaxial bonding was 635 g.

-Epitaxial tabular silver iodobromide emulsion 2-
Preparation of A (Comparative Emulsion)-In tabular silver iodobromide emulsion 1-A, 35 minutes after addition of the sensitizing dye during chemical sensitization, 35 g of ultrafine silver chloride emulsion 2- (a) for epitaxial bonding was added. Thereafter, the amounts of chloroauric acid, sodium thiosulfate, and selenium sensitizer added later were changed so that the sensitivity at the time of exposure for 1 / 10,000 seconds was maximized.

-Epitaxial tabular silver iodobromide emulsion 2-
Preparation of B (photosensitive silver halide emulsion used in the present invention)-In tabular silver iodobromide emulsion 1-B, 10 minutes after addition of a sensitizing dye at the time of chemical sensitization, ultrafine silver chloride for epitaxial bonding was used. Emulsion 2- (a) was added in an amount of 35 g, and the amounts of chloroauric acid, sodium thiosulfate, and selenium sensitizer added thereafter were changed so that the sensitivity at the time of 1 / 10,000 second exposure was maximized. .

-Epitaxial tabular silver iodobromide emulsion 2-
Preparation of C (photosensitive silver halide emulsion used in the present invention)-In tabular silver iodobromide emulsion 1-C, 10 minutes after addition of the sensitizing dye at the time of chemical sensitization, silver chloride fine grain emulsion 2- ( b) was added in an amount of 1/100
Adjustment was made so that the sensitivity at the time of exposure for 00 seconds was maximized.

-Epitaxial tabular silver iodobromide emulsion 2-
Preparation of D (photosensitive silver halide emulsion used in the present invention)-In tabular silver iodobromide emulsion 1-A, 10 minutes after the addition of the sensitizing dye at the time of chemical sensitization, 3 potassium iridium hexachloride was added to iridium. The equivalent of ^{4.5.times.10.sup.-7} mol / mol silver is contained.
The same silver chloride fine grain emulsion 2- (b) as in (a) was added to 35
g, and then changing the amounts of chloroauric acid, sodium thiosulfate and selenium sensitizer to 1/10000
The sensitivity at the time of second exposure was adjusted to be the highest.

-Epitaxial tabular silver iodobromide emulsion 2-
Preparation of E (photosensitive silver halide emulsion used in the present invention)-In tabular silver iodobromide emulsion 1-A, after 10 minutes from the addition of the sensitizing dye at the time of chemical sensitization, the yellow blood salt was changed to 1 equivalent of iron. .5 × 10 ^-3
Except for containing mol / mol, 35 g of silver chloride fine grain emulsion 2- (c), which is the same as ultrafine silver chloride emulsion 2- (a) for epitaxial bonding, is added, and chloroauric acid added thereafter, The amounts of sodium thiosulfate and selenium sensitizer were changed to adjust the sensitivity at the time of 1 / 10,000 second exposure to the maximum. Emulsions 2-A to 2-E consisted of grains which were epitaxially bonded to the corners of hexagonal tabular grains, and their average aspect ratio and average sphere equivalent diameter were almost equal to those of Emulsion 1-A.

In Example 1, 2-A to 2
Except for using -E, samples 201 to 205 were prepared in the same manner as sample 101 in Example 1. The sample was processed, exposed, and heated and developed in the same manner as in Example 1.
Table 8 shows the results. Note that the evaluation criteria for image unevenness in Table 8 are the same as those in Table 5.

[0223]

[Table 8]

From the results shown in Table 8, although the epitaxial tabular grains are highly sensitized, there is a problem that the concentration dependency on the temperature fluctuation during the development processing is further increased. When used, it is clear that the sensitivity is further improved and the stability to the temperature during the development processing is improved.

Example 3 Preparation of (100) Tabular Silver Chlorobromide Emulsion 3-A (Comparative Emulsion) 25 g of deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g and 1 g of sodium chloride, 1200 ml of an aqueous gelatin solution having a pH of 4.3 containing 4.5 ml of 1N nitric acid was placed in a reaction vessel, and the temperature was raised to 40 ° C. While vigorously stirring this solution, 36 ml of 100 ml of an aqueous solution (A) containing 20 g of silver nitrate and 100 ml of an aqueous solution (B) containing 0.71 g of potassium bromide and 6.67 g of sodium chloride were added to this solution. Each was added simultaneously for 45 seconds and mixed. Then, after stirring for 3 minutes,
An aqueous solution 100 containing 1.1 g of potassium bromide is added to the solution.
43.4 ml of solution (C) was added over 30 seconds and mixed. Thereafter, the temperature was lowered to 30 ° C. in 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 in 108 ml each of 2 ml.
It was added and mixed simultaneously for 15 minutes. Thereafter, the mixture was stirred for 1 minute, and 20 ml of a 10% sodium chloride solution and 7 ml of a 1N aqueous solution of sodium hydroxide were added thereto.
After the silver potential was adjusted to 80 mV on the saturated calomel electrode, 2 ml of aqueous hydrogen peroxide (35%) was added. After that, the temperature was set to 7
The temperature was raised to 5 ° C and aged for 5 minutes. Silver bromide content of 5
In addition to the mol%, 1086 g of ultrafine silver chlorobromide emulsion 3- (a) prepared in the same manner as the ultrafine silver chloride emulsion 2- (a) for epitaxial bonding was added for 45 minutes while maintaining the silver potential at 140 mV. . The temperature was lowered to 35 ° C., and desalting was performed according to a conventional method. The obtained tabular silver chlorobromide emulsion 3-A
Has an average particle size of 0.92μ expressed by a diameter equivalent to a sphere.
m, the average grain thickness was 0.128 μm, the average aspect ratio was 15.9, and the emulsion was composed of silver chlorobromide (100) tabular grains having a silver bromide content of 5 mol%. The chemical sensitization of the tabular silver chlorobromide emulsion 3-A was 1% after the addition of the sensitizing dye.
0 ^-3 added KI in a ratio of moles / mole, an outer addition of ribonucleic acid hydrolyzate was carried out as tabular silver iodobromide emulsion 1-A. The following tabular silver chlorobromide emulsions 3-B to 3-D were prepared in the same manner as the tabular silver chlorobromide emulsion 3-A, except for the following points. Obtained tabular silver chlorobromide emulsions 3-B to 3
-D had the same average aspect ratio and average equivalent sphere diameter as tabular silver chlorobromide emulsion 1-A.

-(100) Tabular silver chlorobromide emulsion 3-B
(Photosensitive silver halide emulsion used in the present invention)-Ultrafine silver chlorobromide which is the same as emulsion 3- (a) except that it contains yellow blood salt equivalent to iron at 2 x 10 ^-4 mol / mol. Emulsion 3-
Except that (b) was added, it was prepared in the same manner as in tabular silver chlorobromide emulsion 3-A. Chemical sensitization of tabular silver chlorobromide emulsion 3-B was carried out in the same manner as in emulsion 3-A.

-Epitaxial (100) tabular silver chlorobromide emulsion 3-C (comparative emulsion)-10 minutes after the addition of the sensitizing dye at the time of chemical sensitization, no KI was added, and the content of silver bromide was reduced. Emulsion 2- is 100 mol%
Emulsion 3- (c), the same as (a), was added in the same manner as Emulsion 3-A, except that 35 g of emulsion 3- (c) was added, and sensitization was performed by adding chloroauric acid, sodium thiosulfate, and selenium sensitizer. I got it.

-Epitaxial (100) tabular silver chlorobromide emulsion 3-D (photosensitive silver halide emulsion used in the present invention)-KI was not added 10 minutes after the addition of the sensitizing dye at the time of chemical sensitization. Emulsion 2 except that the content of silver bromide was 100 mol%.
Emulsion 3- (c), which was the same as (b), was added in the same manner as emulsion 3-B except that 35 g was added and chloroauric acid, sodium thiosulfate, and a selenium sensitizer were added. D was prepared.

-Epitaxial (100) tabular silver chlorobromide emulsion 3-E (light-sensitive silver halide emulsion used in the present invention) 35 g of emulsion 3- (d), which is the same as emulsion 3- (c) except that the yellow blood salt is replaced with iron and containing 5 × 10 ^-4 , is added with chloroauric acid and thiosulfate Emulsion 3-E was prepared in the same manner as Emulsion 3-A except that sodium and selenium sensitizers were added.
Was prepared.

Emulsions 3-C, 3-D, and 3-E were emulsions composed of (100) tabular grains epitaxially bonded to rectangular corners.

In Sample 101, emulsions 3-A to 3-D were used in the same manner as in Sample 101, except that the emulsion used was changed and the antifoggant (c) was increased to 8 mg / m ^2. ~ 305 was created.

A sample was processed in the same manner as in Example 1.
Exposure and heat development were performed. Table 9 shows the above results. In Table 9, the sensitivity values are relative values with the sensitivity of the sample 301 being 100. In addition, the evaluation criteria for image unevenness in Table 9 are the same as those in Table 5.

[0233]

[Table 9]

From the results shown in Table 9, even in the high silver chloride tabular grain emulsion, since the high silver chloride emulsion had high activity, the density change due to temperature fluctuation during the development processing was large. However, it is clear that by introducing metal ions and the like which are shallow electron traps into the emulsion, even in a high silver chloride emulsion, it is possible to effectively suppress the density change due to the temperature fluctuation during the development processing while maintaining high sensitivity. . This effect was remarkable also in the epitaxial junction grain emulsion.

Using a (111) tabular high silver chloride emulsion 3-F containing a metal ion or the like which is a shallow electron trap, a photosensitive material was prepared in the same manner as described above, and subjected to the same heat treatment. Did not appear, showing good photographic properties. The (111) tabular high silver chloride emulsion 3-F was prepared according to the following formulation. That is, 1200 ml of an aqueous gelatin solution containing 2.1 g of deionized alkali-treated bone gelatin and 2 g of sodium chloride was placed in a reaction vessel, kept at 35 ° C., and while strongly stirring the solution, 1100 ml of an aqueous solution containing 165 g of silver nitrate (A) Liquid and 59.1 g of sodium chloride
And 1100 ml of the aqueous solution (B) were simultaneously added and mixed in 60 ml portions over 1 minute. One minute after the completion of the addition and mixing, 40 ml of 50 ml of the liquid (C), which is an aqueous solution containing 0.285 g of the compound (3), was added.
30 ml of a 10% aqueous solution of sodium chloride was added. Thereafter, the temperature was raised to 60 ° C. over 25 minutes, and after 16 minutes, 260 ml of an aqueous gelatin solution containing 29 g of phthalated gelatin was added. After 3 minutes, 10 ml of solution (c) was added. One minute later, 768 ml of the solution (A) and the solution (B) were added at an initial velocity of 2.85 ml / min and an acceleration of 0.818 ml / (min) ²
At the same time. 10 minutes before the completion of the addition and mixing of the solution (A) and the solution (B), the solution (D), which is 270 ml of an aqueous solution containing 3.9 g of sodium chloride and 0.1 g of yellow blood salt,
Added over 10 minutes. Two minutes before the completion of the addition of the solution (A) and the solution (B), 34 ml of a 10% aqueous solution of potassium bromide was added.
Was added in 3 seconds. After the addition of solution (A) and solution (B), 3
Then, 27 ml of potassium thiocyanate 1% was added thereto, and sensitizing dye I for green-sensitive emulsion 570 mg, sensitizing dye II for green-sensitive emulsion 60 mg, and sensitizing dye III for green-sensitive emulsion 120 were added.
45 ml of a melt of 100 g of gelatin dispersion containing
1 minute after the addition, 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 performed using 67 g of deionized alkali-treated bone gelatin, zinc nitrate and phenoxyethanol. And it adjusted so that it might be set to pH6.3 and pAg7.7. The resulting emulsion had an average grain size of 0.74 μm expressed as a sphere-equivalent diameter, an aspect ratio of 8.7, and a silver bromide (111) content of 5 mol% silver bromide.
Emulsion 3-F comprising tabular grains. Chemical sensitization
The reaction is performed at 60 ° C., and the compound (4), 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene, sodium thiosulfate, selenium sensitizer, chloroauric acid, and sodium benzenethiosulfonate are sequentially added. It was added for chemical sensitization to obtain the highest sensitivity. Termination of chemical sensitization was performed using compound (4).

[0236]

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Example 4-Tabular silver iodobromide emulsion 4-A (comparative emulsion)-0.74 g of gelatin having an average molecular weight of 12,000 and KB
930 nl of distilled water containing 0.3 g of r was put into the reaction vessel, and the temperature was raised to 35 ° C. While stirring this solution vigorously,
30 ml of an aqueous solution (A) containing 1.2 g of AgNO ₃ and KB
30 ml of an aqueous solution (B) containing 0.82 g of r was added over 20 seconds. After maintaining at 40 ° C. for 1 minute after completion of the addition,
The reaction solution was heated to 75 ° C. Oxidized gelatin 2
After adding 7.0 g together with 200 ml of distilled water, AgN
100 ml of an aqueous solution (C) containing 22.5 g of O ₃ and KBr
80 ml of an aqueous solution (D) containing 15.43 g was added over 11 minutes while increasing the addition flow rate. Subsequently, 250 m of an aqueous solution (E) containing 75.1 g of AgNO ₃
and 210 ml of an aqueous solution (F) (KBr concentration: 26%) containing KI in a molar ratio of 3:97 to KBr while accelerating the addition flow rate and keeping the silver potential of the reaction solution relative to the saturated calomel electrode. To be 0 mV. 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 AgNO ₃ and 320 ml of an aqueous solution (J) containing 7.26 g of KI were added over 5 minutes. After completion of the addition, 5.5 g of KBr was added, and the mixture was kept at 55 ° C. for 1 minute. Then, an aqueous solution (K) further containing 44.3 g of AgNO _3.
Aqueous solution (L) 1 containing 180 ml and 34.0 g of KBr
60 ml were added over 8 minutes. Lower the temperature,
Desalting was performed according to a conventional method. In the resulting emulsion grains, tabular grains account for more than 99% of the total projected area of all grains, have an average equivalent sphere diameter of 0.66 μm, and have an average thickness of 0.
095 μm, the average aspect ratio was 14.9, and the average equivalent circular diameter was 1.4 μm.

-Tabular silver iodobromide emulsion 4-B (light-sensitive silver halide emulsion used in the present invention)-Except that 8 × 10 ^-5 mol of yellow blood salt equivalent to iron was added to solution (K), It was prepared in the same manner as Comparative Emulsion 4-A. The resulting emulsion grains had the same average aspect ratio and equivalent sphere diameter as Emulsion 4-A.

-Tabular silver iodobromide emulsion 4-C (comparative emulsion)
12.5 g gelatin having an average molecular weight of 15,000, KBr
950 m of distilled water containing 4.35 g and 0.32 g of KI
1 was placed in a reaction vessel and heated to 45 ° C. While this solution was vigorously stirred, 50 ml of an aqueous solution (A) containing 8.3 g of AgNO ₃ and 50 ml of an aqueous solution (B) containing 2.67 g of KBr were added over 45 seconds. 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 AgNO ₃ (C) and a 24.8% aqueous solution of KBr (D) were added while accelerating the flow rate, and the silver potential of the reaction solution was adjusted to 0 mV with respect to the saturated calomel electrode. Added over 13 minutes. After maintaining the temperature at 63 ° C. for 2 minutes after completion of the addition, the temperature of the reaction solution was raised to 45 ° C.
The temperature was lowered to ° C. Next, 50 ml of an aqueous solution (E) containing 5.9 g of AgNO ₃ and 320 ml of an aqueous solution (F) containing 5.82 g of KI were added over 5 minutes. Further, 350 m of an aqueous solution (G) containing 104.3 g of AgNO ₃
and a 25% aqueous solution of KI (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 the addition was completed, 1.4 g of KI and 4 mg of sodium ethylthiosulfonate were added, and 45 g of KI was added.
After keeping at 5 ° C. for 5 minutes, the temperature was lowered and desalting was performed according to a standard method. The resulting emulsion particles had an average equivalent spherical diameter of 0.3.
It was a hexagonal tabular grain having a particle diameter of 7 μm and an average particle aspect ratio of 5.8.

[0240] - tabular silver iodobromide emulsion 4-D (light-sensitive silver halide emulsion used in the present invention) - (H) outside of adding iron corresponding 8 × 10 ^-5 mol of potassium ferrocyanide in solution, It was prepared in the same manner as Comparative Emulsion 4-A. The obtained emulsion had almost the same average aspect ratio and average equivalent sphere diameter as Emulsion 4-C.

The chemical sensitization of these emulsions was carried out according to Comparative Emulsion 1-
A was performed in the same manner as in A. The amounts of the chloroauric acid, sodium thiosulfate, and selenium sensitizer were adjusted so as to increase the sensitivity by exposure to 1 / 10,000 seconds. Spectral sensitizing dyes and chemical sensitizers were varied in proportion to the grain surface area of each emulsion.

Comparative tabular silver iodobromide emulsions 1-A and 4-
A and 4-C, and the tabular silver iodobromide emulsions 1-C, 4-B, and 4-D for use in the present invention, the sensitizing dye was a sensitizing dye for a red-sensitive emulsion (a sensitizing dye for a red-sensitive emulsion). 1-A (r), 4-A
(R), 4-C (r), 1-C (r), 4-B (r),
Each emulsion of 4-D (r) was prepared. In addition, the tabular silver chlorobromide emulsions 1-A, 4-A and 4-C for comparison and the tabular silver bromoiodide emulsions 1-C, 4-B and 4-D of the present invention were increased. The sensitizing dye was changed to a sensitizing dye for blue-sensitive emulsion (sensitizing dye IV for blue-sensitive emulsion), and
(B), 4-A (b), 4-C (b), 1-C (b),
Emulsions 4-B (b) and 4-D (b) were prepared. 1-
The emulsions A, 4-A, and 4-C were used for the high-, middle-, and low-speed layers of a green-sensitive magenta color-forming layer, respectively, and used as 1-A (r) and 4-A (r). , 4-C (r) were used for a high-sensitivity layer, a medium-sensitivity layer and a low-sensitivity layer in a red-sensitive cyan color-forming layer, respectively.
The emulsions of 4-A (b) and 4-C (b) were respectively subjected to a high-sensitivity layer, a medium-sensitivity layer, and a blue-sensitive yellow-color-forming layer.
A multilayer photosensitive material (sample 401) shown in Tables 10 to 12 was prepared for the low-sensitivity layer. In addition, Tables 10 to 13 are obtained by dividing one table originally connected in this order into three.

[0243]

[Table 10]

[0244]

[Table 11]

[0245]

[Table 12]

[0246]

Embedded image

[0247]

Embedded image

[0248]

Embedded image

[0249]

Embedded image

A multicolor silver halide color photographic light-sensitive material of the present invention (Sample 402) was prepared in the same manner as in Sample 401 except that the emulsion in Sample 401 was changed as follows. That is, in the sample 401, 1-A, 4-A, 4-A
C is 1-C, 4-B and 4-D, respectively,
C, 4-B and 4-D emulsions were used for the high-, middle- and low-speed layers of the green-sensitive magenta color-forming layer, respectively. , 4-D (r) were used for a high-sensitivity layer, a medium-sensitivity layer, and a low-sensitivity layer in a red-sensitive cyan coloring layer, respectively, and 1-C (b),
The emulsions of 4-B (b) and 4-D (b) were respectively subjected to a high-sensitivity layer, a medium-sensitivity layer, and a blue-sensitive yellow-color-forming layer.
Used for the low sensitivity layer. Further, according to the method of preparing a coupler dispersion in Example 1, cyan and yellow coupler dispersions were also prepared. Further, a colorant dispersion was prepared by combining the above-mentioned yellow, magenta, and cyan leuco dyes with a zinc complex in order to form a colored layer capable of being decolorized during the heat development treatment.

The photographic characteristics of Sample 402 were tested in the same manner as in Example 1 except that the filter at the time of exposure was removed. That is, the sample 402 was first exposed through an optical wedge with a sensitometer MARKVII manufactured by EGG Corporation for 1/10000 second. On the photosensitive layer surface of the sample 402 after the exposure,
20 ml / m ² of hot water at 0 ° C. was applied to the first treated material P
After superimposition with the processing layer surface in No.-3, heat development was performed at 83 ° C. for 30 seconds using a heat drum. Thereafter, the sample 402 is peeled from the processing material P-3, and the sample 40 is removed.
2 was subjected to a second treatment using a second treatment material P-2. In the second treatment, 15 cc / m ² of water is applied to the treatment layer surface of the second treatment material P-2, and the treatment layer surface and the photosensitive layer surface of the sample 402 after the first treatment are applied. They were bonded together and heated at 60 ° C. for 30 seconds. The image of the sample 402 thus processed was measured for the transmission density of a wedge-shaped image of yellow, magenta, and cyan using a blue, green, and red filter to obtain a characteristic curve. The processing material P-3 had a guanidine picolinate content of 4500 mg / m2.
Except for replacing with ² , the same as the processing material P-1 in Example 1. As in Example 1, the fog density was 0.15
The reciprocal of the exposure amount corresponding to the high density was defined as relative sensitivity, the sensitivity value of sample 401 was set to 100, and the sensitivity of sample 402 was expressed as a relative value of the sensitivity value of sample 101. Table 13 shows the results.

[0252]

[Table 13]

From the results shown in Table 13, as in Example 1, the multilayer / multicolor silver halide color photographic light-sensitive material of the present invention (sample 402) has high sensitivity and little image unevenness. The effect of the invention was recognized.

Example 5 In the sample 401, the medium- and low-sensitivity layers of the blue-sensitive yellow coloring layer, the green-sensitive magenta coloring layer, and the red-sensitive cyan coloring layer were removed, and the green photosensitive layer was removed. Emulsion 3-
A-emulsion 3-A (r), which is the same as emulsion 3-A except that a sensitizing dye for a red-sensitive emulsion is used in emulsion 3-A for the high-sensitivity layer in the red-sensitive cyan coloring layer using A Emulsion 3-A (b) which is the same as Emulsion 3-A except that a sensitizing dye for a blue-sensitive emulsion is used in Emulsion 3-A in a high-sensitivity layer in a blue-sensitive yellow color-forming layer. ) Was used to produce a multilayer photosensitive material (sample 501). Next, emulsion 3-D (r) which is the same as emulsion 3-D except that a sensitizing dye for a red-sensitive emulsion was used in emulsion 3-D, and a sensitizing dye for a blue-sensitive emulsion in emulsion 3-D Is the same as Emulsion 3-D except that Emulsion 3-D was used, and in the same manner as in Example 3 except that Emulsion 3-D was used, the silver halide color photographic light-sensitive material of the present invention ( Sample 502) was produced. When these samples were processed in the same manner as in Example 4, the silver halide color photographic light-sensitive material of the present invention (sample 502) was found to have the effect of the present invention that it had high sensitivity and little image unevenness. On the other hand, photosensitive material (sample 501)
No effect of the present invention was observed.

Example 6 A sample was prepared in the same manner as in the multilayer sample 402 prepared in Example 4, except that the support (transparent PET base) was replaced by a support manufactured by the following method. When a test similar to that of Example 4 was performed on this sample,
The same results as those of the sample 402 can be obtained, and by using metal ions and / or metal complex ions that are shallow electron traps, the present invention provides a high sensitivity and little image unevenness in a developing agent built-in system. The effect was confirmed.

The support used in Example 6 was produced by the following method. 100 parts by weight of polyethylene-2,6-naphthalate polymer and Tinuvin as an ultraviolet absorber
After drying 2 parts by weight of P.326 (manufactured by Ciba Geigy),
After melting at 300 ℃, extrude from T-die, 140 ℃
, And then stretched 3.3 times at 130 ° C.
Double stretching was performed twice, followed by heat setting at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. This PE
The N film has a blue dye, a magenta dye and a yellow dye (Publication Technical Report: I- described in Japanese Patent Publication No. 94-6023).
1, I-4, I-6, I-24, I-26, I-27, II-5) were added in appropriate amounts. Furthermore, it is wound around a stainless steel core having a diameter of 20 cm, and
A heat history of 10 ° C. for 48 hours was given to make the support less likely to have curl.

The support was subjected to a corona discharge treatment, a UV discharge treatment, and a glow discharge treatment on both surfaces thereof, and then each surface was provided with gelatin 0.1 g / m ² and sodium α-sulfodi-2-ethylhexyl. Succinate 0.
01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂
CH ^₂ 0.012g / m _2, polyamide - by applying the undercoating liquid epichlorohydrin polycondensate 0.02g / m ² (1
0 cc / m ² , using a bar coater) and an undercoat layer was provided on the high temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

An antistatic layer, a transparent magnetic recording layer, and a sliding layer having the following composition were provided as a back layer on one surface of the support after the undercoating.

-Coating of Antistatic Layer-Tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm, a dispersion of fine powder having a specific resistance of 5 Ω · cm (secondary aggregated particle diameter: about 0.08 μm) the 0.2 g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2
0.02 g / m ^2, and poly (polymerization degree 10) oxyethylene -p- nonylphenol 0.005 g / m ² and resorcin was applied.

Coating of Transparent 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 0.14 μm, single axis 0.03 μm, saturation magnetization 89 emu
/ G, Fe ²⁺ / Fe ³⁺ = 6/94, the surface of which is treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06
g / m ² , diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was carried out using an open kneader and a sand mill), and C ₂ H ₅ C (CH ₂ CONH-C ₆ H ₃ (CH ₃ )) as a curing agent NCO)
_The solution was applied with a bar coater using 0.3 g / m ² of 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
H81 50 mg / m ² , silica particles as matting agent (1.
0 μm) and 3-poly (degree of polymerization 15) oxyethylene-
Abrasive aluminum oxide (0.20 μm and 1.0 μm) coated with propyloxytrimethoxysilane (15% by weight) and 50 mg / m ² and 10 mg respectively
/ M ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 11 ° C.).
5 ° C.). X- light (blue filter) magnetic recording layer of the D color density increment of about 0.1 to ^B in addition,
The saturation magnetization moment of the magnetic recording layer is 4.2 emu / g,
The coercive force was 7.3 × 10 ⁴ A / m, and the squareness ratio was 65%.

Coating of Sliding Layer Hydroxyethylcellulose (25 mg / m ² ), C ₆ H
₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (6 mg / m ² ) and silicone oil BYK-310 (Big Chemie Japan Co., Ltd.)
1.5 mg / m ² was applied. This mixture was melted at 105 ° C. in xylene / propylene glycol monomethyl ether (1/1), poured into and dispersed in propylene monomethyl ether (10-fold amount) at room temperature, and then dispersed in acetone. (Average particle size: 0.01 μm). Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were kept at 115 ° C.). The sliding layer has a dynamic friction coefficient of 0.10 (5 mmφ stainless steel hard ball, load 100 g, speed 6 cm / min)
The coefficient of static friction was 0.08 (clip method), and the coefficient of kinetic friction between the emulsion surface described below and the slipping layer was 0.15, indicating excellent characteristics.

[0262]

According to the present invention, the above-mentioned conventional problems can be solved. Further, according to the present invention, a silver halide color for photographing high quality images which has a low environmental load, is suitable for image formation by simple and quick processing, is highly sensitive, and has no image unevenness during development processing. A photographic light-sensitive material can be provided. Further, according to the present invention, there is provided a color image forming method capable of forming a high-quality image easily and quickly without unevenness by reducing the burden on the environment by using the silver halide color photographic light-sensitive material. can do.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 8/40 502 G03C 8/40 502

Claims (4)

[Claims] 1. A photosensitive silver halide emulsion on a support,
Developing agent, a compound forming a dye by a coupling reaction with an oxidized form of the developing agent, and a photographic component layer including at least one photosensitive layer containing a binder, and after exposure, the The total amount of water required for the maximum swelling of the coating film and the coating film of the processing material obtained by coating the constituent layer including the processing layer containing the base and / or the base precursor on the support is 1/10 to 1 to 1 A double amount of water is supplied to the photosensitive layer surface or the processing layer surface of the processing material, and the photosensitive layer surface and the processing layer surface are bonded to each other and heated and developed to form a silver halide color photograph. In the light-sensitive material, the light-sensitive silver halide emulsion contains at least one selected from metal ions and metal complex ions that are electron traps having a depth of 0.6 eV or less. Te becomes, the silver halide color photographic material having an average aspect ratio characterized in that it contains at least one tabular grain is 4-100. 2. The method according to claim 1, wherein the metal ions and the metal complex ions, which are electron traps having a depth of 0.6 eV or less, include Pb ions, ions containing a cyan ligand and Re, Os, Ru, Fe, Ir, or Co; 2. The silver halide color photographic light-sensitive material according to claim 1, which is an ion containing a halogen ion ligand or a thiocyanate ion ligand and Ir or Pd. 3. The method according to claim 1, wherein the developing agent is represented by the following general formula I:
3. The silver halide color photographic light-sensitive material according to claim 1, which is represented by any one of formulas II, III and IV. Embedded image Embedded image Embedded image Embedded image In the general formulas I to IV, 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, an alkoxy group, an aryl group. Oxy, alkylthio, arylthio, alkylcarbamoyl, arylcarbamoyl, carbamoyl, alkylsulfamoyl, arylsulfamoyl, sulfamoyl, cyano, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl, Represents an aryloxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group or an acyloxy group. R ₅ represents an alkyl group, an aryl group or a heterocyclic group. Z represents a group of atoms forming a (hetero) aromatic ring;
Is a benzene ring, the total value of Hammett constant (σ) of the substituent is 1 or more. R ₆ represents an alkyl group. X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom.
R ₇ and R ₈ represent a hydrogen atom or a substituent. R ₇ and R ₈ may be bonded to each other to form a double bond or a ring. Further, each of the general formulas I to IV has at least one ballast group having 8 or more carbon atoms in order to impart oil solubility to the molecule. 4. After exposing a silver halide color photographic light-sensitive material, said silver halide color photographic light-sensitive material is
Water of 1/10 to 1 times the total water amount required for the maximum swelling of the entire coating film in the processing material obtained by coating the constituent layer including the processing layer containing the base and / or the base precursor on the support. Forming a color image by supplying the photosensitive layer surface in the silver halide color photographic light-sensitive material or the processing layer surface in the processing material, bonding the photosensitive layer surface and the processing layer surface, and developing by heating. 4. A color image forming method according to claim 1, wherein said silver halide color photographic light-sensitive material is the silver halide color photographic light-sensitive material according to claim 1.