JPH11119397A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photographic sensitive material having high sensitivity and a good discrimination with little fog even in a simple and rapid process. SOLUTION: This material has at least one emulsion layer described below and a nonphotosensitive layer on a supporting body. The emulsion layer consists of (1) a developing agent, a compd. which forms a dye by the coupling reaction with an oxidizing agent in the developing agent, or (2) a color material, which releases or diffuses a diffusive dye corresponding to or reversely corresponding to silver development, and a photosensitive silver halide emulsion and a binder. At least one kind of photosensitive silver halide emulsion consists of planer silver halide particles having 0.5 to 20 mol.% average silver iodide content, 0.01 to 0.3 μm average particle thickness. At least one emulsion layer contains at least one kind of mercapto compd. having >=0.6 logarithm of the proportion (distribution coefft.) of solubility with butanol to the solubility with water at 25 deg.C and pH 11.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel heat-developable silver halide color photographic light-sensitive material for recording an image (hereinafter sometimes simply referred to as "light-sensitive material").

[0002]

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

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

For such a classic image forming method,
Recently, image information recorded on a color negative has been converted into digital information by a scanner, and various image processes have been performed on the image information, thereby making it possible to improve the image quality of the resulting print. In fact, minilab systems incorporating this technology have also been announced. Under such circumstances, there is an increasing demand for a color negative image forming method that is simpler. First,
The processing bath for performing the color development, bleaching and fixing described above requires precise control of the composition and temperature thereof.
Requires specialized knowledge and skilled operation. Second, these processing solutions contain substances that must be environmentally regulated, such as color developing agents and iron chelates, which are bleaching agents. Equipment is often required. Third, although the development process has been shortened in recent years, these development processes require time and are still inadequate for the demand for quickly reproducing a recorded image.

[0005] From such a background, there is a demand for reducing the environmental load and improving simplicity by constructing a system that does not use a color developing agent or a bleaching agent used in current color image forming systems. Is growing more and more. In view of these viewpoints, many improved techniques have been proposed. For example, IS &T's 48th Annual Con
On page 180 of ference Proceedings, the dye generated in the development reaction is transferred to the mordant layer and then removed to remove developed silver and unreacted silver halide. A system is disclosed that eliminates the need for a bath. However, the technology proposed here still requires development processing in a processing bath containing a color developing agent, and it cannot be said that environmental problems have been solved.

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

On the other hand, Japanese Patent Application Laid-Open Nos. 9-10506 and 9-34077 disclose heat-development negatives which can be processed simply, quickly and with less environmental load. Since this system is a photographic material, the silver halide emulsion used has been required to have even higher sensitivity. One of the techniques for sensitizing silver halide emulsions is to use tabular grains. The technique of using tabular grains in a heat development system is disclosed in U.S. Pat. No. 4,435,49.
9, JP-B-2-48101, JP-A-61-7704
No. 8, JP-A-62-78555, JP-A-62-794
No. 47. In conventional liquid development photographic systems, tabular grains have already been disclosed in U.S. Pat.
No. 34,226, No. 4,439,520, No. 4,
414,310, 4,433,048, 4,414,306, 4,459,353 JP-A-59-99433, JP-A-62-209445 and the like. Techniques are disclosed. More recently,
European Patent Nos. 0701164A, 0699945A, 06999948A, 06999946A, 069946A, and 06946 regarding the technology for using thin tabular grains having a small average grain thickness of less than 0.07 μm (referred to as ultrathin tabular grains).
No. 9949A, No. 0699951A, No. 069995
Nos. 0A and 0699947A; U.S. Pat.
Nos. 1, 503,970 and 5,494,789, JP-A-8-101476, JP-A-8-101475, and 8-1
No. 01473, No. 8-101472, No. 8-1014
Nos. 74 and 8-69069.

However, in view of the above points, a heat-developing silver halide color photographic light-sensitive material incorporating a color developing agent, which is a photographic material with a low environmental load and capable of simple and rapid image recording, has been developed. Investigations on the use of tabular grains described in Table 1 above revealed that tabular grain emulsions tended to cause fogging, and in particular, when the grain thickness was reduced, high fog was generated, which was insufficient to obtain practical discrimination. It is an essential design requirement for the imaging material to achieve both high sensitivity and low fog, and an imaging material capable of forming an image with low fog and high sensitivity even in a simple, quick, and low-environment process is desired. I was

[0009]

SUMMARY OF THE INVENTION As described above, an object of the present invention is to provide a color photographic light-sensitive material capable of forming an image easily, quickly and with less environmental load. Another object of the present invention is to provide an excellent color photographic light-sensitive material which can provide high sensitivity even with simple and rapid processing and can give good discrimination with less fog.

[0010]

The above objects of the present invention have been effectively achieved by the following present invention. That is, the present invention provides: 1) a photosensitive silver halide emulsion, a color developing agent, a compound capable of forming a dye by a coupling reaction with an oxidized form of the color developing agent, and a binder comprising at least one layer of a photosensitive halogen comprising a binder; In a light-sensitive material provided with a silver halide emulsion layer and a non-light-sensitive layer, at least one of the light-sensitive silver halide emulsions has an average silver iodide content of 0.5.
Mol% or more and 20 mol% or less, comprising tabular silver halide grains having an average grain thickness of 0.01 to 0.3 μm, and further comprising at least one photosensitive silver halide emulsion layer in the photosensitive material. At a temperature of 25 ° C., pH =
11. A silver halide color photographic light-sensitive material containing at least one mercapto compound having a common logarithm of the ratio (partition coefficient) of the dissolution concentration in butanol to the dissolution concentration in water in No. 11 which is 0.6 or more. It is.

2) a photosensitive silver halide emulsion on a support,
In a light-sensitive material comprising at least one light-sensitive silver halide emulsion layer and a non-light-sensitive layer comprising a coloring material and a binder which release or diffuse a diffusible dye corresponding to or reverse to silver development, At least one of the silver halide emulsions has an average silver iodide content of 0.5 mol% or more;
0 mol% or less, comprising tabular silver halide grains having an average grain thickness of 0.01 to 0.3 .mu.m, and at least one of the photosensitive silver halide emulsion layers in the light-sensitive material having a temperature of 25.degree. At least one mercapto compound having a common logarithm of a ratio (distribution coefficient) of a dissolution concentration in butanol to a dissolution concentration in water at pH = 11 of 0.6 or more at 0.6 ° C. It is a silver color photographic light-sensitive material.

3) The mercapto compound is characterized in that the common logarithm of the ratio (partition coefficient) of the concentration dissolved in butanol to the concentration dissolved in water at pH = 11 at a temperature of 25 ° C. is 0.9 or more. The silver halide photographic color photographic material according to 1) or 2). 4) The silver halide color photographic material described in 1) or 2), wherein the mercapto compound is a compound represented by the following formula (1) or (2).

[0013]

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In the formula, Ra and Rb represent an alkyl group, an alkenyl group, an aralkyl group, an aryl or a heterocyclic group. However, the total number of carbon atoms of Ra and Rb is 14 or more. M represents a hydrogen atom, an ammonium or an alkali metal atom. Rc represents an aryl group. However, Rc has 10 or more carbon atoms.

5) The tabular silver halide grains are epitaxial silver halide grains having at least one type of silver salt epitaxy formed on the surface of a host tabular grain, or tabular silver halide grains having dislocation lines. The silver halide color photographic light-sensitive material according to any one of 1) to 4), wherein 6) The color developing agent according to any one of 1), 3) to 5), wherein the color developing agent is at least one compound represented by the following general formulas (3) to (7). It is a silver halide color photographic material.

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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In the formula, R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
Alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyl group, R ₅ represents an alkyl group, an aryl group or a heterocyclic group; Z represents a group of atoms forming an aromatic ring (including a heteroaromatic ring). When Z is a benzene ring, the total value of Hammett constant (σ) of the substituent is 1 or more. R ₆ represents an alkyl group. X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom. R ₇ and R ₈ represent a hydrogen atom or a substituent, and R ₇ and R ₈ may combine with each other to form a double bond or a ring.

7) The silver halide color photographic light-sensitive material as described in any one of 1) to 6) above, wherein the average grain thickness of the tabular silver halide grains is 0.01 to 0.2 μm. is there. 8) The average grain thickness of the tabular silver halide grains is 0.0
1) to 6) characterized in that the thickness is 1 to 0.1 μm.
The silver halide color photographic light-sensitive material according to any one of the above. 9) The mercapto compound is contained in an emulsion layer containing tabular silver halide grains.
8) The silver halide color photographic light-sensitive material as described in any of 8) above.

10) The light-sensitive material contains a dye which is decolorized by a reaction with a decoloring agent at the time of development processing, and the dye is diffusion-resistant. 1) to 9) characterized by diffusion resistance
The silver halide color photographic light-sensitive material according to any one of the above. 11) After the photosensitive material is exposed, a processing material in which a constituent layer including a processing layer containing a base and / or a base precursor is coated on a support, and all coating films except for a back layer of both the photosensitive material and the processing material Water equivalent to 1/10 to 1 times the total amount of water required for the maximum swelling of the photosensitive material between the photosensitive silver halide emulsion layer surface of the photosensitive material and the processing layer surface of the processing material, Any one of 1) to 10), wherein an image is formed by bonding the surface of the silver halide emulsion layer and the processing layer of the processing material and heating at a temperature of 60 ° C. to 100 ° C. for 5 seconds to 60 seconds. Described above.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to construct a photosensitive material used for recording an original scene and reproducing it as a color image in the present invention, color reproduction by a subtractive color method can be basically used. That is, at least three types of photosensitive silver halide emulsion layers (photosensitive layers) having photosensitivity in the blue, green, and red regions are provided, and each photosensitive layer has a complementary color relationship with its own photosensitive wavelength region. The color information of the original scene can be recorded by incorporating a color coupler capable of forming yellow, magenta and cyan dyes. The ornamental image can be reproduced by exposing the color image having the same relationship between the photosensitive wavelength and the color hue through the dye image thus obtained. Further, information of a dye image obtained by photographing an original scene can be read by a scanner or the like, and an ornamental image can be reproduced based on this information.

It is also possible to provide a relationship other than the above-described complementary color between the photosensitive wavelength region and the color hue. In such a case, the original color information can be reproduced by performing image processing such as hue conversion after capturing the image information as described above. As the light-sensitive material of the present invention, a light-sensitive layer having photosensitivity in three or more wavelength regions can be provided.

In a color negative film used in conventional photography, a silver halide emulsion is improved in order to achieve a desired granularity, while a developing reaction is carried out during a coupling reaction with an oxidized form of a developing agent. Techniques such as using so-called DIR couplers that release inhibitory compounds have been incorporated. In the photosensitive material of the present invention,
Excellent granularity is obtained even without using a DIR coupler. In addition, the combination of the DIR compounds results in increasingly better granularity.

In the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention, at a temperature of 25 ° C., a common logarithm of a ratio (partition coefficient) of a dissolution concentration in butanol to a dissolution concentration in distilled water at pH = 11 is used. Is required to contain at least one mercapto compound having a value of 0.6 or more. Conventionally, various mercapto compounds have been incorporated into photographic light-sensitive materials for the purpose of preventing fog or stabilizing performance during storage. However,
In a system for forming an image of a photosensitive material containing a developing agent therein at high temperature and in a short time as in the present invention, it has been difficult to obtain sufficient discrimination with a generally known antifoggant. That is, a fogging inhibitor having a weak development suppression and a small desensitizing effect does not sufficiently prevent fogging during high-temperature development, while a compound exhibiting a sufficient antifogging effect even at high-temperature development tends to impair the sensitivity. Was. As a result of intensive studies by the present inventors, the improvement of discrimination when developing a photosensitive material containing a developing agent at a high temperature and in a short time, at a temperature of 25.degree.
The common logarithm of the ratio (partition coefficient) of the dissolved concentration in butanol to the dissolved concentration in distilled water at H = 11 is 0.6.
It has been found that the above mercapto compounds exhibit specifically excellent effects.

The mercapto compound used in the present invention is
The common logarithm of the distribution coefficient is 0.6 or more, preferably 0.9 or more.

In the present invention, the common logarithm of the distribution coefficient is determined as described below. Brit prepared using 50 ml of an n-butanol solution of a mercapto compound to be measured (2 × 10 ⁻⁴ mol / l) and distilled water
on-Robinsonbuffer (pH = 11) 5
After mixing with 0 ml and shaking at room temperature for 10 minutes with a shaker, the mixture was allowed to stand and separated to separate an n-butanol phase (solution A) and an aqueous phase (solution B). Extracted solution A and solution B
-Dilute to 100 ml with butanol and buffer solution,
The concentrations of the two were measured at a measurement temperature of 25 ° C. using a spectral absorption measurement method or an HPLC measurement method, and the common logarithm (log P ′) of the distribution coefficient was determined by the following equation. logP ′ = log ([concentration of butanol phase] / [bu
concentration of ffer phase])

The mercapto compound used in the present invention is
It is represented by the following general formula (8).

[0031]

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In the above formula, Z represents an atomic group necessary for forming a heterocyclic ring with C. Examples of the heterocyclic ring include an oxazole ring, a thiazole ring, an imidazole ring,
Selenazole ring, triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring, pentazole ring, pyrimidine ring, thiazine ring, triazine ring, thiadiazine ring, or a ring bonded to another carbon ring or hetero ring, such as a benzoxazole ring Benzothiazole ring, benzoselenazole ring, benzimidazole ring, naphthoxazole ring, triazeindolizine ring, diazaindolizine ring, and triazaindolizine ring. M ₁ represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group or a quaternary phosphonium group.

The heterocyclic ring formed by Z together with C may have a substituent. As such a substituent, for example,
Hydroxyl group, alkyl group, aralkyl group, aryl group, halogen group (fluorine, chlorine, bromine, iodine), nitro group, cyano group, heterocyclic group, alkenyl group, alkoxy group, -SO
₃ M ₂ group, -COOR group, -NR ₁ R _2, -CONR ₁
R ₂ groups, —NHSO ₂ R ₁ groups, —SO ₂ NR ₁ R ₂ groups, and the like. M ₂ is a hydrogen atom, an alkali metal atom,
Represents quaternary ammonium or quaternary phosphonium;
Is a hydrogen atom, an alkali metal atom, a quaternary ammonium,
Quaternary phosphonium, alkyl group, aralkyl group, aryl group, -COR ₃ group, -COOR ₃ group, or -SO ₂
Represents an R ₃ group, and R ₃ represents a hydrogen atom, an aliphatic group, or an aromatic group, and these groups may further have a substituent. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, —OR ₃
A group, —COOR ₃ group, or —SO ₂ R ₃ group,
₃ represents a hydrogen atom, an aliphatic group, or an aromatic group, and these groups may further have a substituent. These substituents may have one or more, or may have several kinds. As a substituent, for example, a phenyl group,
A benzyl group and a naphthyl group are preferable, and these substituents may include an alkyl group, a —NHCOR ₄ group, and a —CONHR ₄ group (R ₄ is an alkyl group).

Below, at a temperature of 25 ° C., pH = 11
Specific examples of the mercapto compound in which the common logarithm of the ratio (partition coefficient) of the dissolved concentration in butanol to the dissolved concentration in water is 0.6 or more are shown, but the present invention is of course not limited thereto.

[0035]

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[0036]

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[0037]

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[0038]

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In the present invention, at a temperature of 25 ° C., p
Among the mercapto compounds having a common logarithm of the ratio (partition coefficient) of the dissolution concentration in butanol to the dissolution concentration in water at H = 11 of 0.6 or more, particularly preferred is represented by the following general formula (1). Or a mercaptotetrazole compound represented by the general formula (2).

[0040]

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In the formula, Ra and Rb are substituted or unsubstituted,
Alkyl group (butyl, hexyl, octyl, decyl group, etc.), alkenyl group (butenyl, octenyl group, etc.),
R is selected from aralkyl groups (such as benzyl and phenethyl groups), aryl groups (such as phenyl, biphenyl, amidophenyl, phenoxyphenyl, naphthyl and anthracenyl groups) and heterocyclic groups (such as pyridyl and thienyl groups);
The total number of carbon atoms of a and Rb is 14 or more. Further, it preferably has an aromatic ring, and more preferably, the aromatic ring is directly connected to the triazole ring. M is a hydrogen atom,
Represents an ammonium or alkali metal atom. Rc is a substituted or unsubstituted aryl group (phenyl, naphthyl group, etc.), and the substituent is butyl, pentyl, hexyl, nonyl group-substituted carbamoyl group, similar alkyl-substituted amide group, alkylcarboxylate group Or an alkyl-substituted ureido group, but the total number of carbon atoms is 10 or more. Further, it is preferable that an aromatic ring is directly connected to the tetrazole ring.

The mercapto compound used in the present invention is
It can be synthesized with reference to the following literature. U.S. Pat. Nos. 2,585,388 and 2,541,924
No., JP-B-42-21,842, JP-A-53-50,
169, British Patent No. 1,275,701; A.
Burgess et al., “Journal of Heterocyclic Chemistry” (DABerges et.al., “Journal of Het”
erocyclic Chemistry ") Vol. 15 No. 981 (1978)
No.), “The Chemistry of Heterocyclic.
Chemistry ", Imidazole and Derivatives, Part I (" The Chemistry of Heterocyclic Chem
istry "Imidazole and Derivatives part I), 336
-9 pages, Chemical Abstract (Chemical Abstrac)
t), 58, 7921 (1963), p.
Hogarth, "Journal of Chemical Societty" (E. Hoggarth "Journal of Chemical Societty" 1
160-7 (1949); R. Saudler W. Caro, “Organic Functional Group Preparation”, Academic Press (S.
R. Saudler, W. Karo, “Organic Fanctional Group Prepa
ration ”Academic Press, pages 312-5 (1968),
M. Shamdom et al. (M. Chamdon, et.al.,), Burtan
De la societe simique de france (Bulletin
de la Societe Chimique de France), 723 (19
54); A. Shirley, D. W. Array, Journal of the American Chemical Society (DAShirley, DWAlley, J. Amer. Chem. Soc.), 79,
4922 (1954); Ball, W. Marchch, A. Wohl, W. Marchwald, Ber. (German Chemistry), 22, 568 (1889), Journal of American Chemical Society (J. Amer. C)
hem. Soc.), 44, 1502-10, U.S. Pat.
017,270, British Patent No. 940,169, JP-B-49-8,334, JP-A-55-59,463,
Advanced in Heterocyclic Chemistry, West German Patent No. 2,716,707, The Chemistry of Heterocyclic Chemistry, The Chemistry of Heterocyclic Chemistry
Conpounds Imidazole and Derivatives) Vol. 1,
385, Organic Synthesis IV.,
569 (1963), Belitzite (Ber.) 9, 465
(1976), Journal of American Chemical Society (J. Amer. Chem. Soc.) 45, 2390
(1923), JP-A-50-89034, and JP-A-53-2
No. 8426, No. 55-21007, Japanese Patent Publication No. 40-28
No. 496.

The amount of the mercapto compound used in the present invention is in the range of 10 ^-6 to 10 ^-1 mol, preferably 5 × 10 ^-5 to 1 mol per mol of silver halide in the added emulsion layer.
Within the range of 5 × 10 ⁻² mol, more preferably 5 × 10 ⁻² mol.
^{-4 to} 5 × 10 ^-3 mol.

The method of adding the mercapto compound to the emulsion layer may be in accordance with the usual method of adding a photographic emulsion additive.
For example, it can be dissolved in methyl alcohol, ethyl alcohol, water, methylpropyl glycol, or a mixed solvent thereof, and added as a solution. Further, the solution may be concentrated by adding an acid, an alkali or the like.

The above-mentioned mercapto compound can be added at any stage in the production process of a photographic emulsion, or at any stage immediately after the emulsion production and immediately before coating. Preferably, when preparing the coating liquid,
Before, during, or after chemical sensitization, and after the addition of the sensitizing dye.

Next, the emulsion of the present invention will be described.

In the present invention, tabular grains (hereinafter referred to as "tabular grains") are silver halide grains having two opposing parallel main planes.

In the present invention, the tabular grains have one twin plane or two or more parallel twin planes.

The twin plane is defined as (111) when ions at all lattice points on both sides of the (111) plane are in a mirror image relationship.
Surface.

In the tabular grains of the present invention, the twin plane spacing is 0.012 as described in US Pat. No. 5,219,720.
μm or less, or as described in JP-A-5-249585, the ratio of (111) interplanar distance / twin plane spacing may be 15 or more.

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

In the emulsion of the present invention, the projected area of tabular grains preferably accounts for 100 to 50% of the total projected area of all grains, more preferably 100 to 80%, particularly preferably 100 to 90%.

If it is less than 50%, the advantages of tabular grains (improvement in sensitivity / granularity ratio and sharpness) cannot be fully utilized, which is not preferable.

The average grain thickness of the tabular grains in the present invention is from 0.01 to 0.3 μm, more preferably from 0.01 to 0.2 μm, even more preferably from 0.0 to 0.3 μm.
It is 1 to 0.1 μm, particularly preferably 0.01 to 0.07 μm. The average grain thickness is the arithmetic average of the grain thickness of all tabular grains in the emulsion.

If the average particle thickness is less than 0.01 μm, the pressure property is undesirably deteriorated. If it exceeds 0.3 μm, it is difficult to obtain the effects of the present invention, which is not preferable.

The average equivalent circle diameter of the tabular grains in the present invention is preferably 0.3 to 5 μm, more preferably 0.4 to 4 μm, and particularly preferably 0.5 to 3 μm.

The average equivalent circle equivalent diameter is the arithmetic mean of the equivalent circle equivalent diameters of all tabular grains in the emulsion.

If the average equivalent circle diameter is less than 0.3 μm, the effects of the present invention are hardly obtained, which is not preferable. If the thickness exceeds 5 μm, the pressure property deteriorates, which is not preferable.

The ratio of the equivalent circle equivalent diameter to the thickness of silver halide grains is called the aspect ratio. That is, it is a value obtained by dividing the equivalent circle diameter of the projected area of each silver halide grain by the grain thickness.

As an example of the method of measuring the aspect ratio, there is a method in which a transmission electron micrograph is taken by a replica method to determine the diameter (equivalent circle equivalent diameter) and thickness of a circle having an area equal to the projected area of each particle. is there. In this case, the thickness is calculated from the length of the shadow of the replica.

The emulsion of the present invention preferably has an average aspect ratio to all tabular grains of 2 to 100, more preferably 5 to 80, and still more preferably 8 to 100.
To 50, particularly preferably 12 to 50. The average aspect ratio is the arithmetic average of the aspect ratios of all tabular grains in the emulsion.

If the average aspect ratio is less than 2, the advantages of tabular grains cannot be fully utilized, which is not preferable. If it exceeds 100, the pressure property deteriorates, which is not preferable.

In the present invention, the grain thickness and the aspect ratio in the above ranges may be selected according to the purpose, but it is preferable to use tabular grains having a small grain thickness and a high aspect ratio.

Various methods can be used for forming tabular grains. For example, US Pat.
No. 789 can be used. In order to form tabular grains having a high aspect ratio, it is important to generate twin nuclei having a small size. Low temperature,
It is preferable to form nuclei in a short period of time at a high pBr, a low pH, and a low gelatin amount. As a kind of gelatin, a low molecular weight gelatin, a low methionine content, and a phthalated gelatin are preferable. After nucleation, only tabular grain nuclei (parallel multiple twin nuclei) are grown by physical ripening, and other normal crystal nuclei, single twin nuclei, and non-parallel multiple twin nuclei are eliminated, and parallel multiplexing is selectively performed. Leave twin nuclei. Thereafter, a soluble silver salt and a soluble halogen salt are added and the grains are grown to prepare an emulsion composed of tabular grains. It is also preferable to add silver halide fine particles separately prepared in advance or simultaneously prepared in another reaction vessel to supply silver and halide to grow the grains.

In the emulsion of the present invention, hexagonal tabular grains having a ratio of the length of the longest side having the maximum length to the length of the shortest side having a minimum length of 2 to 1 are contained in the whole emulsion. It preferably occupies 100 to 50% of the projected area of the grain, more preferably 100 to 70%, particularly preferably 100 to 90%. Mixing of tabular grains other than the above hexagons is not preferred in terms of homogeneity between grains. The emulsion of the present invention is preferably monodisperse.

In the present invention, the variation coefficient of the grain size distribution of the projected area of all silver halide grains is preferably 35% or less, more preferably 25 to 3%, and particularly preferably 20 to 3%. . If it exceeds 35%, it is not preferable in terms of homogeneity between particles.

The variation coefficient of the grain size distribution is a value obtained by dividing the variation (standard deviation) of the equivalent sphere diameter of each silver halide grain by the average equivalent sphere diameter.

The tabular grains in the present invention include silver bromide,
Silver chlorobromide, silver iodobromide, silver iodochloride, silver chloride, silver chloroiodobromide and the like can be used, but silver bromide, silver iodobromide and silver chloroiodobromide are preferably used.

When there is a phase containing iodide or chloride, these phases may be uniformly distributed or localized in the grains.

Other silver salts, for example, rhodan silver, silver sulfide,
Silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as part of silver halide grains.

The preferred range of the average silver iodide content of the tabular grains in the present invention is 0.5 to 20 mol%, more preferably 1.0 to 15 mol%, particularly preferably 2.0 to 10 mol%. It is.

If the amount is less than 0.5 mol%, it is difficult to obtain effects such as enhancement of dye adsorption and increase in intrinsic sensitivity, which is not preferable. 20
If it exceeds mol%, the developing speed is generally slow, which is not preferable.

The coefficient of variation of the intergranular silver iodide content distribution of the tabular grains in the present invention is preferably 30% or less, more preferably 25 to 3%, and particularly preferably 20 to 3%. If it exceeds 30%, it is not preferable in terms of homogeneity between particles.

The silver iodide content of each tabular grain can be measured by analyzing the composition of each grain using an X-ray microanalyzer.

The coefficient of variation of the silver iodide content distribution is a value obtained by dividing the standard deviation of the silver iodide content of each grain by the average silver iodide content.

The tabular grains in the present invention may have dislocation lines. A dislocation line is a linear lattice defect on the slip plane of a crystal at the boundary between an already slipped region and a region that has not yet slipped.

Regarding the dislocation lines of the silver halide crystal,
1) C.I. R. Berry, J.M. Appl. Phys. ,
27, 636 (1956), 2) C.I. R. Berry,
D. C. Skilman, J .; Appl. Phys. ,
35, 2165 (1964), 3) J.I. F. Hamil
ton, Photo. Sci. Eng. , 11,57 (1
967), 4) T.I. Shiozawa, J .; Soc. P
hot. Sci. Jap. , 34, 16 (1971),
5) T. Shiozawa, J .; Soc. Photo. S
ci. Jap. , 35, 213 (1972), which can be analyzed by an X-ray diffraction method or a direct observation method using a low-temperature transmission electron microscope.

When dislocation lines are directly observed using a transmission electron microscope, the silver halide grains taken out of the emulsion are carefully examined so as not to apply enough pressure to generate the dislocation lines. Then, observation is performed by a transmission method in a state where the sample is cooled so as to prevent damage (for example, printout) by an electron beam.

In this case, the thicker the particle, the more difficult it is for the electron beam to pass. Therefore, it is necessary to use a high-pressure electron microscope (200 kV or more for a thickness of 0.25 μm) to observe the image more clearly. Can be.

JP-A-63-220238 describes a technique for introducing dislocation lines into silver halide grains while controlling the dislocation lines.

It has been shown that tabular grains into which dislocation lines are introduced have superior photographic properties such as sensitivity and reciprocity law as compared with tabular grains without dislocation lines.

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

In the case where the tabular grains in the present invention have dislocation lines, their positions can be selected from, for example, those limited to the apexes and fringe parts of the grains or introduced over the entire main plane part, and can be arbitrarily selected. However, it is particularly preferable to limit to the fringe portion.

The fringe portion in the present invention refers to the outer periphery of a tabular grain. More specifically, in the distribution of silver iodide from the side to the center of the tabular grain, the silver iodide-containing point at the first point when viewed from the side is considered. Outside the point where the ratio exceeds or falls below the average silver iodide content of the whole grain.

When dislocation lines are introduced into the tabular grains of the present invention,
For example, it is preferable to form silver halide grains while rapidly generating iodide ions as described in US Pat. No. 5,496,694. In particular, US Pat.
It is preferable to use a method of releasing an iodine atom from an organic compound described in 496,694 or the like in the form of iodine ions.

In the case where the tabular grains in the present invention have dislocation lines, the density of the dislocation lines is arbitrary, and 1
0 or more, 30 or more, 50 or more may be selected according to the case.

The tabular grains in the present invention may be epitaxial silver halide grains having at least one type of silver salt epitaxy formed on the surface of a host tabular grain.

In the present invention, silver salt epitaxy may be formed at selected sites on the surface of the host tabular grains, and the corners and edges of the host tabular grains (when the tabular grains are viewed from above, the side faces and sides of the grains). May be limited to the part on the side of.

When silver salt epitaxy is formed, it is preferable to form silver salt epitaxy uniformly at selected sites on the surface of the host tabular grains within and between grains.

As a specific method for the site direct of silver salt epitaxy, a spectral sensitizing dye (for example, a cyanine dye) or an amino design compound is added to the host particles before silver salt epitaxy described in US Pat. No. 4,435,501. (Eg, adenine) or a method in which silver iodide is contained in host grains. These methods may be used.

In addition, iodide ions may be added before the formation of silver salt epitaxy to precipitate the particles on the host grains.

These site direct methods may be selected according to the case, or may be used in combination.

When silver salt epitaxy is formed, the proportion occupied by the silver salt epitaxy with respect to the surface area of the host tabular grains is preferably 1 to 50%, more preferably 2 to 40%, and particularly preferably 3 to 30%. %.

When silver salt epitaxy is formed, the silver content of the silver salt epitaxy is preferably from 0.3 to 50 mol%, more preferably from 0.3 to 50 mol%, based on the total silver content of the silver halide tabular grains. It is 25 mol%, particularly preferably 0.5 to 15 mol%.

The composition of the silver salt epitaxy can be selected depending on the case, and may be a silver halide containing any of chloride ion, bromide ion and iodide ion.
It is preferable that the silver halide contains at least chloride ions.

When forming silver salt epitaxy, the preferred silver halide epitaxy is silver chloride containing epitaxy. Since silver chloride forms the same face-centered cubic lattice structure as silver bromide and silver iodobromide, which are host tabular grains, epitaxy is easy. However, there is a difference in the lattice spacing formed by the two types of silver halide, and this difference forms an epitaxy junction which contributes to an increase in photographic sensitivity.

The silver chloride content in silver halide epitaxy is preferably at least 10 mol% higher than the silver chloride content in host tabular grains.
It is more preferably at least 5 mol%, particularly preferably at least 20 mol%.

If the difference between the two is less than 10 mol%, the effect of the present invention is hardly obtained, which is not preferable.

It is preferable to introduce iodide ions into silver halide epitaxy for increasing the sensitivity.

When silver halide epitaxy is formed, the proportion of silver contained as silver iodide in the silver halide epitaxy is preferably at least 1 mol% with respect to the total silver content in the silver halide epitaxy. ,
More preferably, it is 1.5 mol% or more.

When introducing halide ions into silver halide epitaxy, it is preferable to introduce halide ions in an order corresponding to the composition of the epitaxy in order to increase the amount of the introduced halide ions.

For example, when epitaxy is formed in which the inside contains a large amount of silver chloride, the middle portion contains a large amount of silver bromide, and the outside contains a large amount of silver iodide, chloride ions,
By adding these halides in the order of bromide ion and iodide ion, the solubility of the silver halide containing the added halide ion is made lower than the solubility of other silver halide, and the silver halide is precipitated. To form a layer rich in the silver halide.

Silver salts other than silver halide, for example, silver rhodanate, silver sulfide, silver selenide, silver carbonate, silver phosphate and organic acid silver may be contained in the silver salt epitaxy.

Methods for forming silver salt epitaxy include a method of adding a halide ion, a method of adding an aqueous solution of silver nitrate and an aqueous solution of a halide by a double jet method, and a method of adding fine silver halide particles. It may be selected according to the case, or a plurality of them may be used in combination.

The temperature, pH, pAg, type and concentration of protective colloid such as gelatin, and the presence or absence, type, and concentration of a silver halide solvent in forming a silver salt epitaxy can be widely selected.

With respect to silver halide tabular grain emulsions having silver salt epitaxy formed on the surface of host tabular grains, recently, for example, European Patent Nos. 0699944A and 0701165A are disclosed.
Nos. 0701164A, 0699945A, 0699948A, 0699946A, 069
No. 9949A, No. 0699951A, No. 069995
Nos. 0A and 0699947A; U.S. Pat.
Nos. 1, 503,970, 5,494,789, JP-A-8-101476, JP-A-8-101475, and 8-
No. 101473, No. 8-101472, No. 8-101
Nos. 474 and 8-69069, the particle forming methods described in these patents can be used in the present invention.

In the case of epitaxial silver halide grains,
In order to maintain the shape of the host tabular grain or to direct the site to the grain edge / corner part of silver halide epitaxy,
It is preferable that the outer region of the host tabular grain (the last precipitated portion, which forms the edge / corner portion of the grain) has a silver iodide content at least 1 mol% higher than the silver iodide content of the central region. .

At this time, the silver iodide content of the outer region is preferably 1 to 20 mol%, more preferably 5 to 20 mol%.
To 15 mol%. If the amount is less than 1 mol%, the above effects are hardly obtained, and if it exceeds 20 mol%, the developing speed is undesirably slow.

In this case, the ratio of the total silver amount in the outer region containing silver iodide to the total silver amount of the host tabular grains is preferably 10 to 30%, more preferably 10 to 25%. If it is less than 10% or more than 30%, it is difficult to obtain the above effects, which is not preferable.

The silver iodide content in the central region at that time is preferably 0 to 10 mol%, more preferably 1 to 8 mol%, and particularly preferably 1 to 6 mol%.
If it exceeds 10 mol%, the developing speed is undesirably slow.

In one preferred embodiment of the present invention,
On a transparent support, at least photosensitive silver halide grains,
A light-sensitive material comprising a color developing agent, a coupler and a binder, having at least three types of photosensitive layers having mutually different photosensitive wavelength regions, and having mutually different absorption wavelength regions of a dye formed from the color developing agent and the coupler; Using a processing material having thereon a processing layer containing at least a base and / or a base precursor, 0.1 to 1 times the amount required for maximally swelling the entire coating film excluding the back layer of both the photosensitive material and the processing material. In the presence of the corresponding water, the photosensitive material and the processing material are overlapped with the photosensitive layer and the processing layer facing each other, and this is heated at a temperature of 60 ° C. to 100 ° C. for 5 seconds to 60 seconds to form at least An image based on three non-diffusible dyes is formed, and a color image is obtained on another recording material based on the image information.

The emulsions of the present invention and other photographic emulsions used in combination with the emulsions are described below. Specifically, U.S. Pat. No. 4,500,626, column 50,
No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as “RD”) No. 17,029 (1
No. 17,643 (December 1978)
Nos. 18,716 (November 11, 1979)
No. 307, 105 (November 1989)
Mon.) pp.863-865, JP-A-62-253,159.
No. 64-13,546, JP-A-2-236,54
No. 6, No. 3-110, 555 and "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glafkides, C.
hemie et Phisque Photographique, Paul Montel, 196
7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry,
Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions" by Zerikman et al., Published by Focal Press (VLZelikman et.
al., Making and Coating Photographic Emulusion, Fo
cal Press, 1964) and the like.

The silver halide used in the present invention may be any of silver iodobromide, silver bromide, silver chlorobromide, silver iodochloride, silver chloride and silver iodochlorobromide. The size of silver halide grains is 0.1 to 2 μm, particularly 0.2 to
1.5 μm is preferred. The shape of the silver halide grains may be those having a shape of normal crystals such as cubic, octahedral or tetradecahedral, and those having a hexagonal or rectangular tabular shape. Is preferably 8 or more, more preferably 20 or more tabular grains, and in such tabular grains, 50% or more, preferably 80% or more, more preferably 90% of the projected area of all grains.
It is preferable to use an emulsion occupying the above. U.S. Patent Nos. 5,494,789 and 5,503,970
No. 5,503,971, No. 5,536,632 and the like, particles having a smaller thickness than 0.07 μm and a higher aspect ratio can also be preferably used. U.S. Patent Nos. 4,400,463 and 4,7,
High silver chloride tabular grains having a (111) plane as a main plane described in US Pat. Nos. 13,323 and 5,217,858, and US Pat. Nos. 5,264,337, 5,
High silver chloride tabular grains having a (100) plane as a main plane described in JP-A-292,632 and JP-A-5,310,635 can also be preferably used. Examples of actually using these silver halide grains are described in Japanese Patent Application Nos. 8-46822, 8-97344 and 8-238672.

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

The binder of the light-sensitive material is preferably hydrophilic, and examples thereof include RD described in the preceding section and those described on pages 71 to 75 of JP-A-64-13546. Among them, gelatin and a combination of gelatin with another water-soluble binder such as polyvinyl alcohol, modified polyvinyl alcohol, cellulose derivative, acrylamide polymer and the like are preferable. The coating amount of the binder is from 1 to 20 g / m ^2, preferably 2 to 15 g / m ^2, more preferably 3~12g / m ²
Is appropriate. Among them, gelatin is 50% to 10%.
It is used at a rate of 0%, preferably 70% to 100%.

As the color developing agent, p-phenylenediamines or p-aminophenols may be used, but the compounds represented by formulas (3) to (7) are preferably used.

The compound represented by the general formula (3) is a compound generally called sulfonamidophenol. In the general formula (3), R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom (for example, a chloro group, a bromo group), an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-group).
-Butyl group), an aryl group (for example, phenyl group, tolyl group, xylyl group), an alkylcarbonamide group (for example, acetylamino group, propionylamino group, butyroylamino group), an arylcarbonamide group (for example, benzoylamino group), Alkylsulfonamide group (for example, methanesulfonylamino group, ethanesulfonylamino group), arylsulfonamide group (for example, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy group (for example, methoxy group, ethoxy group, butoxy group), aryloxy Group (eg, phenoxy group), alkylthio group (eg, methylthio group, ethylthio group, butylthio group), arylthio group (eg, phenylthio group,
Tolylthio group), alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenyl) Carbamoyl group,
Ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, dibutylsulfamoyl group) , Piperidylsulfamoyl group, morpholylsulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), Sulfamoyl group, cyano group, alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), Xycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, propionyl group, butyroyl group), arylcarbonyl group (for example, benzoyl group) Group, alkylbenzoyl group) or acyloxy group (eg, acetyloxy group, propionyloxy group, butyroyloxy group)
Represents Among R _{1 to} R ₄ , R ₂ and R ₄ are preferably a hydrogen atom. Also, Hammett's constant σ of R _{1 to} R ₄
It is preferable that the sum of the p values is 0 or more.

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

The compound represented by the general formula (4) is a compound generically called sulfonylhydrazine. The compound represented by the general formula (6) is a compound generally called carbamoylhydrazine.

In the general formulas (4) and (6), R ₅
Is a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, butyl group, octyl group, lauryl group, cetyl group, stearyl group), an aryl group (eg, phenyl group, tolyl group, xylyl group, 4- Methoxyphenyl group, dodecylphenyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, nitrochlorophenyl group, triisopropylphenyl group, 4-dodecyloxyphenyl group, 3,5-di (methoxy) carbonyl group), or heterocyclic group (For example, a pyridyl group).
Z represents an atomic group forming an aromatic ring. The aromatic ring formed by Z imparts silver developing activity to the present compound.
It must be sufficiently electron-attracting. 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 preferred.

When the aromatic ring formed by Z is a benzene ring, examples of the substituent include an alkylsulfonyl group (eg, a methanesulfonyl group and an ethanesulfonyl group).
Halogen atom (for example, chloro group, bromo 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, alkylsulfamoyl group (eg, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group) Sulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, morpholylsulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group) Amamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), and arylsulfonyl group (for example, Phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group ( For example, an acetyl group, a propionyl group, a butyroyl group) or an arylcarbonyl group (for example, a benzoyl group or an alkylbenzoyl group) can be mentioned. Is 1 or more.

The compound represented by the general formula (5) is a compound generally called sulfonylhydrazone. The compound represented by the general formula (7) is a compound generally called carbamoylhydrazone.

In the general formulas (5) and (7), R ₅
Is a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, butyl group, octyl group, lauryl group, cetyl group, stearyl group), an aryl group (eg, phenyl group, tolyl group, xylyl group, 4- Methoxyphenyl group, dodecylphenyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, nitrochlorophenyl group, triisopropylphenyl group, 4-dodecyloxyphenyl group, 3,5-di (methoxy) carbonyl group), or heterocyclic group (For example, a pyridyl group).
R ₆ represents a substituted or unsubstituted alkyl group (for example, a methyl group or an ethyl group). X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl- or aryl-substituted tertiary nitrogen atom, preferably an alkyl-substituted tertiary nitrogen atom. R ₇ and R ₈ represent a hydrogen atom or a substituent,
R ₇ and R ₈ may combine with each other to form a double bond or a ring.

The specific examples of the compounds represented by formulas (3) to (7) are shown below, but the present invention is of course not limited thereto.

[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

Embedded image

[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

Embedded image

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

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

As another embodiment of the present invention, at least one layer comprising a photosensitive silver halide emulsion, a coloring material which releases or diffuses a diffusible dye corresponding to or reversely corresponds to silver development, and a binder is provided on a support. It can take the form of a light-sensitive material comprising a light-sensitive silver halide emulsion layer and a non-light-sensitive layer. The coloring material used at that time is a compound that contains a dye portion in its own structure and has a capability of releasing or diffusing a diffusible dye in correspondence with silver development or inversely. Simultaneously with or subsequent to the development, part or all of the diffusible dye is removed from the photosensitive material. An image is obtained on the photosensitive material by the residual color material after the development.

This compound can be represented by the following general formula (LI). ((Dye) mY) nZ (LI) Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, and Z represents an image A difference in the diffusivity of the compound represented by ((Dye) m-Y) nZ corresponding to or opposite to a photosensitive silver salt having a latent image, or (Dye) m-
Y, and released (Dye) m-Y and ((Dy)
e) mY) represents a group having the property of causing a difference in diffusibility with nZ, m represents an integer of 1 to 5,
n represents 1 or 2, and when m and n are not 1, both Dyes may be the same or different. General formula (L
Specific examples of the dye-donating compound represented by I) are described in JP-A-9-112265, p. 10 to p. Compounds described in (1) to (12) can be mentioned. The compounds of the formula (1) release or diffuse a diffusible dye in a manner corresponding to the development of silver halide, and release or diffuse a diffusible dye in accordance with the development of a silver halide. .

Further, US Pat. No. 4,362,806,
As described in JP-A-3,719,489 and JP-A-4,375,507, a compound which reacts with a silver ion or an organic silver ion complex to release a diffusible dye can also be used.

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

In the present invention, a yellow filter layer, a magenta filter layer, and an antihalation layer can be used as a coloring layer using an oil-soluble dye that can be decolorized by a development treatment. Thereby, for example, when the photosensitive layer is provided in order of the red photosensitive layer, the green photosensitive layer, and the blue photosensitive layer from the side closest to the support, between the blue photosensitive layer and the green photosensitive layer. A yellow filter layer, a magenta filter layer between the green photosensitive layer and the red photosensitive layer, and a cyan filter layer (antihalation layer) between the red photosensitive layer and the support can be provided. These colored layers may be in direct contact with the photosensitive layer (emulsion layer), or may be arranged so as to be in contact with an intermediate layer such as gelatin. The dye is used in such an amount that the transmission density of each layer is 0.03 to 3.0, more preferably 0.1 to 1.0, for blue, green and red light, respectively. Specifically, although it depends on ε and the molecular weight of the dye, it may be used in an amount of 0.005 to 2.0 mmol / m ² , and more preferably 0.05 to 1.
0 mmol / m ² . The dye used is a dye that is decolorized by a reaction with a decoloring agent during the development processing, the dye is diffusion-resistant, and at least a part of the dye that has been decolorized after the development processing has diffusion resistance. Are preferred.

The dyes preferably used are described in Japanese Patent Application No.
-329124 (for example, 2-pyrazolin-5-one, 1,2,3,6-
Tetrahydropyridine-2,6-dione, rhodanin, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolopyridine, hydroxypyridine, pyrazolidine Zeon, 2,
5-dihydrofuran-2-one, pyrrolin-2-one)
Or an electron-withdrawing methylene group sandwiched between groups (e.g. _{-CN, -SO 2 R 1, -COR} 1, -COOR 1,
_{CON (R 2) 2, -SO} 2 N (R 2) 2, -C [= C
(CN) ₂ ] R ₁ , —C [C (CN) ₂ ] N (R ₁ )
₂ (R ₁ represents an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, a heterocyclic group, and R ₂ represents a hydrogen atom or a methylene group sandwiched by R ₁ ). Acidic nuclei, basic nuclei (eg, pyridine, quinoline, indolenine, oxazole, imidazole, thiazole, benzoxazole, benzimidazole, benzothiazole, oxazoline, naphthoxazole, pyrrole), aryl groups (eg, phenyl group, naphthyl group) and Heterocyclic groups such as pyrrole, indole, furan, thiophene, imidazole,
Pyrazole, indolizine, quinoline, carbazole,
Phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran,
A compound having a structure comprising a methine group and two of thiopyran, oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin) and (N
_{C) 2 C = C (CN} ) -R 3 (R 3 is an aryl group or a heterocyclic group).

The dye used in the present invention will be described in more detail. Preferred dyes used in the present invention are those represented by the following formulas (9) to (12). General formula (9) A51 = L51-(L52 = L53) _m51-
Q51 General formula (10) A51 = L51-(L52 = L53) _n51-
A52 General formula (11) A51 (= L51-L52) _p51 = B51 General formula (12) (NC) ₂ C = C (CN) -Q51 (wherein, = represents a double bond and-represents a single bond. A51,
A52 represents an acidic nucleus, and B51 represents a basic nucleus. Q51 represents an aryl group or a heterocyclic group. L5
1, L52 and L53 each represent a methine group. m51
Represents 0, 1, and 2. n51 and p51 are each 0,
1, 2, and 3 are represented. When a plurality of L51, L52 or L53 is present in each molecule, they may be the same or different. However, the general formulas (9) to (1)
The compound represented by 2) has no carboxyl group and / or sulfo group, and has the general formula (9) to (1)
The compound represented by the formula (2) has a diffusion-resistant group, and the product after development (decoloration) is also diffusion-resistant and does not substantially elute from the photosensitive material. Further, the compounds represented by the general formulas (9) to (12) do not have a group that causes an oxidation-reduction reaction during development processing, subsequently causes a bond to be broken, and is split into a plurality of molecules. )

The acidic nucleus represented by A51 or A52 is preferably a cyclic ketomethylene compound or a compound having a methylene group sandwiched between electron-withdrawing groups. Examples of the cyclic ketomethylene compound include 2-pyrazolin-5-
On, 1,2,3,6-tetrahydropyridine-2,6
-Dione, rhodanin, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolopyridine, hydroxypyridine, pyrazolidinedione, 2,5- Dihydrofuran-2
-One and pyrrolin-2-one. These may have a substituent. Among these, preferred compounds are 2-pyrazolin-5-one, 1,2,3,6
-Tetrahydropyridine-2,6-dione, isoxazolone, dioxopyrazolopyridine, hydroxypyridine, pyrazolidinedione, barbituric acid, and particularly preferably 2-pyrazolin-5-one, 1,2,3,
6, -tetrahydropyridine-2,6-dione, isoxazolone, hydroxypyridine, pyrazolidinedione and barbituric acid.

The compounds having a methylene group sandwiched between electron attractive groups can be represented as Z51-CH ₂ -Z52, wherein Z51, Z52 are each -CN, -SO
₂ R51, -COR51, -COOR51, -CON
_{(R52) 2, -SO 2 N} (R52) 2, -C [= C
(CN) ₂ ] R51, -C [= C (CN) ₂ ] N (R5
1) represents ₂ , R51 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group;
Represents a hydrogen atom or a group exemplified for R51. R51, R
52 may each have a substituent, and when there are a plurality of R51 or R52 in the molecule, they may be the same or different. Z51 and Z52 may be the same.

Examples of the basic nucleus represented by B51 include:
Examples thereof include pyridine, quinoline, indolenine, oxazole, imidazole, thiazole, benzoxazole, benzimidazole, benzothiazole, oxazoline, naphthoxazole, and pyrrole. Each of these may have a substituent. Preferred compounds among these are indolenine, benzoxazole,
Benzimidazole, benzothiazole and pyrrole are particularly preferred, and indolenine and benzoxazole are particularly preferred. Examples of the aryl group represented by Q51 include a phenyl group and a naphthyl group, each of which may have a substituent (preferably an electron donating group).
Of these, a phenyl group substituted with a dialkylamino group, a hydroxyl group, an alkoxy group, or an alkyl group is preferred, and a phenyl group substituted with a dialkylamino group is particularly preferred. Examples of the heterocyclic group represented by Q51 include pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran Oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin, and chroman, each of which may have a substituent. Of these, pyrrole and indole are preferred.

The methine groups represented by L51, L52 and L53 may have a substituent, and the substituents may be linked to each other to form a 5- or 6-membered ring (for example, cyclopentene, cyclohexene). . Examples of the substituent which the above group may have include a sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, octanesulfonamide) and a sulfamoyl group (eg, sulfamoyl, methylsulfamoyl, phenylsulfamoyl, butylsulfamoyl) Moyl), a sulfonylcarbamoyl group (eg, methanesulfonylcarbamoyl, benzenesulfonylcarbamoyl), an acylsulfamoyl group (eg, acetylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl), a linear or cyclic alkyl group (eg, Methyl, isopropyl, cyclopropyl, cyclohexyl, 2-ethylhexyl, dodecyl, octadecyl, 2-phenethyl, benzyl), alkenyl group (eg, vinyl, allyl), alkoxy group (eg, Alkoxy, octyloxy, dodecyloxy, 2-methoxyethoxy), an aryloxy group (e.g., phenoxy), halogen atom (e.g. F, Cl, Br), amino group (e.g., diethylamino, ethyl dodecyl amino),
Ester groups (eg, ethoxycarbonyl, octyloxycarbonyl, 2-hexyldecyloxycarbonyl), acylamino groups (eg, acetylamino, pivaloylamino, benzoylamino), carbamoyl groups (eg, unsubstituted carbamoyl, ethylcarbamoyl, diethylcarbamoyl, phenylethylcarbamoyl) ), Aryl groups (eg, phenyl, naphthyl), alkylthio groups (eg, methylthio, octylthio), arylthio groups (eg, phenylthio, naphthylthio), acyl groups (eg, acetyl, benzoyl, pivaloyl), sulfonyl groups (eg, methanesulfonyl, benzenesulfonyl) A ureido group (e.g., 3-propylureido, 3,
3-dimethylureide), urethane group (eg, methoxycarbonylamino, butoxycarbonylamino), cyano group, hydroxyl group, nitro group, heterocyclic group (eg, benzoxazole ring, pyridine ring, sulfolane ring, furan ring, pyrrole ring, pyrrolidine ring) , A morpholine ring, a piperazine ring, a pyrimidine ring) and the like.

The dye used in the present invention is preferably represented by formula (9), (10) or (11), and more preferably represented by formula (9) or (10).
It is represented by

The dye represented by the general formula (9) is generally called an arylidene dye.
When the dye represented by the formula (1) is a yellow or magenta dye, the dye represented by the general formula (13) is preferably used.

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(Wherein = represents a double bond,-represents a single bond. A ₆₁ represents an acidic nucleus, L ₆₁ , L ₆₂ and L ₆₃ each represent a methine group, and L ₆₄ and L ₆₅ represent Each independently represents an alkylene group having 1 to 4 carbon atoms, and R ₆₂ and R ₆₃ are each independently a cyano group, a —COOR ₆₄ group, or a —CONR ₆₅ R ₆₆
Group, -COR ₆₄ group, -SO ₂ R ₆₄ group, -SO ₂ NR ₆₅ R
₆₆ represents a group, R ₆₄ represents an alkyl group, an alkenyl group, a cycloalkyl group, and an aryl group, and R ₆₅ and R ₆₆ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, and an aryl group. . R ₆₁ represents a substituent, m
₆₁ represents 0 or 1 and n ₆₁ represents an integer of 0 to 4. Note that R
_65, and R ₆₆ are linked to each other may form a ring L _62, L
_{When a} plurality of ₆₃ exist, they may be the same or different. )

Hereinafter, the dye represented by formula (13) will be described in detail. In the compound (dye) represented by the general formula (13), m ₆₁ is 0 or 1, and when m ₆₁ is 0, it is called a benzylidene dye, often a yellow dye, and m ₆₁ is 1 In this case, it is called a cinnamylidene dye and is often a magenta dye. In the present invention,
M ₆₁ in the general formula (13) is preferably 0, and the compound of the general formula (13) is preferably a yellow dye.

In the general formula (13), A ₆₁ represents an acidic nucleus;
The same as A51 and A52 in formulas (9) to (11), but more preferably 2-pyrazolin-5-one, isoxazolone, hydroxypyridine, pyrazolidinedione, and barbituric acid, and further more preferably Are isoxazolones, pyrazolidinedione, barbituric acid, most preferably pyrazolidinedione.

L ₆₁ , L ₆₂ and L ₆₃ in the general formula (13)
Examples of the methine group represented by the general formulas (9) to (1)
The same as L ₅₁ , L ₅₂ and L ₅₃ in 1) can be mentioned, but the methine group represented by L ₆₁ , L ₆₂ and L ₆₃ is preferably ＣＲCR ₆₇ — (R ₆₇ is the number of carbon atoms ( (Hereinafter referred to as "C number") 1 to 10 alkyl groups or hydrogen atoms)
It is represented by Further, as a combination of L _61, L _62, L _63, or L _61, L _62, L ₆₃ both R ₆₇ is a hydrogen atom,
Or preferably R ₆₇ in L ₆₂ in R ₆₇ is a hydrogen atom L _61, L ₆₃ is a methyl _{group, L 61, L 62, L} 63 both R
Most preferably, ₆₇ is a hydrogen atom.

In the general formula (13), L ₆₄ and L ₆₅ each independently represent an alkylene group having 1 to 4 carbon atoms, preferably a methylene group or an ethylene group. It is preferred that the L ₆₄ and L ₆₅ are the same.

In the general formula (13), R ₆₂ and R ₆₃ are each independently a cyano group, a —COOR ₆₄ group, a —CONR
₆₅ R ₆₆ groups, -COR ₆₄ groups, -SO ₂ R ₆₄ groups, -SO ₂ N
R ₆₅ represents R ₆₆ . R ₆₄ is an alkyl group (eg, methyl,
Ethyl, i-propyl, t-butyl, benzyl, trifluoromethyl, 2-chloroethyl, 2-ethoxyethyl), alkenyl group (eg, vinyl, allyl, oleyl), cycloalkyl group (eg, cyclopentyl, cyclohexyl), aryl group (For example, phenyl, 2-naphthyl, 4-chlorophenyl, 2-methoxyphenyl, 3
-Dimethylaminophenyl), preferably an alkyl group or an alkenyl group, more preferably a straight-chain unsubstituted alkyl group. R ₆₅ and R ₆₆ each independently represent a group or a hydrogen atom described above for R ₆₄ , and are preferably an alkyl group, an aryl group, or a hydrogen atom, and more preferably an unsubstituted alkyl group or a hydrogen atom. When R ₆₅ and R ₆₆ are other than a hydrogen atom, it preferably has 1 to 20 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 8 to 16 carbon atoms. As R ₆₂ and R ₆₃ , a cyano group, —C
OOR ₆₄ groups and —CONR ₆₅ R ₆₆ groups are more preferred, cyano groups and —COOR ₆₄ groups are particularly preferred, and —COOR ₆₄ groups are most preferred. When R ₆₂ and R ₆₃ are cyano groups, L ₆₄ and L ₆₅ are each preferably an ethylene group, and when R ₆₂ and R ₆₃ are COOR ₆₄ groups, L ₆₄ and L ₆₅ are each a methylene group. It is preferably a group. The R ₆₂ and R _63, may be different even in the same, but is preferably the same.

In the general formula (13), R ₆₁ represents a substituent, preferably a group given as an example of a substituent of the methine group of L ₆₁ , L ₆₃ and L ₆₃ , more preferably an alkyl group,
It represents an alkoxy group, a dialkylamino group or an alkoxycarbonyl group, particularly preferably represents an alkyl group or an alkoxy group, and most preferably represents a methyl group or a methoxy group.

In the general formula (13), n ₆₁ represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0. When n ₆₁ is 1, R ₆₁ is preferably substituted at the m-position of the amino group. Specific examples of the dye used in the present invention are shown below, but the present invention is not limited to these.

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The dyes used in the present invention are described in International Patent WO
88/04794, European Patent EP 274,723,
276,556, 299,435, U.S. Pat. Nos. 2,527,583, 3,486,897, 3,746,539, 3,933,798, 4,130, 429, 4,040,841, JP-A-48-68,623, 52-92,716, 55-155,350, 55-155,351,
No. 61-205,934, JP-A-2-173,630
No. 2-230,135 and 2-277,044
Nos. 2-282, 244, 3-7,931, 3-167,546, 3-13,937, 3-
Nos. 206,443, 3-208,047, 3-1
Nos. 92,157, 3-216,645 and 3-27
4,043, 4-37,841, 4-45,4
No. 36, No. 4-138, 449, No. 5-197, 07
No. 7, Japanese Patent Application No. 5-273, 811 and No. 6-7,761
And the methods described in JP-A Nos. 6-155727, and the like, or can be synthesized according to the methods.

Specific examples of the synthesis of the exemplified compounds (A10), (A100) and (A134) of the present invention are shown below as typical examples. (Synthesis Example-1) Synthesis of Exemplified Compound (A10)

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A solution of (A10-2) (0.52 mol) in acetonitrile (250 ml) was dissolved in an ice-methanol bath.
Cool to 7 ° C and add phosphorus oxychloride (0.55mo
l) was added dropwise while maintaining the temperature of the reaction solution at 15 ° C or lower. Subsequently, a solution of (A10-1) (0.5 mol) in acetonitrile (150 ml) was added dropwise while keeping the internal temperature at 5 ° C. or lower, and then the cooling bath was removed and the mixture was further stirred for 1 hour. Then, the reaction solution was poured into ice water (1 l), and a solution of sodium hydroxide (100 g) in water (500 ml) was added thereto. The reaction mixture was extracted twice with ethyl acetate (500 ml), and the organic layer was washed with brine and concentrated. The resulting residue was recrystallized from methanol to give (A10-
3) was obtained with a yield of 49%.

(A10-3) (0.05 mol) and (A10-3)
10-4) (0.05 mol), potassium carbonate (0.1
0 mol) with N, N-dimethylacetamide (200 m
In l), the reaction was carried out at 100 ° C. for 3 hours. After cooling to room temperature
Ethyl acetate (200 ml) was added, and the insoluble matter was removed by filtration. The filtrate was washed with 2N hydrochloric acid, water and brine, and concentrated to give (A10-5) quantitatively. (A10-5)
(0.03 mol) and (A10-6) (0.03 mol)
1) was refluxed in ethanol (80 ml) for 5 hours, after which the solvent was distilled off. The residue was subjected to silica gel column chromatography (eluent, methylene chloride / hexane = 4/1 to 1).
1/0) to give Exemplified Compound (A10)
Was obtained in a yield of 76%.

(Synthesis Example-2) Illustrative Compound (A-100)
Synthesis of

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76.4 g (0.55 mol) of bromoacetic acid (a), 93.2 g (0.5 mol) of dodecanol (b),
1.4 g of p-toluenesulfonic acid monohydrate in toluene 2
1 ml while dissolving in water and azeotropically removing generated water.
Refluxed for hours. After washing three times with a 2% aqueous sodium carbonate solution, drying over magnesium sulfate and concentration were carried out to obtain a transparent liquid ester (c). (100% yield)

Aniline 21.1 g (0.227 mol),
0.5 mol of the above ester (c), 105 g of potassium carbonate
(0.75 mol), 11.2 g of sodium iodide (0.
075 mol) was dissolved in 300 ml of dimethylacetamide, and the mixture was heated and stirred at 80 ° C. for 4 hours under a nitrogen atmosphere. After cooling, water and ethyl acetate were added to carry out liquid separation, and the mixture was washed twice with water. Concentrate after drying with magnesium sulfate and aniline (d)
Was obtained as a main component.

300 ml of dimethylformamide at 10 ° C.
Stir while cooling below, and add phosphorus oxychloride 6
9.6 g (0.454 mol) was added dropwise so that the temperature did not exceed 20 ° C., and the mixture was further stirred at 20 ° C. for 30 minutes.
A solution containing aniline (d) was added thereto, and the temperature was further increased to 60 ° C.
For 1 hour. After cooling, 1 liter of water and 110 g of potassium hydroxide were carefully added in that order to adjust the pH to 8, and the mixture was extracted with ethyl acetate and washed twice with water. After drying over magnesium sulfate, the mixture was concentrated, acetonitrile was added, and the mixture was cooled to crystallize benzaldehyde (e) as light brown crystals, which was separated by filtration and washed with cold acetonitrile. Benzaldehyde (e) was obtained in a yield of 74.2 g (57% yield (from aniline)).

6.31 g of pyrazolidinedione (f)
(0.025 mol), the above-mentioned benzaldehyde (e) 1
5.8 g (0.0275 mol), 7.7 g of acetic anhydride
(0.075 mol) was dissolved in 50 ml of ethanol.
Refluxed for hours. Upon cooling, crystals were precipitated, separated by filtration and washed with cold ethanol to obtain pale yellow crystals of Exemplified Compound (A-100). The yield was 16.4 g (81.2% yield (from pyrazolidinedione (f)).

(Synthesis Example-3) Illustrative Compound (A-134)
Synthesis of

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(A134-1) 102 was placed in a three-necked flask.
0 g, 24.3 ml of pyridine and 2 liters of N, N-dimethylacetamide were added, and 347 ml of diketene was added dropwise over 30 minutes while heating and stirring at an internal temperature of 85 ° C. After continuing to heat and stir for 3 hours, the mixture was cooled to room temperature, extracted with 4 l of ethyl acetate and 4 l of water, and the obtained ethyl acetate layer was washed 5 times with a mixed solution of 500 ml of saturated saline and 2 l of water. And dried over anhydrous sodium sulfate. This was concentrated with a rotary evaporator, and the residue obtained was added with 2.5 liters of isopropyl alcohol and the precipitated crystals were separated by filtration to obtain 944 g of compound (A134-2) (yield 74%).

The above compound (A134-
2) 424 g and 900 ml of isopropyl alcohol are added, and 119 ml of piperidine is added thereto while stirring at room temperature.
Was added dropwise over 5 minutes. After completion of the dropwise addition, 128 ml of ethyl cyanoacetate was added dropwise thereto over 10 minutes while stirring under heating and refluxing, and stirring was continued under heating and refluxing for 3 hours, followed by cooling to room temperature. The resulting ethyl acetate layer was washed five times with a mixed solution of 300 ml of a saturated saline solution and 1 liter of water, and extracted.
It was dried over anhydrous sodium sulfate. This was concentrated by a rotary evaporator, and 1.2 liters of acetonitrile was added to the residue obtained. 129 ml of concentrated hydrochloric acid was added dropwise thereto over 20 minutes while stirring under ice-cooling, and the precipitated crystals were separated by filtration to obtain the compound ( A134-3) 393 g was obtained.
(83% yield).

The above compound (A134-
4) Put 142 g and 1.5 liter of acetonitrile,
While stirring at room temperature, 202 ml of pyridine is added to 25 ml.
After dropwise addition over a period of 94 minutes, 94 ml of acetic anhydride was continuously added dropwise over a period of 10 minutes. After stirring for 10 minutes after the completion of dropping, 473 g of (A134-3) was added thereto over 20 minutes, stirring was continued for 3 hours as it was, and the mixture was further stirred for 1 hour under ice-cooling, and the precipitated crystals were separated by filtration. Compound (A134) 3
88 g were obtained (77% yield).

The structures of these compounds were confirmed by NMR, MS spectrum and elemental analysis.

The light-sensitive material of the present invention may be used by mixing two or more dyes in one colored layer. For example, three kinds of dyes of yellow, magenta and cyan can be mixed and used in the above-mentioned antihalation layer. In the present invention,
Preferably, an oil droplet in which a decolorable dye is dissolved in oil and / or an oil-soluble polymer is used in a state of being dispersed in a hydrophilic binder. An emulsification dispersion method is preferable as the preparation method, and for example, a method described in US Pat. No. 2,322,027 can be used. In this case, US Pat.
No. 55,470, No. 4,536,466, No. 4,58
7,206, 4,555,476 and 4,59
No. 9,296, Japanese Patent Publication No. 3-62,256, etc., a high-boiling oil, if necessary, having a boiling point of 50 ° C. to 160 ° C.
It can be used in combination with an organic solvent having a low boiling point of ° C. Further, two or more high boiling oils can be used in combination. In addition, an oil-soluble polymer can be used in place of or in combination with oil, and examples thereof include PCT International Publication No. W
O88 / 00723. The amount of the high boiling oil and / or the polymer is 0.01 g to 10 g, preferably 0.1 g, per 1 g of the dye used.
Use up to 5 g. As a method of dissolving the dye in the polymer, it is also possible to use a latex dispersion method,
Specific examples of the process and the latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) 2,5.
No. 41,274, No. 2,541,230, No. 5
3-41091 and European Patent Publication No. 029104. When dispersing the oil droplets in the hydrophilic binder, various surfactants can be used.
For example, surfactants described in JP-A-59-157,636, pp. 37-38, and publicly known technique No. 5 (March 22, 1991, published by Aztec Co., Ltd.), pp. 136-138, can be used. Also, Japanese Patent Application No. 5-204,
No. 325, No. 6-19247 and West German Offenlegungsschrift 1,932,299A can also be used.

The hydrophilic binder is preferably a water-soluble polymer. Examples are gelatin, proteins of gelatin derivatives, or cellulose derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan and polyvinyl alcohol, polyvinylpyrrolidone,
Synthetic polymer compounds such as acrylamide polymers are exemplified. These water-soluble polymers can be used in combination of two or more. Particularly preferred is a combination with gelatin. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and may be used in combination. The dye decolorizes during the development processing in the presence of the decoloring agent. Examples of the decoloring agent include alcohols or phenols, amines or anilines, sulfinic acids or salts thereof, sulfurous acids or salts thereof, thiosulfuric acids or salts thereof, carboxylic acids or salts thereof, hydrazines, guanidines, aminoguanidines, and amidines. , Thiols, cyclic or chain active methylene compounds, cyclic or chain active methine compounds, and anionic species generated from these compounds. Of these, those preferably used are hydroxyamines, sulfinic acids, sulfurous acid, guanidines, aminoguanidines, heterocyclic thiols, cyclic or linear active methylene, and active methine compounds, and guanidine is particularly preferred. , Aminoguanidines.

It is considered that the above-mentioned decolorizing agent comes into contact with the dye during the treatment and decolorizes the dye by nucleophilic addition to the dye molecule. Preferably, the silver halide light-sensitive material containing the dye is heated after imagewise exposure or at the same time as the imagewise exposure, by superposing the film surfaces together in the presence of water and a processing material containing a decolorant or a decolorant precursor. Thereafter, by peeling off both, a color-developed image is obtained on the silver halide light-sensitive material and the dye is decolorized. In this case, the density of the dye after decoloring is 1/3 or less, preferably 1/5 or less of the original density. The amount of the decoloring agent used is 0.1 to 20 times the dye.
It is 0 mole, preferably 0.5 to 100 mole.

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

The light-sensitive material may contain, for various purposes, a hardener, a surfactant, a photographic stabilizer, an antistatic agent, a slipping agent, a matting agent,
Latex, formalin scavenger, dye, UV absorber and the like can be used. Specific examples of these are described in the aforementioned RD and Japanese Patent Application No. 8-30103. Examples of particularly preferred antistatic agents are ZnO, Ti
O ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ ,
Metal oxide fine particles such as MgO, BaO, MoO ₃ , and V ₂ O ₅ .

As the support of the photosensitive material, a photographic support described in “Basics of Photographic Engineering-Silver Salt Photography” edited by the Photographic Society of Japan, Corona Co., Ltd. (1979), pages 223 to 240, is preferred. Specific examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, syndiotactic polystyrene, and celluloses (eg, triacetyl cellulose). These supports can be subjected to heat treatment (crystallinity and orientation control), uniaxial and biaxial stretching (orientation control), blending of various polymers, surface treatment, etc. to improve optical and physical properties. it can. Further, as a support, for example,
-124645, 5-40321, 6-350
It is preferable to record photographic information and the like by using a support having a magnetic recording layer described in JP-A-92-92 and JP-A-6-31875.

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

As a method for developing the photographed photosensitive material of the present invention, a heat development system incorporating a color developing agent is preferable.
An image is formed by developing the light-sensitive material of the present invention with an activator method using an alkali processing solution or a processing solution containing a developing agent / base, while aiming for quick and easy and low environmental load. It is also possible.

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

Activator processing refers to a processing method in which a color developing agent is incorporated in a photosensitive material and development is performed using a processing solution containing no color developing agent. The processing solution in this case is characterized in that it does not contain a color developing agent contained in a normal developing solution component, and may contain other components (for example, an alkali, an auxiliary developing agent, etc.). Regarding the activator treatment, European Patent No. 545,
No. 491A1, No. 565, 165A1, and the like.

A method of developing with a processing solution containing a developing agent / base is described in RD No. 17643, pp. 28-29, and RD No. 18
716, left column to right column, and No. 307105
On pages 880-881.

Next, a processing material and a processing method used in the case of heat development processing in the present invention will be described.

In the present invention, a processing material different from the photosensitive material can be used for developing the photographed photosensitive material. The treatment material contains at least a base and / or a base precursor. The most preferred are EP210,
No. 660, U.S. Pat. No. 4,740,445, a basic metal compound which is sparingly 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. Is a method of generating a base by a combination of In this case, it is preferable to add the basic compound which is hardly soluble in water to the light-sensitive material and the complex-forming compound to the processing material, and vice versa. A preferred combination of compounds is a system using zinc hydroxide fine particles as a photosensitive material and a picolinic acid salt such as guanidine picolinate as a processing material. A mordant may be used as the treatment material, and in this case, a polymer mordant is preferable. The processing material contains a physical development nucleus such as colloidal silver or palladium sulfide, and a silver halide solvent such as hydantoin as described in Japanese Patent Application No. 7-322454, and is exposed to light simultaneously with development. The silver halide of the material may be solubilized and fixed to the processing material. The processing material may further contain a development stopping agent, a printout preventing agent, and the like.

The processing material may have a protective layer, an undercoat layer, a back layer and other auxiliary layers in addition to the processing layer. The processing material is preferably provided with a processing layer on a continuous web, fed from a feed roll, and wound up on another roll without being cut even after being used for processing. An example is described in Japanese Patent Application No. 7-240445. The support of the processing material is not limited, and a plastic film or paper as described for the photosensitive material is used. The thickness is 4 μm-1
It is 20 μm, preferably 6 μm to 70 μm. A film on which aluminum is deposited as described in Japanese Patent Application No. 8-52586 can be preferably used.

In the present invention, a light-sensitive material photographed by a camera or the like is used in the presence of water equivalent to 0.1 to 1 times the amount required for maximally swelling the entire coating film excluding the back layer of both the light-sensitive material and the processing material. Then, the photosensitive material and the processing material are overlapped so that the photosensitive layer and the processing layer face each other.
It is preferable to develop by heating at a temperature of ° C. for 5 to 60 seconds.

As a method for applying water, there is a method in which a photosensitive material or a processing material is immersed in water and excess water is removed with a squeeze roller. Further, as described in Japanese Patent Application No. 8-196945, a plurality of nozzle holes for injecting water are linearly arranged at regular intervals along a direction intersecting the conveying direction of the photosensitive material or the processing material. It is also preferable to spray water using a water application device having a nozzle that has been moved and an actuator that displaces the nozzle toward a photosensitive material or a processing material on a transport path. A method of applying water with a sponge or the like is also preferable.

As a heating method in the developing step, a heated block or plate may be brought into contact, or a heat roller, a heat drum, an infrared or far-infrared lamp, or the like may be used. In the present invention, another bleach-fixing step for further removing the silver halide and the developed silver remaining in the light-sensitive material after the development is not essential. However, a fixing step and / or a bleaching step may be provided in order to reduce the load of reading image information and to enhance image storability. In that case, normal liquid treatment may be used,
It is preferable to perform a heat treatment together with another sheet coated with a treatment agent as described in Japanese Patent Application No. 8-89977.

In the present invention, after obtaining an image on a photosensitive material, it is preferable to obtain a color image on another recording material based on the information. As a method, using a photosensitive material such as color paper, ordinary projection exposure may be used, but image information is photoelectrically read by measuring the density of transmitted light, converted into a digital signal, and after image processing, the signal is used. It is preferable to output to another recording material. The material to be output may be a sublimation type thermosensitive recording material, a full color direct thermosensitive recording material, an ink jet material, an electrophotographic material, or the like, in addition to a photosensitive material using silver halide.

Next, a processing solution containing a developing agent / base for a color negative film used in the present invention will be described. The color developing solution used in the present invention includes JP-A-4-14-1.
No. 21739, page 9, upper right column, line 1 to page 11, lower left column, line 4 can be used. In particular, 2-methyl-4 is used as a color developing agent for rapid processing.
-[N-ethyl-N- (2-hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N-
(3-Hydroxypropyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline are preferred.

As a preservative for the color developing solution, hydroxylamine can be used in a wide range, but when higher preservation is required, an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group and the like can be used. A hydroxylamine derivative having a substituent is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) ) Hydroxylamine is preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferred. These may be used in combination with hydroxylamine, but it is preferable to use one or more of them instead of hydroxylamine. Further, the pH of the color developing solution is preferably in the range of 9.8 to 11.0, particularly preferably 10.0 to 11.0.
The range of 10.5 is preferable, and in the replenisher,
It is preferable to set a high value in the range of 0.1 to 1.0 from these values. In order to stably maintain such a pH, a known buffer such as a carbonate, a phosphate, a sulfosalicylate, and a borate is used.

The processing solution having the bleaching ability in the present invention includes, from page 4, lower left column, line 16 to page 4 of JP-A-4-125558.
The compounds and processing conditions described on page 7, lower left column, line 6, can be applied. The bleach has a redox potential of 150 m
V or more are preferable, and specific examples thereof include those described in JP-A-5-72694 and JP-A-5-17312, and in particular, 1,3-diaminopropanetetraacetic acid,
A ferric complex salt of the compound of Example 1 on page 7 of JP-A-5-17312 is preferred. Further, in order to improve the biodegradability of the bleaching agent, JP-A-4-251845 and 4-268.
552, EP 588,289, 591,934
It is preferable to use a ferric complex salt of a compound described in JP-A-6-208213 as a bleaching agent.

For the processing solution having a fixing ability, the compounds and processing conditions described in JP-A-4-125558, page 7, lower left column, line 10 to page 8, lower right column, line 19 can be applied. Particularly, in order to improve the fixing speed and the preservability, the compounds represented by the general formulas (I) and (II) of JP-A-6-301169 are contained alone or in combination in a processing solution having a fixing ability. Is preferred. It is also preferable to use the sulfinic acid described in JP-A 1-2224762, in addition to the p-toluene sulfinate, from the viewpoint of improving the preservation.

The washing and stabilizing steps are described in JP-A-4-125558, page 12, lower right column, line 6 to 1
The contents described in page 16, lower right column, line 16 can be preferably applied. In particular, azolylmethylamines described in EP 504,609 and EP 519,190 and N-methylolazoles described in JP-A-4-362943 are used in place of formaldehyde as the stabilizer,
Dimerizing the magenta coupler into a surfactant solution that does not contain an image stabilizer such as formaldehyde,
It is preferable from the viewpoint of preserving the working environment. To reduce the adhesion of dust to the magnetic recording layer applied to the photosensitive material,
Stabilizers described in JP-A-6-289559 can be preferably used.

Next, the processing solution for a color reversal film used in the present invention will be described. For the processing for the color reversal film, see page 6, line 5 to page 10, line 5 and page 15, line 8 to page 24, 2 of the publicly known technique No. 6 (April 1, 1991) issued by Aztec Co., Ltd. Each row is described in detail, and any of the contents can be preferably applied. In processing color reversal films, the image stabilizer is contained in the conditioning or final bath. Examples of such an image stabilizer include formaldehyde sodium bisulfite and N-methylolazole besides formalin. From the viewpoint of working environment, sodium formaldehyde sodium bisulfite or N-methylolazole is preferable, and N-methylol is preferred. As the azoles, N-methyloltriazole is particularly preferred. Further, the contents relating to the color developing solution, bleaching solution, fixing solution, washing water and the like described in the processing of the color negative film can be preferably applied to the processing of the color reversal film. Preferred processing agents for the color reversal film containing the above contents include E-6 processing agent of Eastman Kodak Company and Fuji Photo Film Co., Ltd.
CR-56 treating agent.

[0230]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) Preparation of emulsion Tabular silver iodobromide emulsion 1-A (comparative emulsion) (Step 1) Low molecular weight gelatin (molecular weight 15,000) 0.5
g and KBr of 0.37 g were stirred at 40 ° C. while maintaining the temperature at 40 ° C., and 7.8 cc of 0.3 M AgNO ₃ aqueous solution and 7.8 cc of 0.3 M KBr aqueous solution were simultaneously added by a double jet for 40 seconds. Then pAg
After adjusting to 9.9, the temperature was raised to 75 ° C. in 35 minutes,
After adding 35 g of gelatin (lime-processed gelatin),
33 cc of a 1.2 M AgNO ₃ aqueous solution and 440 cc of a 1.4 M KBr aqueous solution containing 10 mol% of KI while maintaining the pAg at 7.86 while increasing the flow rate (the flow rate at the end is 5.2 times that at the start) 33 Minutes. (Step 2) Thereafter, the temperature was lowered to 55 ° C. and 0.4M AgNO
₃ 104cc aqueous solution and 279c of 0.12M KI aqueous solution
c was added in a fixed amount for 5 minutes, and subsequently, an aqueous KBr solution was added to adjust the pAg to 8.8, and then 1.8 M AgNO ₃ was added.
110cc aqueous solution and 125cc 1.8M KBr aqueous solution
Was added. (Step 3) Thereafter, the emulsion was cooled to 35 ° C., washed with water by a conventional flocculation method, and 75 g of gelatin was added thereto.
= 5.5 and pAg = 8.2.

The grains in the obtained emulsion had an aspect ratio of 3
The above tabular grains accounted for more than 95% of the total projected area of all grains, and the average equivalent sphere diameter was 0.90 μm (the same applies to the following emulsions 1-B to 1-E). The average particle thickness was 0.321 μm. The average grain thickness was determined by taking a transmission electron microscope photograph by a replica method (the same applies to the following emulsions 1-B to 1-E). The average silver iodide content was 3.9 mol%. Observation of dislocation lines with a high-pressure electron microscope for 200 grains in the emulsion revealed that the ratio (number) of grains containing 10 or more dislocation lines in the fringe portion of the grains exceeded 50% per grain. (Emulsions 1-B to 1 below)
The same was true for -D).

Tabular Silver Iodobromide Emulsion 1-B (Emulsion of the Present Invention) An emulsion was prepared in the same manner as in Emulsion 1-A, except that Step 1 was changed as follows. At 75 ° C. the pAg is 8.5 instead of 7.86
8 while increasing the flow rate. After the temperature was lowered to 55 ° C., the pAg was adjusted to the same as that of Emulsion 1-A, and then the subsequent addition was performed. The average grain thickness of the grains in the obtained emulsion was 0.290 μm. The average silver iodide content was 3.9 mol%.

Tabular silver iodobromide emulsion 1-C (emulsion of the present invention) Prepared similarly to emulsion 1-A except that step 1 was changed as follows. 0.5 g of oxidized gelatin and KBr.
H ₂ SO ₄ was added to 1000 cc of an aqueous solution containing 37 g to adjust pH = 2, and stirred at 40 ° C.
7.8 cc of an aqueous AgNO ₃ solution and 7.8 cc of a 0.3 M aqueous KBr solution were simultaneously added by a double jet for 40 seconds. Then, the pAg was adjusted to 9.9, the pH was adjusted to 5.0 by adding NaOH, the temperature was raised to 75 ° C. in 35 minutes, 35 g of oxidized gelatin was added, and a 1.2 M AgNO ₃ aqueous solution was added. 512 cc and 440 cc of a 1.4 M KBr aqueous solution were added for 33 minutes while increasing the flow rate while maintaining the pAg at 7.86 (the flow rate at the end was 5.2 times that at the start). The average grain thickness of the grains in the obtained emulsion was 0.179.
μm. The average silver iodide content is 3.9 mol%
Met.

Tabular silver iodobromide emulsion 1-D (emulsion of the present invention) Except for the following, emulsion emulsion 1-D was prepared in the same manner as emulsion 1-C. In step 1, pAg was added at 75 ° C. in the same manner while increasing the flow rate while keeping the pAg at 8.15 instead of 7.86. After the temperature was lowered to 55 ° C., the pAg was adjusted to the same as that of the emulsion 1-C, and then the subsequent addition was performed. In step 2, instead of adding 104 cc of a 0.4 M AgNO ₃ aqueous solution and 279 cc of a 0.12 M KI aqueous solution for 5 minutes, an aqueous solution 1 containing 12.8 g of sodium p-iodoacetamidobenzenebenzenesulfonate was used.
Then, the pH was adjusted to 9.0 by adding NaOH, and then an aqueous solution 42 containing 4.2 g of sodium sulfite was added.
cc in 1 minute, and 5 minutes later, H ₂ SO ₄ was added to p.
H was adjusted to 5.0. The average grain thickness of the grains in the obtained emulsion was 0.094 μm. The average silver iodide content was 3.9 mol%.

Tabular silver iodobromide emulsion 1-E (Emulsion of the present invention) H ₂ SO ₄ was added to 1000 cc of an aqueous solution containing 0.5 g of oxidized gelatin and 0.37 g of KBr, and the pH was adjusted to 2 while maintaining the temperature at 40 ° C. Stir and add 0.3M AgNO
₃ aqueous solution 7.8cc and 0.3M KBr aqueous solution 7.8c
c was added simultaneously with a double jet for 40 seconds. After adjusting the pAg to 9.9, the temperature was raised to 75 ° C. in 35 minutes, 35 g of oxidized gelatin was added, and 549 cc of a 1.1 M AgNO ₃ aqueous solution was added while increasing the flow rate (when the flow rate at the end was At the same time, a 1.1 M (KBr + KI) aqueous solution containing 2 mol% of KI was added so as to keep the pAg at 8.58. afterwards,
After adding a solution containing K ₂ IrCl ₆ in an amount of 2 × 10 ⁻⁸ mol / mol Ag with respect to the total silver, 185 cc of a 1.1 M AgNO ₃ 3 aqueous solution was added in a fixed amount for 6 minutes, and at the same time, KI was added to the mixture. 1.2 M (KBr + K
I) The aqueous solution was added to keep the pAg at 8.58.
Thereafter, the emulsion was cooled to 35 ° C., washed with water by a conventional flocculation method, 75 g of gelatin was added, and the pH was adjusted to 5.5.
pAg was adjusted to 8.2. The average grain thickness of the grains in the obtained emulsion was 0.061 μm. The average silver iodide content was 4.4 mol%.

(2) Chemical sensitization For emulsions 1-A to 1-D, 58 ° C., pH = 6.2, p
The following green-sensitive spectral sensitizing dyes I and II under the condition of Ag = 8.4
After adding III and III, a mixed solution of potassium thiocyanate and chloroauric acid was added, and then sodium thiosulfate, the following selenium sensitizer and compound I were added to perform spectral sensitization and chemical sensitization. The termination of chemical sensitization was performed using the following mercapto compounds. At this time, the amounts of the spectral sensitizing dye and the chemical sensitizer were adjusted so that the sensitivity of the emulsion at 1/100 second exposure was maximized. The sensitivity mentioned here is
It is the logarithm of the reciprocal of the exposure amount that gives a density of fog + 0.15 on the characteristic curve obtained when the photosensitive material is exposed and developed as described later (the same applies to emulsion 1-E described below).

Emulsion 1-E: 40 ° C., pH = 6.
2. 0.06 M KI aqueous solution under the condition of pAg = 9.0
After addition of the following green-sensitive spectral sensitizing dyes I, II and III, 30 cc of a 1.2 M NaCl aqueous solution was added, and then a 1.2 M KBr aqueous solution 30 c was added.
c, followed by 21 cc of a 0.64 M KI aqueous solution
And further added 70 cc of a 1.2 M AgNO ₃ aqueous solution.
Was added, followed by the addition of a mixed solution of potassium thiocyanate and chloroauric acid, followed by sodium thiosulfate, the following selenium sensitizer and Compound I to perform spectral sensitization and chemical sensitization. The termination of chemical sensitization was performed using the following mercapto compounds. At this time, the amounts of the spectral sensitizing dye and the chemical sensitizer were adjusted so that the sensitivity of the emulsion at 1/100 second exposure was maximized. When the final grain of Emulsion 1-E was observed with a scanning electron microscope, silver halide epitaxy was mainly observed at the grain corners and grain edges.

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[0240]

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

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

[0243]

[Table 1]

[0244]

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[0245]

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<Preparation of Dye Composition for Filter Layer> The dye compositions for the yellow, magenta and cyan filter layers were prepared and added as emulsified dispersions as described below. Table 2
The oil phase component and the water phase component having the compositions shown in
Make a homogeneous solution at 0 ° C. The oil phase component and the aqueous phase component are combined, and 10,000 r. p. m. For 5 minutes. To the resulting emulsified dispersion, warm water in an amount shown in Table 2 was added as post-water, and 2000 r. p. m.
For 5 minutes.

[0247]

[Table 2]

[0248]

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These dispersions and emulsions 1-A to 1-E were used for the high-sensitivity layer of the magenta color-forming layer, and were combined with antifoggants A to E shown in Table 3 below. It is prepared in the same manner as in the preparation of a tabular emulsion described in No. 1-322931, the grain size is adjusted, and the spectral sensitizing dyes for blue-sensitive and red-sensitive emulsions are shown below. , VI, VII and sensitizing dyes IV for blue-sensitive emulsions, except that emulsions A to F other than the high-sensitivity layer of the magenta color-forming layer were used. Produced. The antifoggant was added during the preparation of the coating solution (in addition, samples 101 to 101).
See Table 8 below for a breakdown of 125).

[0250]

[Table 3]

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[0252]

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[0253]

[Table 4]

[0254]

[Table 5]

[0255]

[Table 6]

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The emulsions A to F used are shown in Table 5 below.

[0258]

[Table 7]

The prepared sample was stored at 25 ° C. and a relative humidity of 65% for 7 days and then cut.

Next, processing materials P-1 shown in Table 6 below were produced.

[0261]

[Table 8]

[0262]

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Further, a processing material P-2 shown in Table 7 below was prepared.

[0264]

[Table 9]

[0265]

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The photosensitive materials of Samples 101 to 125 were exposed to light at 1000 lux for 1/100 second through an optical wedge.
15 ml / m ² of warm water of 40 ° C. is applied to the surface of the photosensitive material after exposure.
After applying, the processing material P-1 and the respective film surfaces were overlapped with each other, the resultant was thermally developed at 83 ° C. for 17 seconds using a heat drum. When the photosensitive material was peeled off after the processing, a gray wedge-shaped image was obtained. The sample exposed using the blue filter has a wedge-shaped image of yellow color, the sample exposed with the green filter has a wedge-shaped image of magenta color, and the sample exposed with the red filter has a wedge-shaped image of cyan color. An image was obtained. The processing material P-
Using No. 2, the second process (fixing process) was performed. In the processing of the second step, 10 cc / m ² of water is applied to the processing material P-2, and the processing material P-2 is bonded to the photosensitive material after the first processing.
Heated at 60 ° C. for 30 seconds. The transmission density of the obtained color sample was measured with a green filter to obtain a so-called characteristic curve. The reciprocal of the exposure corresponding to the density 0.15 higher than the fog density was defined as the relative sensitivity, and was expressed as a relative value with the value of sample 101 being 100. Also, the highest color density and the lowest color density were shown. Table 8 shows the results.

[0268]

[Table 10]

As is evident from the results, simply using a tabular emulsion having a small grain thickness results in high fog and good discrimination cannot be obtained. Only by using the mercapto compound in the present invention, a sample having high sensitivity and good discrimination with little fog can be obtained.

Example 2 A sample was prepared in the same manner as in Example 1 except that the support was changed to the support manufactured by the following method. Further, a test similar to that of Example 1 was performed, but similarly good results were obtained, and the effect of the present invention was confirmed. 1) Support The support used in this example was produced by the following method.

100 parts by weight of polyethylene-2,6-naphthalate polymer and Tinuvin P.326 as an ultraviolet absorber
After drying 2 parts by weight (manufactured by Ciba-Geigy) and melting at 300 ° C., it was extruded from a T-die, and
The film was longitudinally stretched 3.3 times at 40 ° C., then transversely stretched 3.3 times at 130 ° C., and heat-set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. The PEN film has a blue dye, a magenta dye and a yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I-26 described in Japanese Patent Publication No. 94-6023). 27, II-5) was added in an appropriate amount. Further, the support was wound around a stainless steel winding core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled.

2) Coating of Undercoat Layer The support was subjected to a corona discharge treatment, a UV discharge treatment and a glow discharge treatment on both surfaces thereof, and then 0.1 g of gelatin was applied.
/ M ^2, Sodium α- Suruhoji-2-ethylhexyl succinate 0.01 g / m ^2, salicylic acid 0.04 g /
m ² , 0.2 g / m ^{2 of} p-chlorophenol, (CH ₂
= CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.01
2 g / m ² , and an undercoat solution of polyamide-epichlorohydrin polycondensate 0.02 g / m ² was applied (10 cc /
m ² , using a bar coater), and an undercoat layer was provided on the surface on which the photosensitive layer was provided. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

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

3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm has a specific resistance of 5 Ω · cm, a dispersion of fine particle powder (secondary aggregated particle diameter of about 0.08 μm). ) and 0.2 g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 C
H ₂ NHCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 10) oxyethylene-p-nonylphenol 0.0
Coated with 05 g / m ² and resorcin.

3-2) 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, surface treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06 g
/ M ² of diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was carried out with an open kneader and a sand mill),
C ₂ H ₅ C (CH ₂ CONH—C ₆ H ₃ —
(CH ₃ ) NCO) ₃ was applied by a bar coater using 0.3 g / m ² of acetone, methyl ethyl ketone, cyclohexanone and dibutyl phthalate as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. C ₆ H ₁₃ as a lubricant
CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ 50 mg / m ² ,
Abrasive aluminum oxide (0.20 μm and 1.0 μm) coated with silica particles (1.0 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) as a matting agent ) was added in an amount of 50 mg / m ² and 10 mg / m ^2, respectively. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.). Saturation magnetization moment of the X- light (blue filter) The increase of the color density of about 0.1 D _B of the magnetic recording layer in, also the magnetic recording layer is 4.2 emu / g, coercive force was 7.3 × 10 ⁴ A / M, and the squareness ratio was 65%.

3-3) Preparation of Sliding Layer Hydroxyethylcellulose (25 mg / m ² ), C _{6
H 13 CH (OH) C 10} H 20 COOC 40 H 81 (6mg / m
² ) 1.5 kg / m ² of silicone oil BYK-310 (manufactured by BYK Japan KK) 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) and then added. Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.).
° C). The sliding layer had an excellent dynamic friction coefficient of 0.10 (5 mmφ stainless steel hard ball, load of 100 g, speed of 6 cm / min), static friction coefficient of 0.08 (clip method), and a dynamic friction coefficient of 0.15 between the emulsion surface and the sliding layer. Characteristics.

Example 3 The same procedures as in Example 1 were carried out except that the emulsion 1 was used in the high-sensitivity layer of the magenta coloring layer.
Instead of using -A to 1-E, an emulsion was prepared in which the sensitizing dyes of Emulsions 1-A to 1-E were replaced with sensitizing dye IV for blue-sensitive emulsion, and this was used as a yellow-sensitive layer. A sample was prepared in the same manner as in Example 1 except for using this. Furthermore, when the same evaluation as in Example 1 was performed, good results were obtained, and the effect of the present invention was confirmed. Further, in Example 1, instead of using the emulsions 1-A to 1-E in the high-sensitivity layer of the magenta coloring layer, the sensitizing dyes of the emulsions 1-A to 1-E were replaced with the sensitizing dye V for a red-sensitive emulsion.
Samples were prepared in the same manner as in Example 1 except that emulsions were prepared in the same manner as in Example 1 except that the emulsions were replaced by the emulsions VII to VII. Furthermore, when the same evaluation as in Example 1 was performed, good results were obtained, and the effect of the present invention was confirmed.

Example 4 In the emulsions 1-A to 1-E, the grain size was adjusted so that the average sphere equivalent diameter was 0.65 μm for the medium-speed layer and 0.49 μm for the low-speed layer. Prepared sensitizing dyes as sensitizing dyes I to III for green-sensitive emulsion, sensitizing dye I for blue-sensitive emulsion
V, green-sensitive, blue-sensitive and red-sensitive emulsions for the high-sensitivity layer and low-sensitivity layer were prepared in place of the sensitizing dyes V to VII for the red-sensitive emulsion, respectively. Samples were prepared in the same manner as in Example 2 except for using these emulsions. Further, the same evaluation as in Example 2 was performed, but good results were obtained, and the effect of the present invention was confirmed.

Example 5 In Example 1 of JP-A-9-112265, emulsions 1-A to 1-E of Example 1 of the present invention were used in place of the photosensitive silver halide emulsion (4). A sample was prepared by combining the antifoggants A to E of Example 1 and evaluated in the same manner as in Example 1 of the present invention. However, good results were obtained, and the effect of the present invention was confirmed.

Example 6 Sample 125 produced in Example 2 and a color negative film Super G Ace manufactured by Fuji Photo Film Co., Ltd.
400 was exposed in the same manner as in Example 1 and processed in the following color negative processing steps. The processing solution used had been subjected to a running process until the replenishment amount of the color developing solution was three times that of the mother liquor.

(Processing step) Step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 37.8 ° C. 20 ml 10 liter Bleaching 45 seconds 38.0 ° C. 5 ml 5 liters Fixing (1) 45 seconds 38.0 ° C. -5 liters fixed (2) 45 seconds 38.0 ° C 30ml 5 liters stable (1) 20 seconds 38.0 ° C-5 liters stable (2) 20 seconds 38.0 ° C-5 liters stable (3) 20 seconds 38. 0 ℃ 40ml 5 liter Dry 1 minute 55 ℃ -5 liter

In the above process, * 1: The replenishment amount is 35 mm width, 1.1 m (24E
x. * 2: Fixing is a countercurrent method from step (2) to step (1). * 3: Stability is a countercurrent method from step (3) to step (1). The amount brought into the bleaching step and the amount brought into the stabilizing step of the fixing solution were 2.5 ml and 2.0 m, respectively, per 1 m of the length of the photosensitive material having a width of 35 mm.
l.

The composition and pH of each of the above-mentioned treatment solutions are shown below. (Color developing solution) Replenisher for tank solution-Diethylenetriaminepentaacetic acid 5.0 g 6.0 g-Sodium sulfite 4.0 g 5.0 g-Potassium carbonate 30.0 g 37.0 g-Potassium bromide 1.3 g 0.5 g-Iodide Potassium 1.2 mg-・ Hydroxylamine sulfate 2.0 g 3.6 g ・ 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.7 g 6.2 g ・ Water In addition 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.10.15

(Bleaching solution) Tank solution Replenisher • Ferric ammonium 1,3-diaminopropanetetraacetic acid monohydrate 144.0 g 206.0 g • 1,3-Diaminopropanetetraacetic acid 2.8 g 4.0 g • Odor Ammonium fluoride 84.0 g 120.0 g Ammonium nitrate 17.5 g 25.0 g Ammonia water (27%) 10.0 g 1.8 g Acetic acid 51.1 g 73.0 g Potassium carbonate 10.0 g 1.0 liter 1.0 liter pH (adjusted with ammonia water and acetic acid) 4.3 3.4

(Fixing solution) Common to tank solution and replenisher ・ 1.7 g of disodium ethylenediaminetetraacetate ・ 14.0 g of sodium sulfite ・ 10.0 g of sodium bisulfite ・ 210.0 ml of aqueous solution of ammonium thiosulfate (700 g / liter) ・ Thiocyan 163.0 g of ammonium acid ・ 1.8 g of thiourea ・ 1.0 liter with addition of water pH 6.5

(Stabilizing solution) Common to tank solution and replenisher ・ Surfactant [C ₁₀ H ₂₁ —O— (CH ₂ CH ₂ O) ₁₀ —H] 0.2 g ・ Polymaleic acid (average molecular weight 2,000) 0.1 g, 1,2-benzisothiazolin-3-one 0.05 g, hexamethylenetetramine 5.5 g, water is added, and 1.0 liter pH 8.5 is added.

The processed samples were measured in the same manner as in Example 1, and the yellow, magenta, and cyan densities of the unexposed portions of each sample were determined. The results are shown in Table 9 below.

[0288]

[Table 11]

From the results in Table 9, it can be seen that even when the light-sensitive material of the present invention was processed with a processing solution containing a developing agent / base, the unexposed portions of yellow, magenta, and cyan still had the density of Super G which is the current product. It was found that the value was close to Ace400. It was also found that the sensitivity, the maximum color density and the like were close to those of Super G Ace400.

[0290]

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

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/83 G03C 1/83 7/305 7/305 7/407 7/407

Claims (11)

[Claims] 1. A photosensitive silver halide emulsion comprising at least one layer comprising a photosensitive silver halide emulsion, a color developing agent, a compound capable of forming a dye by a coupling reaction with an oxidized form of the color developing agent, and a binder on a support. In a light-sensitive material provided with an emulsion layer and a non-light-sensitive layer, at least one of the light-sensitive silver halide emulsions has an average silver iodide content of 0.5 mol% or more and 20 mol% or less, At least one photosensitive silver halide emulsion layer in a light-sensitive material at a temperature of 25 ° C, comprising tabular silver halide grains having an average grain thickness of 0.01 to 0.3 µm;
a silver halide color photograph containing at least one mercapto compound having a common logarithm of a ratio (partition coefficient) of a dissolution concentration in butanol to a dissolution concentration in water at pH = 11 of 0.6 or more. Photosensitive material. 2. A light-sensitive silver halide emulsion layer comprising at least one light-sensitive silver halide emulsion layer, a color material capable of releasing or diffusing a diffusible dye corresponding to or inversely corresponding to silver development, and a binder on a support. And in a light-sensitive material having a non-light-sensitive layer in between, at least one of the light-sensitive silver halide emulsions has an average silver iodide content of 0.5 mol% to 20 mol%.
Mol% or less, comprising tabular silver halide grains having an average grain thickness of 0.01 to 0.3 .mu.m, and at least one photosensitive silver halide emulsion layer in the light-sensitive material, having a temperature of 25.degree. Characterized in that it contains at least one mercapto compound having a common logarithm of a ratio (partition coefficient) of a dissolution concentration in butanol to a dissolution concentration in water at pH = 11 of 0.6 or more. Color photographic light-sensitive material. 3. The common logarithm of the ratio (partition coefficient) of the concentration of a mercapto compound dissolved in butanol to the concentration dissolved in water at pH = 11 at a temperature of 25 ° C. is 0.1.
3. The silver halide color photographic light-sensitive material according to claim 1, wherein the number is 9 or more. 4. A mercapto compound represented by the following general formula (1)
3. A silver halide color photographic light-sensitive material according to claim 1, which is a compound represented by (2). Embedded image In the formula, Ra and Rb represent an alkyl group, an alkenyl group, an aralkyl group, an aryl or a heterocyclic group. Where Ra, R
The total number of carbon atoms of b is 14 or more. M represents a hydrogen atom, an ammonium or an alkali metal atom. Rc
Represents an aryl group. However, Rc has 10 or more carbon atoms. 5. The tabular silver halide grain is an epitaxial silver halide grain having at least one type of silver salt epitaxy formed on the surface of a host tabular grain, or a tabular silver halide grain having dislocation lines. The silver halide color photographic light-sensitive material according to any one of claims 1 to 4, wherein 6. A color developing agent represented by the following general formula (3):
6. The silver halide color photographic light-sensitive material according to claim 1, which is at least one of the compounds represented by the formula (7). Embedded image Embedded image Embedded image Embedded image Embedded image In the formula, R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group. Group, arylthio group, alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group , An alkylcarbonyl group, an arylcarbonyl group or an acyloxy group, and R ₅ represents an alkyl group, an aryl group or a heterocyclic group. Z represents a group of atoms forming an aromatic ring (including a heteroaromatic ring). When Z is a benzene ring, the total value of Hammett constant (σ) of the substituent is 1 or more. R ₆ represents an alkyl group. X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom. R ₇ and R ₈ represent a hydrogen atom or a substituent, and R ₇ and R ₈ may combine with each other to form a double bond or a ring. 7. The silver halide color photographic light-sensitive material according to claim 1, wherein the average grain thickness of the tabular silver halide grains is 0.01 to 0.2 μm. 8. The silver halide color photographic light-sensitive material according to claim 1, wherein the average grain thickness of the tabular silver halide grains is 0.01 to 0.1 μm. 9. The silver halide color photographic light-sensitive material according to claim 1, wherein the mercapto compound is contained in an emulsion layer containing tabular silver halide grains. 10. The light-sensitive material contains a dye which is decolorized by a reaction with a decoloring agent at the time of development processing, the dye is diffusion-resistant, and at least a part of the dye which has been decolorized after the development processing is used. 10. Anti-diffusion property.
A silver halide color photographic light-sensitive material according to any one of the above. 11. A processing material in which a constituent layer containing a processing layer containing a base and / or a base precursor is coated on a support after exposing the photosensitive material, and a back layer of both the processing material and the processing material are excluded. Water corresponding to 1/10 to 1 time of the total amount of water required for the maximum swelling of the entire coating film is present between the surface of the photosensitive silver halide emulsion layer of the photosensitive material and the surface of the processing layer of the processing material. Attach the photosensitive silver halide emulsion layer surface to the processing layer
The silver halide color photographic light-sensitive material according to any one of claims 1 to 10, wherein an image is formed by heating at a temperature of 0C or less for 5 seconds to 60 seconds.