JPH0682998A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material improved in storage stability and reduced in stains due to coor fog on the white background. CONSTITUTION:The silver halide color photographic sensitive material contains the compound to be allowed to release an elutable dye by coupling with the oxidation product of a color developing agent and this compound is represented by general formula in which R is a nonmetallic atomic group necessary to form a hetero cyclic ring together with -C(=N-)-; each of Y and Z is H, or an aliphatic residue, an aromatic residue, or a heterocyclic residue; and X is a diffusion-resistant group to be released when the compound of formula I reacts with the oxidation product of the color developing agent and forms the elutable dye.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having an improved white background.

[0002]

2. Description of the Related Art In a color-reducing color photographic light-sensitive material, a technique for suppressing unnecessary color fog that occurs during color development is an important technique for controlling image quality. Above all, it is particularly important to improve the white background of the reflective light-sensitive material, and a method of adding various hydroquinones to the light-sensitive material for this purpose has been known for a long time, and US Pat. No. 2,728,659 is known.
Issue 3, Issue 3, 700, 453, Issue 2, 360, 290
And Japanese Patent Publication Nos. 56-40816 and 56-21145.

In recent years, the demand for improvement of white background has increased,
There has been a demand for more effective white background improvement techniques. In addition, there is an increasing demand for speeding up the development process of silver halide color photographic light-sensitive materials. However, speeding up the color development process is apt to cause color fog. The construction of technology is essential. One solution is to increase the amount of hydroquinone added. Although it is possible to use more active hydroquinone, these methods may change the performance of the silver halide emulsion.In particular, the silver halide light-sensitive material before development is stored under high temperature and high humidity conditions for a long time. In that case, it was found that there was a problem in terms of performance due to fogging and large disturbance in gradation. It is considered that the property of hydroquinone as a reducing agent adversely affected the silver halide emulsion, and it is a fatal problem for a compound that prevents color fog by a redox reaction with an oxidized product of a developing agent.

On the other hand, a compound which undergoes a coupling reaction with an oxidized product of a developing agent but does not form a dye or a water-soluble or alkali-soluble dye is formed by a coupling reaction with an oxidized product of a developing agent to substantially form a color image. Compounds that do not contribute to JP-A Nos. 62-171955 and 62-1956
52, 62-195654, 63-2050.
And Japanese Patent Application Laid-Open Nos. 1-129252 and 2-16542. These compounds have the effect of improving the graininess by adding them to the silver halide emulsion layer, and by adding them to the non-photosensitive layer, the oxidant of the developing agent which is excessively generated in the photosensitive layer causes other photosensitivity. It is known to prevent the occurrence of color turbidity by preventing the migration to the organic layer. In particular, in JP-A-62-195652, when a light-sensitive silver halide emulsion is used together with an internal latent image type silver halide emulsion and a compound which undergoes a coupling reaction with an oxidized product of a developing agent but does not contribute to color image formation, fog occurs. Although it is described that the graininess can be improved without deteriorating the above, these known compounds have not necessarily reached sufficient performance in terms of prevention of color fog, and further improvement was necessary. .

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material which is free from contamination of a white background due to color fog and is excellent in storage stability.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to contain a compound represented by the following general formula (I) which forms a efflux dye by a coupling reaction with an oxidant of a color developing agent. Achieved by a characteristic silver halide color photographic light-sensitive material. General formula (I)

[0007]

[Chemical 2]

In the formula, R represents a group of non-metal atoms necessary for forming a heterocycle together with -C (= N-)-, and Y and Z are a hydrogen atom, an aliphatic residue and an aromatic residue, respectively. Or X represents a heterocyclic residue, and X represents a diffusion-resistant group that is released when the compound represented by the general formula (I) reacts with an oxidized product of a color developing agent to form a efflux dye. . As a result of intensive studies by the inventors, the silver halide emulsion was not adversely affected, the coupling reaction with the oxidized product of the developing agent was fast,
In addition, the produced dye reaches a group of compounds having a property of quickly flowing out from the emulsion layer.

The compound represented by formula (I) of the present invention will be described in detail below. In the general formula (I), the heterocycle represented by the general formula (II) contains at least one nitrogen atom, but the remaining ring-forming atoms are all carbon atoms or some of them (for example, 1 to 2). ) A hetero atom, that is, a nitrogen atom, an oxygen atom or a sulfur atom may be substituted. The basic heterocycle thus formed is preferably a 5- to 7-membered ring. These heterocycles may have a substituent or may have another condensed ring. These fused rings may be further substituted. General formula (II)

[0010]

[Chemical 3]

Y and Z are a hydrogen atom and a carbon number of 1 to 1, respectively.
10 linear, branched or cyclic alkyl groups (for example, methyl, ethyl, isopropyl, 1-butyl, t-butyl, 2-methanesulfonylethyl, trifluoromethyl, cyclopentyl, cyclohexyl), C6 to C1
0 aryl groups (eg, phenyl, p-tolyl, 4-
t-butylphenyl, 4-chlorophenyl, 4-nitrophenyl, 4-ethoxyphenyl, 1-naphthyl), a heterocyclic group having 1 to 10 carbon atoms (for example, 2-thienyl, 4
-Pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl) and the like. Y and Z may combine with each other to form a 5- to 7-membered ring together with the nitrogen atom. The ring represented by the general formula (II) and Y and Z may further have a substituent, and preferable substituents include a halogen atom (for example, a fluorine atom and a chlorine atom), an aliphatic group (carbon Number 1-6
A linear, branched or cyclic alkyl group, aralkyl group, alkenyl group, alkynyl group, such as methyl, ethyl, isopropyl, 1-butyl, t-butyl, 2-methanesulfonylethyl, trifluoromethyl, cyclopentyl), Aryl group (an aryl group having 10 or less carbon atoms, for example, phenyl, p-tolyl, 4-t-butylphenyl, 4-chlorophenyl, 4-nitrophenyl, 4
-Ethoxyphenyl, 1-naphthyl), a heterocyclic group (for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-
Pyrimidinyl, 1-pyridyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (alkoxy group having 1 to 6 carbon atoms, for example, methoxy, ethoxy, 1-butoxy), aryloxy group (for example, phenoxy, 4-methoxyphenoxy, 4-nitrophenoxy, 3-butanesulfonamidophenoxy, 2-naphthoxy), heterocyclic oxy group (eg, 2-furyloxy), acyloxy group (eg, acetoxy, pivaloyloxy, benzoyloxy), alkoxycarbonyl Oxy group (eg, ethoxycarbonyloxy, t-butoxycarbonyloxy), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy) carbamoyloxy group (eg, N, N-dimethylcarbamoyloxy, N-butyl Carbamoyloxy), a sulfamoylamino group (e.g., N, N- diethyl-sulfamoyloxy, N- propyl-sulfamoyl-oxy)
Sulfonyloxy group (eg, methanesulfonyloxy, benzenesulfonyloxy), acyl group (eg,
Acetyl, pivaloyl, benzoyl), alkoxycarbonyl group (eg, ethoxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl),

Carbamoyl group (eg, N, N-dimethylcarbamoyl, N-propylcarbamoyl), amino group (eg, amino, N-methylamino, N, N-dimethylamino), anilino group (eg, N-methylanilino) , Heterocyclic amino groups (eg, 4-pyridylamino), amide groups (eg, acetamide, benzamide, trifluoroacetamide), alkoxycarbonylamino groups (eg, isobutyloxycarbonylamino, ethoxycarbonylamino), aryloxycarbonylamino groups (For example, phenoxycarbonylamino), a ureido group (for example, N-phenylureido,
N, N-dimethylureido), a sulfonamide group (for example, methanesulfonamide), a sulfamoylamino group (for example, N, N-dimethylsulfamoylamino),
Alkylthio group (eg, ethylthio), arylthio group (eg, phenylthio), sulfinyl group (eg, benzenesulfinyl), sulfonyl group (eg,
Methanesulfonyl, p-toluenesulfonyl), a sulfamoyl group (for example, N, N-dimethylsulfamoyl, N-ethylsulfamoyl), and a sulfo group. Of the above-mentioned substituents, particularly preferable substituents are halogen atom, acyloxy group, amide group, alkoxycarbonylamino group, sulfonamide group, sulfo group, sulfamoyl group, carboxyl group, alkoxycarbonyl group, hydroxyl group or the following general groups. It is a group having a divalent group represented by the formula (III).

General formula (III) --A ₁ --NH--A ₂ --wherein A ₁ and A ₂ represent --SO ₂ -or --CO--. In particular, sulfonamide group, sulfo group, sulfamoyl group. A group having a carboxyl group, an alkoxycarbonyl group, a hydroxyl group and a divalent group represented by the general formula (III) is formed by reacting a compound represented by the general formula (I) with an oxidized product of a developing agent. It is preferable in terms of enhancing the outflow of the dye.

The preferable ranges of X, Y, Z and the ring represented by the general formula (II) will be described below. Y is preferably a substituted or unsubstituted phenyl group or alkyl group. Y may further have a substituent, but the total number of carbon atoms including the substituent is preferably 18 or less,
More preferably, it is 12 or less. When Y has a substituent, preferred substituents are halogen atom, nitro group, alkyl group, alkoxy group, acyloxy group, amide group, alkoxycarbonylamino group, sulfonamide group, sulfo group, sulfamoyl group, carboxyl group, alkoxycarbonyl. A group having a group, a hydroxyl group and a group represented by the general formula (III). Z is preferably a hydrogen atom or an alkyl group having 10 or less carbon atoms. Z may further have a substituent, but the total number of carbon atoms including the substituent is 15
It is preferably 10 or less, more preferably 10 or less. Among the rings represented by the general formula (II), preferred ones are those represented by the general formulas (a), (b), (c), (d), (e),
The rings are (f), (g), (h), (I), (j), and (k).

[0015]

[Chemical 4]

[0016]

[Chemical 5]

In the formula, Q ₀ represents a substituted or unsubstituted 1,2-fused benzene ring. Preferred as Q ₁ is a hydrogen atom,
C1-C10 alkyl group, substituted alkyl group (for example, methyl, methoxyethyl, chloroethyl), C7-
10 aralkyl groups (eg benzyl, phenethyl),
It is an aryl group having 6 to 10 carbon atoms (eg, substituted phenyl such as phenyl, tosyl, chlorophenyl), and particularly preferable is a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. Substituents on Q ₀ and R ₁ , R ₂ , R ₃ , R ₄
Are preferred as the hydrogen atom and the preferred substituents on Y.

The group represented by X in the general formula (I) is a group which is released when the compound represented by the general formula (I) reacts with an oxidized product of the developing agent, and is a group represented by the general formula (I) before the reaction. It is a group that imparts diffusion resistance to the compound represented by. Preferred as X is an imide group bonded to the coupling position at a nitrogen atom (eg, 2,4-dioxo-1,3-imidazolidin-3-yl, 2,4-dioxo-1,3-oxazolidine-3-. Yl, 3,5-dioxo-1,2,4
-Triazolidin-4-yl, succinimide, phthalimide, 2,4-dioxo-1,3-imidazolidine-
1-yl), an unsaturated nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom (for example, 1-imidazolyl, 1-
Pyrazolyl, 1,2,4-triazol-1-yl,
1,2,4-triazol-4-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-2
-Yl, benzotriazol-1-yl, benzotriazol-2-yl, 3-pyrazolin-5-one-1-yl) or aryloxy groups (eg phenoxy, 1
-Naphthoxy), and these groups preferably further have a substituent having 8 or more carbon atoms. Preferred substituents are an alkyl group (for example, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl), an aryl group (for example, 4-dodecyloxyphenyl), a heterocyclic group (for example, 4-decyl-1-pyrazolyl), an alkoxy group. (For example, dodecyloxy, tetradecyloxy,
Octadecyloxy), aryloxy groups (eg 4
-T-octylphenoxy), an acyloxy group (for example, tetradecanoyloxy), an alkoxycarbonyloxy group (for example, hexadecyloxycarbonyloxy),

Aryloxycarbonyloxy group (eg 4-nonylphenoxycarbonyloxy), carbamoyloxy group (eg N-dodecylcarbamoyloxy), sulfamoyloxy group (eg N-octadecylsulfamoyloxy), sulfonyl Oxy group (eg, dodecylbenzenesulfonyloxy), acyl group (eg, tetradecanoyl, hexadecanoyl), alkoxycarbonyl group (eg, dodecyloxycarbonyl, hexadecyloxycarbonyl), aryloxycarbonyl group (eg, 4- t-octylphenoxycarbonyl), a carbamoyl group (for example, N-
Dodecylcarbamoyl), amino group (for example, 3-
(2,4-di-t-aminophenoxy) propylamino), anilino group (for example, N-decylanilino), amide group (for example, tetradecane amide, octadecanamide), alkoxycarbonylamino group (for example, dodecyloxycarbonylamino) , An arylonoxycarbonylamino group (for example, 4-dodecylphenoxycarbonylamino), a ureido group (for example, N-decylureido), a sulfonamide group (for example, dodecylbenzenesulfonamide), a sulfamoylamino group (for example,
N, N-dioctylsulfamoylamino), alkylthio group (for example, dodecylthio, tetradecylthio, hexadecylthio), arylthio group (for example, 2-butoxy-5-t-octylphenylthio), sulfinyl (for example, dodecylbenzene) Sulfinyl) group, sulfonyl group (for example, hexadecanesulfonyl, dodecylbenzenesulfonyl), sulfamoyl group (for example, N,
N-dioctylsulfamoyl).

Specific examples of preferable X are shown below, but the present invention is not limited thereto.

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Chemical 8]

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

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

[0029]

[Chemical 13]

Synthesis Example Synthesis of Exemplified Compound (1) The compound was synthesized by the following synthetic route.

[0031]

[Chemical 14]

25.0 g (200 mmol) of the compound (1-a) is dissolved in 100 ml of meconol, and 43.0 g (220 mmol) of the compound (1-b) is added with stirring. After stirring at room temperature for 3 hours, the mixture is poured into water, extracted with ethyl acetate, the organic layer is washed with water, dehydrated and concentrated under reduced pressure. Compound (1-c) (41.8 g, 200 mmol) was added thereto, and the pressure was reduced by an aspirator at 170 ° C.
Stir for 4 hours. After cooling to 100 ° C., it was dissolved in 30 ml of N, N-dimethylformamide (DMF), allowed to cool to room temperature, and 200 ml of ethyl acetate was added.
Precipitate crystals. The crystals are collected by filtration and washed with ethyl acetate to obtain the compound (1-d) (17.0 g, 22%). 9 g (23.4 mmol) of compound (1-d) was dissolved in 30 ml of N, N-dimethylacetamide (DMAc),
3.16 g (23.4 mol mol) of sulfuryl chloride was added to 20
Drip over a period of minutes. After stirring at room temperature for 1 hour, the mixture is poured into water, extracted with ethyl acetate, the organic layer is washed with water, dehydrated and concentrated under reduced pressure. Dissolve this in 20 ml DMAc,
12.1 g (28.1 mmol) of compound (1-e) was added to 4
It was dissolved in 0 ml of DMAc, 8.55 g (56.2 mmol) of 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) was added, and the mixture was added dropwise while stirring. The reaction solution is stirred at 60 ° C. for 3 hours, poured into hydrochloric acid water, and extracted with ethyl acetate. After washing the organic layer with water,
After dehydration, concentration under reduced pressure, and purification by silica gel column, compound (1-f) (12.0 g, 63%) is obtained as a solid. Compound (1-f) (4.0 g, 4.92 mmol) was dissolved in isopropyl alcohol (20 ml), sodium hydroxide (760 mg, 17.7 mmol) was dissolved in water (2 ml), and the mixture was stirred for 1 hour. Pour and extract with ethyl acetate. The organic layer is washed with water, dried, concentrated under reduced pressure, and purified with a silica gel column to obtain the exemplary compound (1) (2.78 g, 72%) as a solid.

The amount of the compound represented by formula (I) of the present invention used in a silver halide color photographic light-sensitive material is in the range of 0.5 to 50 mol% based on the color image forming coupler used in the same layer. And preferably 1.0 to 10 mol%.

The silver halide grains of the silver halide emulsion which can be used in the light-sensitive material of the present invention are silver chloroiodide, silver iodobromide and silver chloroiodobromide. Other silver salts such as silver rhodanide, silver sulfide, silver selenide, silver carbonate, silver phosphate and silver organic acid may be contained as separate grains or as a part of silver halide grains. It is important to control the halogen composition near the surface of the grain. Increasing the silver iodide content in the vicinity of the surface or increasing the silver chloride content can change the adsorbability of the dye and the developing rate and can be selected according to the purpose. When changing the halogen composition near the surface,
Either a structure that encloses the entire particle or a structure that adheres only to a part of the particle can be selected. For example (10
This is the case where the halogen composition is changed only on one surface of the tetrahedral grain composed of the (0) plane and the (111) plane, or on one of the main plane and the side surface of the tabular grain.

The silver halide grains of the emulsion that can be used in the light-sensitive material of the present invention, even if it is a normal crystal that does not contain twin planes, are edited by The Photographic Society of Japan, Fundamentals of the Photographic Industry, Silver Salt Photography (Corona Publishing Co.), P. 163, eg, single twin containing one twin plane, parallel multiple twin containing two or more parallel twin planes, non-parallel containing two or more non-parallel twin planes. It can be selected and used from multiple twins and the like according to the purpose. An example of mixing particles having different shapes is disclosed in US Pat. No. 4,865,964, but this method can be selected as necessary. In the case of a normal crystal, a cube having a (100) plane, an octahedron having a (111) plane, JP-B-55-42737, and JP-A-60-222.
The dodecahedral grains having the (110) plane disclosed in No. 842 can be used. In addition, the Journal of Ima
ging Science, Vol. 30, p. 247, (h11) plane particles typified by (211), (hh1) plane particles typified by (331), and (2) as reported in 1986.
The (hk0) plane particles typified by the 10) plane and the (hk1) plane particles typified by the (321) plane may be selected and used according to the purpose although the preparation method requires some contrivance. A tetrahedral grain in which the (100) plane and the (111) plane coexist in one grain,
Depending on the purpose, particles having two or many surfaces such as particles having both (100) surface and (110) surface or particles having both (111) surface and (110) surface may be selected and used according to the purpose. You can

A value obtained by dividing the circle-equivalent diameter of the projected area by the grain thickness is called an aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio of more than 1 can be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Practice (19
30)), p. 131; Gatov, Photographic Science and Engineering (Gutoff, Photogr.
aphic Science and Engineering), Volume 14, 248
~ 257 (1970); U.S. Pat. No. 4,434,2.
No. 26, No. 4,414, 310, No. 4,433, 04
No. 8, 4,439,520 and British Patent No. 2,1.
It can be prepared by the method described in No. 12,157. When tabular grains are used, the covering power increases,
The sensitizing dye has advantages such as an increase in color sensitization efficiency, which is described in detail in the above-cited US Pat. No. 4,434,226. The average aspect ratio of 80% or more of the total projected area of the grains is preferably 1 or more and less than 100. It is more preferably 2 or more and less than 20, and particularly preferably 3 or more and less than 10. The shape of tabular grains can be selected from triangles, hexagons, circles, and the like. A regular hexagon with approximately six sides of equal length, as described in U.S. Pat. No. 4,797,354, is a preferred form. The equivalent circle diameter of the tabular grains is preferably 0.15 to 5.0 μ. The thickness of the tabular grains is preferably 0.05 to 1.0 µ.

The tabular grains preferably account for 50% or more, more preferably 80%, and particularly preferably 90% of the total projected area of tabular grains having an aspect ratio of 3 or more.
% Or more.

Further, more preferable results may be obtained by using monodisperse tabular grains. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A-63-151618.
According to the description of No. etc., but its shape is simply stated, 70% or more of the total projected area of silver halide grains is such that the length of the side having the maximum length with respect to the length of the side having the minimum length. Of hexagons with a ratio of 2 or less and parallel 2
The hexagonal tabular silver halide grains are occupied by tabular silver halide having an outer surface as the outer surface, and the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains (the variation in grain size represented by the circle-converted diameter of the projected area (standard Deviation) divided by the average particle size) has a monodispersity of 20% or less.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select particles containing no dislocation lines, particles containing several dislocations or particles containing many dislocations according to the purpose. It is also possible to select a dislocation or a curved dislocation introduced linearly with respect to a specific direction of the crystal orientation of the particles, or to introduce the dislocations throughout the particles or only in a specific part of the particles, for example, The dislocation can be introduced only in the fringe portion of the grain. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of regular grains or amorphous grains typified by potato grains. In this case as well, it is a preferable form to limit the particles to specific portions such as vertices and edges.

The silver halide emulsion used in the present invention is a treatment for rounding grains as disclosed in European Patent Nos. 96,727B1 and 64,412B1 or West German Patent No. 2,306,447C2. , JP Sho 60
The surface may be modified as disclosed in US Pat.

The grain size of the emulsion used in the present invention depends on the circle equivalent diameter of the projected area using an electron microscope, the sphere equivalent diameter of the grain volume calculated from the projected area and grain thickness, or the sphere equivalent diameter of the volume by the Coulter counter method. Can be evaluated. It can be used by selecting from ultrafine particles having a sphere-equivalent diameter of 0.05 micron or less, and coarse particles having a sphere-equivalent diameter of more than 10 microns. Preferably, grains having a size of 0.1 micron or more and 3 microns or less are used as the photosensitive silver halide grains.

The normal crystal emulsion used in the present invention may be a so-called polydisperse emulsion having a wide grain size distribution or a monodisperse emulsion having a narrow size distribution, and can be selected and used according to the purpose. As a scale representing the size distribution, the variation coefficient of the projected area circle diameter of particles or the sphere equivalent diameter of volume may be used. When using a monodisperse emulsion, the coefficient of variation is 25%
Or less, more preferably 20% or less, still more preferably 1
It is preferable to use an emulsion having a size distribution of 5% or less.

In some cases, the monodisperse emulsion is defined as a grain size distribution such that 80% or more of all grains fall within ± 30% of the average grain size in terms of number of grains or weight. In order to satisfy the target gradation of the light-sensitive material, the emulsion layers having substantially the same color sensitivity have different grain sizes.
One or more kinds of monodisperse silver halide emulsions can be mixed in the same layer or multi-layered in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The emulsion of the present invention and the photographic emulsion used in combination with it are described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P. Glafkides, Chemie et Phisique Photogra.
Phique, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Phot)
ographic Emulsion Chemistry (Focal Press, 196
6)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VLZelikman et al, Making and
Coating Photographic Emulsion, Focal Press, 19
64) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof or the like. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole. You can As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Photo.Japan. 16, p3
0 (1966), an enzyme-treated gelatin may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature for washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 ° C to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane,
It can be selected and used from a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the grains are doped, they are preferably added at the time of grain formation, when the grains are modified, or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Mg, Ca, Sr, Ba, Al, S
c, Y, La, Cr, Mn, Fe, Co, Ni, Cu,
Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides or hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example CdB
_{r 2, CdCl 2, Cd (} NO 3) 2, Pb (NO 3) 2,
Pb (CH ₃ COO) ₂ , K ₃ [Fe (CN) ₆ ], (N
H _{4) 4} [Fe (CN) _{6], K 3 IrCl 6, (NH} 4) 3
RhCl ₆ , K ₄ Ru (CN) _{6 and the} like can be mentioned. The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but may use two types or a combination of three or more types.

The silver halide grain of the present invention is subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or noble metal sensitization and reduction sensitization in any step of the silver halide emulsion production process. Can be applied with. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nuclei can be selected depending on the purpose, but it is generally preferable to form at least one chemically sensitized nucleus near the surface. Examples of the nucleating agent that can be used in the present invention include those described in Research Disclosure, No.
22534 (January 1983), pp. 50-54, No.
15162 (November 1976) pages 76-77, same magazine N
o. 23510 (November 1983) pp. 346-352, quaternary heterocyclic compounds, hydrazine compounds and the like. Two or more kinds of these nucleating agents may be used in combination. The nucleating agent used in the present invention is disclosed in JP-A-2-90154 or JP-A-3-155.
No. 543 publication. A quaternary heterocyclic compound represented by the formula (NI) or a hydrazine compound represented by the formula (N-II) described in JP-A-2-90154 or JP-A-3-95546. Is preferred.

Typical nucleating agents represented by the above formulas (NI) and (N-II) are as follows. (N-I-1) 7- (3-cyclohexylmethoxythiocarbonylaminobenzamide) -10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (N-I-2) 6- ( 3-Ethoxythiocarbonylaminobenzamido) -1-propargyl-2,3-trimethylenequinolinium trifluoromethanesulfonate (N-I-3) 6-ethoxythiocarbonylamino-
2-Methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-4) 7- [3- (5-mercaptotetrazol-1-yl) benzamide] -10-propargyl-1,2,3,4 -Tetrahydroacridinium perchlorate (N-II-1) 1-formyl-2- {4- [3- {3
-[3- (5-Mercaptotetrazol-1-yl) phenyl] ureido} benzsulfonamide] phenyl}
Hydrazine (N-II-2) 1-formyl-2- {4- [3- (5
-Mercaptotetrazol-1-yl) benzenesulfonamide] phenyl} hydrazine

In the present invention, it is preferable to use the quaternary heterocyclic compound and the hydrazine compound in combination. In the present invention, the addition amount of the nucleating agent varies depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent and the developing conditions, and therefore can be varied over a wide range. About 1 x 1 per mole of silver
A range of 0 ^-8 moles to about 1 x 10 ^-2 moles is practically useful, with about 1 x 10 ^-5 moles to about 1 x 10 moles per silver mole being preferred.
^-3 mol range. The nucleating agent may be added to the treatment liquid. In particular, it is effective when directly performing the fogging process on the positive color photographic light-sensitive material. In this case, it is preferable to add it to a low pH pre-bath as described in JP-A-58-178350. When the nucleating agent is added to the treatment liquid, the amount used is preferably 10 ^-8 to 10 ^-1 mol per liter of the treatment liquid, and 10 ^-7 to 10 ^-3.
Molar is more preferred.

In the present invention, the direct fog processing of the positive color photographic light-sensitive material is carried out in combination with the "chemical fog method" using the above nucleating agent or separately in the "light fog method".
You may carry out using. The overall exposure in the "light fog method", that is, fog exposure is performed after imagewise exposure, before color development processing or during color development processing. That is, the imagewise exposed light-sensitive material is exposed in a color developing solution or in a pre-bath of the color developing solution, or is taken out from these solutions and dried before being exposed. Is most preferred. As a light source for fogging exposure,
For example, JP-A-56-137350 and JP-A-58-702.
A light source having a high color rendering property (as close to white as possible) as described in JP-A No. 23 is preferable. The illuminance of light is 0.01-
2000 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux is suitable. The light-sensitive material using a higher-sensitivity emulsion is preferred to have low illuminance. The illuminance may be adjusted by changing the luminous intensity of the light source, or by changing the light exposure by various filters, the distance between the light-sensitive material and the light source, or the angle between the light-sensitive material and the light source. It is also possible to increase the illuminance of the fog light from low illuminance to high illuminance continuously or stepwise.
It is preferable to immerse the light-sensitive material in a color developing solution or a solution of its pre-bath so that the solution sufficiently penetrates into the emulsion layer of the light-sensitive material before irradiation with light. The time from the permeation of the liquid to the exposure to light fog is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, and more preferably 10 seconds to 30 seconds. The exposure time for fogging is generally 0.01 second to 2 minutes, preferably 0.1 second to 1 minute, more preferably 1 second to 40 seconds.

In the embodiment of the color photographic light-sensitive material of the present invention, particularly the direct positive color photographic light-sensitive material, it is preferable to use a nucleation accelerator. A nucleation accelerator does not substantially function as a nucleating agent, but is necessary for promoting the nucleation action to increase the maximum density of the direct positive image and / or to obtain a certain maximum density of the direct positive image. A substance that acts to accelerate the development time. In the present invention, Japanese Patent Laid-Open No. 2-8
The nucleation accelerator described in 9048 can be preferably used. The nucleation accelerator may be contained in either the silver halide emulsion layer or the adjacent non-photosensitive layer (intermediate layer, protective layer, etc.), but it is formed by using the specific protective colloid of the present invention. It is preferably contained in the emulsion layer containing the silver halide grains. The addition amount of the nucleation accelerator is preferably 10 ⁻⁶ to 10 ⁻² mol, and more preferably 10 ⁻⁵ to 10 ⁻² mol, per mol of silver halide. The nucleation accelerator may be contained in the processing solution (that is, the developing solution or the pre-bath thereof). In that case, the amount is 1 per liter of the processing solution.
0 ^-8 to 10 ^-3 mol is preferable, and 10 ^-7 is more preferable.
It is from 10 to ⁴ mol.

Known photographic additives that can be used in the present invention are described in Research Disclosure No. 17643
(December 1978) and the same No. 18716 (197
(November 1997), and the relevant parts are summarized in the table below. Additive type RD17643 RD18716 1. Chemical sensitizer, page 23, page 648, right column 2. Sensitivity enhancer, same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent page 24 5. Antifoggant, pages 24 to 25, page 649, right column ~ stabilizer, page 650, right column 6. Light absorber, page 25, right column, page 649, right column ~ filter dye, page 650, left column UV light Absorber 7. Anti-staining agent page 25 right column 8. Dye image stabilizer page 25 9. Hardener 26 pages 651 left column 10. Binder page 26 same as above

In the color photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are flexible supports commonly used in photographic light-sensitive materials such as plastic films, papers and cloths, or rigid such as glass, ceramics and metals. Is coated on a support. What is useful as the flexible support is a film, a baryter layer or an α-olefin polymer made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, and polycarbonate. Examples include paper coated or laminated with (eg, polyethylene, polypropylene, ethylene / butene copolymer).
The support may be colored with a dye or pigment. For coating the silver halide photographic emulsion layer and other hydrophilic colloid layers, various known methods such as dip coating method, roller coating method, curtain coating method and extrusion coating method can be used. Also, if necessary, US Patent No. 2
No. 681294, No. 2761791, No. 3526
Multiple layers may be simultaneously coated by the method described in each specification such as No. 528 and No. 3508947.

Next, a color image forming method using the color photographic light-sensitive material of the present invention will be described. The color image forming method of the present invention forms a color image by subjecting the above color photographic light-sensitive material to image exposure, and then performing development processing with a developer containing a specific color developing agent represented by the formula (D). It is characterized by The development processing method may be a conventionally known method. Various exposure means can be used for exposing the light-sensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination light source or the writing light source.
Natural light (sunlight), incandescent lamp, halogen atom sealed lamp, mercury lamp, fluorescent lamp and flash light source such as strobe or metal burning flash bulb or semiconductor laser,
Light emitting diodes and plasma light sources can also be used as recording light sources. In addition, a phosphor screen (CRT or the like) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LC
D) or lanthanum-doped lead titan zirconate (PLZT) or the like may be used as an exposure means in which a linear or planar light source is combined with a microshutter array. If necessary, the spectral distribution used for exposure can be adjusted with a color filter. Particularly, a high-density beam light such as various lasers such as a gas laser (He-Ne laser, Ar laser, He-Cd laser) and a semiconductor laser is used as a light source and is moved relatively to a photosensitive material. Image exposure by. Exposure means by a so-called scanning exposure method is preferable for exposing the light-sensitive material of the present invention. As the scanning exposure device, for example, a color copying machine AP-5000 manufactured by Fuji Photo Film Co., Ltd. can be used.

A scanner system such as DP460 manufactured by Dainippon Screen is also preferable. In the case of exposure by a scanning exposure method (scanner method), the time for exposing silver halide is the time required for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from digital data is generally used, and is called a pixel. Therefore, the exposure time per pixel varies depending on the size of the pixel. The size of this pixel depends on the pixel density, and is practically 50 to 2000 dpi. In the color photographic light-sensitive material of the present invention, the pixel size when the pixel density is 400 dpi is 1 pixel,
The exposure time per pixel is 10 ^-3 seconds or less (preferably,
Scan exposure is performed under the condition of 10 ⁻⁶ to 10 ⁻⁴ seconds).

An internal latent image type silver halide emulsion which has not been previously fogged is an emulsion in which the surface of the silver halide grains is not fogged and which contains a latent image mainly inside the grains. More specifically, a certain amount of silver halide emulsion (0.5-3 g /
m ² ), and exposed to light for a fixed time of 0.01 to 10 seconds, in the following developer (internal developer)
When developed at 0 ° C. for 5 minutes, the maximum density measured by a usual photographic density measuring method was the same as the above coating, and the silver halide emulsion exposed in the same manner was developed in the following developing solution (surface type developing solution). Those having a density at least 5 times higher than the maximum density obtained when developed at 18 ° C. for 6 minutes are preferable, and those having a density at least 10 times higher are more preferable. Internal type developer Metol 2.0 g Sodium sulfite (anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.8 g KBr 5.0 g KI 0.5 g Water-added 1000 ml Surface type developer Metol 2 0.5 g L-ascorbic acid 10.0 g NaBO ₂ .4H ₂ O 35.0 g KBr 1.0 g Water added 1000 ml

Specific examples of the internal latent image type silver halide emulsion include, for example, conversion type silver halide emulsions described in US Pat. No. 2,592,250; or US Pat. Nos. 3,761,276, 3,850,637 and 3,923,513. , 4035185 and 43954.
78, 4504570, JP-A-52-
No. 156614, No. 55-127549, No. 53-6
0222, 56-22681, 59-2085
No. 40, No. 60-107641, No. 61-1337.
No. 62-215272, German Patent No. 2332802c2, Research Disclosure No. 23510 (issued in November 1983)
Patent disclosed on page 236; Specification of U.S. Pat. No. 4,789,627, which further has a silver chloride shell; JP-A 63-10160 and 6 regarding silver chlorobromide core-shell emulsion.
JP-A-3-47766 and Japanese Patent Application No. 1-2467
The core / shell type silver halide emulsions described in JP-A-63-191145 and JP-A-1-52146 relating to emulsions doped with metal ions can be mentioned. The internal latent image type silver halide grains which have not been fogged in the present invention are preferably core / shell type. The molar ratio of the core and shell silver halide in the internal latent image type core / shell silver halide emulsion is 20/1 or less, and 1/100 or more is particularly preferable.

[0059]

【Example】

Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated to form a layer structure shown below. A multilayer color printing paper (101) was prepared. The coating liquid was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-3) 16.0 g, solvent (Solv-1) 25 g, solvent (Solv-2) 25
g and 180 cc of ethyl acetate, and the solution is 10%
An emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of a 10% gelatin aqueous solution containing 60 cc of sodium dodecylbenzenesulfonate and 10 g of citric acid. On the other hand, a silver chlorobromide emulsion A (a cube, a 3: 7 mixture of a large size emulsion A having an average grain size of 0.90 μm and a small size emulsion A having a grain size of 0.72 μm (silver molar ratio). The variation coefficient of the grain size distribution is , 0.08 and 0.10 respectively, and silver bromide 0.
3 mol% localized on a part of the particle surface) was prepared.
In this emulsion, blue-sensitive sensitizing dyes A and B shown below were added to the large-sized emulsion A per mol of silver of 2.0 ×, respectively.
10 ⁻⁴ , and for small size emulsion A, 2.
5 × 10 ⁻⁴ mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A are mixed and dissolved,
The first layer coating liquid was prepared so as to have the composition shown below.
The emulsion coating amount represents the coating amount in terms of silver.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. Also, Cpd-14 and C are added to each layer.
The total amount of pd-15 is 25.0 mg / m ² and 50 mg / m ² , respectively.
It was added so as to be m ² . The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

Further, 1- (5-methylureidophenyl) is added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
-5-Mercaptotetrazole was added in an amount of 8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol and 2.5 x 10 ^-4 mol per mol of silver halide, respectively. Further, 4-hydroxy-6-methyl- was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
1,3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0066]

[Chemical 15]

[0067]

[Chemical 16]

[0068]

[Chemical 17]

[0069]

[Chemical 18]

[0070]

[Chemical 19]

[0071]

[Chemical 20]

[0072]

[Chemical 21]

[0073]

[Chemical formula 22]

[0074]

[Chemical formula 23]

[0075]

[Table 4]

[0076]

[Table 5]

[0077]

[Table 6]

[0078]

[Table 7]

Preparation of Samples 102 to 107 Sample 101 except that the comparative compound A in the fifth layer was replaced with equimolar compounds shown in Table 8 in Sample 101.
Was prepared in the same manner as in.

Evaluation of Color Fog A sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) was applied to the sample prepared as described above.
Was subjected to gradation exposure through a three-color separation filter for sensitometry, and development processing was carried out by the processing step 1 described below. The density of the developed sample was measured, and the fog density value (cyan density) was used to evaluate the color fog. Evaluation of storability A sample which has been left standing under conditions of 50 ° C. and 80% Rh for 3 days and subjected to a aging test is subjected to exposure, development processing and density measurement in the same manner as above, and fog density value (cyan density), cyan color image I asked for the sensitivity of. The storage stability was evaluated by the fog density value before and after the aging test and the difference in sensitivity (value after the aging test-value before the aging test). The results are summarized in Table 8.

[0081]

[Table 8]

[0082]

[Chemical formula 24]

[Processing Step 1] After the above light-sensitive material was imagewise exposed, a continuous processing (running test) was carried out using a paper processor until replenishing twice the tank capacity for color development in the following processing step. . Treatment process Temperature Time Replenishment amount ^* Tank capacity Color development 38.5 ℃ 45 seconds 73 ml 20 liter Bleach fixing 35 ℃ 45 seconds 60 ml ^** 20 liter Rinse (1) 35 ℃ 30 seconds -10 liter Rinse (2) 35 ℃ 30 seconds −10 liters Rinse (3) 35 ℃ 30 seconds 360 milliliters 10 liters Dry 80 ℃ 60 seconds * Replenishment amount per 1 m ^{2 of} light-sensitive material ** In addition to the above 60 ml, from rinse (1) 120 per 1 m ^{2 of} light-sensitive material Pour milliliters.
(Rinse was a three-tank countercurrent system from (3) to (1))

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher] Water 800 ml 800 ml Ethylenediaminetetraacetic acid 3.0 g 3.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g 0.5 g Triethanolamine 12.0 g 12.0 g Potassium chloride 6.5 g-Potassium bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX 4 manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 3.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis (sulfo Natoethyl) hydroxylamine 5.0 g 10.0 g Sodium triisopropylnaphthalene (β) sulfone 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid / 1 Water salt 5.0g 11.5g Add water 1000ml 1000ml pH (25 ° C / hydroxide) (With sulphur and sulfuric acid) 10.00 11.00

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Water 600 ml 150 ml Ammonium thiosulfate (700 g / liter) 100 ml 250 ml Ammonium sulfite 40 g 100 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g 135 g Ethylenediaminetetraacetic acid 5g 12.5g Ammonium bromide 40g 75g Nitric acid (67%) 30g 65g Water added 1000 ml 1000 ml pH (at 25 ° C / acetic acid and ammonia water) 5.8 5.6

[Rinse Solution] (tank solution and replenisher are the same) Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

Example 2 Preparation of Sample 201 A paper support (thickness 10) laminated on both sides with polyethylene.
(0 micron), the following 1st to 14th layers were multilayer-coated and the 15th to 16th layers were coated on the back side to prepare a color photographic light-sensitive material. The polyethylene coated on the first layer contains titanium oxide (4 g / m ² ) as a white pigment and a trace amount (0.003 g / m ² ) of ultramarine blue as a bluing dye (the chromaticity of the surface of the support is L 88 in the ^* , a ^* , and b ^* systems.
It was 0, -0.20, -0.75. ).

(Photosensitive layer composition) The components and coating amount (g /
m ² unit). For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was produced according to the production method of Emulsion EM1. However, as the emulsion of the 14th layer, a Lippmann emulsion which was not surface-sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver 0.10 Color Mixing Inhibitor (Cpd-7) 0.05 Gelatin 0.70

Second layer (intermediate layer) gelatin 0.70

Third Layer (Low Sensitivity Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (average grain size 0.25 μ, grain size distribution [variation coefficient ] 8%, octahedron) 0.04 Silver chlorobromide (5 mol% silver chloride, spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3), average grain size 0.40μ, grain size) Distribution 10%, octahedron) 0.08 gelatin 1.00 cyan coupler (ExC-1, 2, 3 1: 1: 0.2) 0.30 anti-fading agent (Cpd-1, 2, 3, 4, 30 equivalents) 0.18 Anti-staining agent (Cpd-5) 0.003 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) 0.12

Fourth Layer (High-sensitivity Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (average grain size 0.60 μ, grain size distribution 15%, Octahedral) 0.14 Gelatin 1.00 Cyan coupler (ExC-1, 2, 3 1: 1: 0.2) 0.30 Anti-fading agent (Cpd-1, 2, 3, 4, 30 equivalents) 0.18 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) 0.12

Fifth Layer (Intermediate Layer) Gelatin 1.00 Color mixing inhibitor (Cpd-7) 0.09 Color mixing inhibitor solvent (Solv-4, 5 equivalents) 0.16 Polymer latex (Cpd-8) 0. 10

Sixth Layer (Low Sensitivity Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (average grain size 0.25 μ, grain size distribution 8%, octahedron) 0 .04 Silver chlorobromide spectrally sensitized with a green sensitizing dye (ExS-4) (5 mol% silver chloride, average grain size 0.40 μ, grain size distribution 10%, octahedron) 0.06 Gelatin 0 .80 Magenta coupler (ExM-1, 2, 3 equivalents) 0.11 Anti-fading agent (equal amounts of Cpd-9, 26, 30) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13) 10: 7: 7: 1 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6 equivalents) 0.15

Seventh Layer (High Sensitivity Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (average grain size 0.65 μ, grain size distribution 16%, octahedron) 0 .10 Gelatin 0.80 Magenta coupler (ExM-1, 2, 3 equivalents) 0.11 Anti-fading agent (Cpd-9, 26, 30 equivalents) 0.15 Anti-staining agent (Cpd-10, 11, 12) , 13 in a 10: 7: 7: 1 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6 equivalents) 0.15

8th layer (intermediate layer) Same as 5th layer

Ninth layer (yellow filter layer) Yellow colloidal silver (particle size 100Å) 0.12 Gelatin 0.70 Color mixing inhibitor (Cpd-7) 0.03 Color mixing inhibitor solvent (Solv-4, 5 equivalents) 0.10 Polymer latex (Cpd-8) 0.07

10th layer (intermediate layer) Same as 5th layer

Eleventh Layer (Low Sensitivity Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.42 μ, grain size distribution 8%, octahedron). 0.08 Silver chlorobromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (silver chloride 8 mol%, average grain size 0.61 μ, grain size distribution 11%, octahedron) 0.15 Gelatin 0.82 Yellow coupler (ExY-1, 2, 3 equivalents) 0.37 Anti-fading agent (Cpd-14) 0.10 Anti-fading agent (Cpd-30) 0.05 Comparative compound (A) 0.032 Anti-staining agent (Cpd-5, 15 in 1: 5 ratio) 0.004 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10.

Twelfth Layer (High Sensitivity Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.82 μ, grain size distribution 18%, octahedron). 0.15 Gelatin 0.61 Yellow coupler (ExY-1, 2, 3 equivalents) 0.28 Anti-fading agent (Cpd-14) 0.10 Anti-fading agent (Cpd-30) 0.05 Comparative compound (A) 0.02 Anti-staining agent (Cpd-5, 15 in 1: 5 ratio) 0.004 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.12

Thirteenth layer (UV absorbing layer) Gelatin 1.00 UV absorber (Cpd-2, 4, 16 equivalents) 0.50 Color mixing inhibitor (Cpd-7, 17 equivalents) 0.03 Dispersion medium ( Cpd-6) 0.02 UV absorber solvent (Solv-2, 7 equivalents) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 at 10: 10: 13: 15: 20) Ratio) 0.05

Fourteenth Layer (Protective Layer) Fine-grain silver chlorobromide (silver chloride 97 mol%, average size 0.1 μ) 0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight 50,000) 0.01 Polymethyl Methacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent 0.05 Gelatin 1.80 Gelatin hardening agent (H-1, H-2 equivalent) 0.18

Fifteenth layer (back layer) Gelatin 2.50 UV absorber (Cpd-2, 4, 16 equivalents) 0.50 Dye (Cpd-18, 19, 20, 21, 27 equivalents) 0. 06

Sixteenth Layer (Back Layer Protective Layer) Polymethylmethacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent 0.05 gelatin 2.00 Gelatin hardener (H- 1, H-2 equivalent) 0.14

Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 75 ° C. over 15 minutes with vigorous stirring,
Octahedral silver bromide grains having an average grain size of 0.35μ were obtained. At this time, 0.3 g of 3,4-dimethyl-1,3 per mol of silver was used.
-Thiazolin-2-thione was added. 1 silver in this emulsion
Chemical sensitization was carried out by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol and heating at 75 ° C. for 80 minutes. Using the particles thus obtained as a core, the particles are further grown in the same precipitation environment as the first time,
Finally, an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.7 µ was obtained. Coefficient of variation of particle size is about 10%
Met. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver.
The mixture was heated at 0 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

ExZK-1 is used as a nucleating agent in each photosensitive layer.
And ExZK-2 is 1 for each silver halide
0 ^-3, 10 ^-2 wt%, Cpd-22 as a nucleation accelerator,
28 and 29 were used at 10 ^-2 wt% each. Further, in each layer, alkanol XC (Dupont) and sodium alkylbenzenesulfonate were used as emulsification / dispersion aids, and succinic acid ester and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. (Cpd-23, 24, 25) was used as a stabilizer in the layer containing silver halide and colloidal silver. This sample was designated as sample number 201. The compounds used in the examples are shown below.

[0107]

[Chemical 25]

[0108]

[Chemical formula 26]

[0109]

[Chemical 27]

[0110]

[Chemical 28]

[0111]

[Chemical 29]

[0112]

[Chemical 30]

[0113]

[Chemical 31]

[0114]

[Chemical 32]

[0115]

[Chemical 33]

[0116]

[Chemical 34]

[0117]

[Chemical 35]

[0118]

[Chemical 36]

[0119]

[Chemical 37]

Preparation of Samples 202 to 207 The comparative compound A of the 11th and 12th layers in Sample 201
Sample 201 was prepared in the same manner, except that an equimolar compound shown in Table 9 was used instead. Evaluation of color fog A sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200 ° K) was applied to the sample manufactured as described above.
Was subjected to gradation exposure, and development processing was carried out in processing step 2 described below. The density of the developed sample was measured, and color fog was evaluated by the fog density value (yellow density). Evaluation of storability A sample subjected to a aging test by leaving it under conditions of 40 ° C. and 70% Rh for 5 days was subjected to exposure, development treatment and density measurement in the same manner as above to obtain a fog density value (yellow density). The preservability was evaluated by the fog density value before and after the aging test (the value after the aging test and the value before the aging test). The results are summarized in Table 9
Note.

[0121]

[Table 9]

After the silver halide color photographic light-sensitive material prepared as described above was imagewise exposed, the cumulative replenishment amount of the solution was increased to 3 times the tank capacity by the method described below using an automatic processor. It processed continuously until it became. Processing process time Temperature Tank capacity Replenishment amount Color development 135 seconds 38 ° C 11 liters 350 ml / m ² Bleach fixing 40 seconds 34 ° C 3 liters 300 ml / m ² Washing with water (1) 40 seconds 32 ° C 3 liters-washing with water (2) 40 Second 32 ℃ 3 liter 350 ml / m ² Dry 30 s 80 ℃ Replenishment method of washing water is to replenish the washing bath (2) with the washing bath (2).
The so-called countercurrent replenishment system was used in which the overflow liquid of (1) was introduced into the washing bath (1). At this time, the carry-out amount of each processing solution by the light-sensitive material was 35 ml / m ² .

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] D-Sorbit 0.15g 0.20g Sodium naphthalenesulfonate / formalin condensate 0.15g 0.20g Nitrilotris (methylenephosphonic acid) pentasodium salt 1.8g 1.8g Diethylenetriaminepentaacetic acid 0.5 g 0.5 g 1-hydroxyethylidene-1,1-diphosphonic acid 0.15 g 0.15 g diethylene glycol 12.0 ml 16.0 ml benzyl alcohol 13.5 ml 18.0 ml potassium bromide 0.70 g-benzotriazole 0.003 g 0.004 g sodium sulfite 2.4 g 3.2 g disodium -N, N-bis (sulfonate ethyl) hydroxylamine 8.0g 10.6g triethanolamine 6.0g 8.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid 1 water salt 6.0g 8.0g Potassium carbonate 30.0g 25.0g Optical brightener (diaminostilbene type) 1.3g 1.7g Add water 1000ml 1000ml pH (25 ° C) (adjust pH with KOH or sulfuric acid) 10.30 10.79

[Bleach-fixing solution] [Tank solution] [Replenishing solution] ethylenediaminetetraacetic acid ・ 2 sodium ・ dihydrate 4.0 g Same as tank solution ethylenediaminetetraacetic acid ・ Fe (III) ・ ammonium ・ dihydrate 55.0 g thio Ammonium sulfate (750 g / liter 168 ml sodium p-toluenesulfinate 30.0 g Ammonium sulfite 35.0 g 5-mercapto-1,3,4-triazole 0.5 g Ammonium nitrate 10.0 g Water was added to 1000 ml pH (25 ° C) (ammonia water) Or adjust the pH with acetic acid) 6.5

[Washing Water] [Both tank solution and replenisher] Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

Example 3 In samples 201 to 205 of Example 2, ExZK-
1, except that ExZK-2 was omitted, Sample 201 of Example 2
~ 205, and these are prepared as samples 301 to 3 respectively.
It was set to 05. These samples were treated in the same manner as in Example 2 except that, in the processing step 2 of Example 2, 20 seconds after the start of color development, the sample was subjected to full exposure for 10 seconds by a high color rendering light source (fluorescent lamp) having a color temperature of 5200K. Testing / evaluation was performed. As a result, similarly to Example 2, it was found that the sample to which the compound of the present invention was added had a small color fog and a small change in the color fog due to the storage of the light-sensitive material.

Example 4 In samples 201 to 205 of Example 2, ExZK-
The same tests and evaluations as in Example 2 were carried out except that the developing treatment was carried out by the following treatment step 4 except for 1, ExZK-2 and Cpd-22, 28 and 29. As a result, in the same manner as in Example 2, the sample to which the compound of the present invention was added showed small color fog, and the change in color fog due to storage of the light-sensitive material was also small.

[Processing Step 4] After the silver halide color photographic light-sensitive material prepared as described above is exposed, the cumulative replenishment amount of the solution is determined by the method described below using an automatic processor. It processed until it tripled. Treatment process time Temperature Tank capacity Replenishment amount First development 75 seconds 38 ° C 8 liters 330 ml / m ² First water washing (1) 45 seconds 33 ° C 5 liters-First water washing (2) 45 seconds 33 ° C 5 liters 5000 ml / m ² reversal exposure 15 seconds 100lux color development 135 sec 38 ° C. 15 liters 330 ml / m ² second wash 45 seconds 33 ° C. 5 liters 1,000 ml / m ² bleach-fixing (1) 60 sec 38 ° C. 7 liters - blix (2 ) 60 seconds 38 ℃ 7 liter 220 ml / m ² Third water wash (1) 45 seconds 33 ℃ 5 liter − Third water wash (2) 45 seconds 33 ℃ 5 liter − Third water wash (3) 45 seconds 33 ℃ 5 liter 5000 ml / m ² dry 45 seconds 75 ° C. Here, the first washing and the third washing were countercurrent washing methods. That is, flush water is flown to the first flush (2), the overflow is led to the first flush (1), and rinse water is flushed to the third flush (3), and the overflow is led to the third flush (2).
The overflow of the third washing (2) was led to the third washing (1).

The composition of each processing liquid was as follows. [First developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylene phosphonic acid / 5-sodium salt 1.0 g 1.0 g Diethylenetriamine 5 acetic acid / 5 sodium salt 3.0 g 3.0 g Potassium sulfite 30.0 g 30.0 g Potassium thiocyanate 1.2g 1.2g Potassium carbonate 35.0g 35.0g Hydroquinone potassium monosulfonate 25.0g 25.0g 1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0g 2.0g Potassium bromide 0.5g- Potassium iodide 5.0 mg-water was added to 1000 ml 1000 ml pH 9.60 9.70 The pH was adjusted with hydrochloric acid or potassium hydroxide.

[Color developer] [Tank liquid] [Replenisher] Benzyl alcohol 15.0 ml 15.0 ml Diethylene glycol 12.0 ml 14.0 ml 3,6-dithia-1,8-octane-diol 0.20 g 0.25 g Nitrilo-N, N, N-trimethylene phosphonic acid-5 sodium salt 0.5g 0.5g diethylenetriamine pentaacetic acid / 5 sodium salt 2.0g 2.0g sodium sulfite 2.0g 2.5g hydroxylamine sulfate 3.0g 3.6g N-ethyl-N- (β-methanesulfonamide ethyl ) -3-Methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 8.0 g Optical brightener (diaminostilbene type) 1.0 g 1.2 g Potassium bromide 0.5 g-Potassium iodide 1.0 mg-Water In addition 1000 ml 1000 ml pH 10.25 10.40 pH is hydrochloric acid or potassium hydroxide. It was adjusted without.

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Ethylenediaminetetraacetic acid / 2 sodium salts / dihydrate 5.0 g Same as mother liquor Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonium ・ monohydrate 80.0 g Sulfite Sodium 15.0 g Ammonium thiosulfate (700 g / l) 160 ml 2-mercapto-1,3,4-triazole 0.5 g Water was added to 1000 ml pH 6.50 pH was adjusted with acetic acid or aqueous ammonia.

Example 5 Preparation of Sample 501 A paper support (thickness 10) laminated on both sides with polyethylene.
(0 micron), the following first to eleventh layers were applied to the front side, and the twelfth to thirteenth layers were applied to the back side to form a color photographic light-sensitive material. The polyethylene coated on the first layer contains titanium oxide (4 g / m ² ) as a white pigment and a trace amount (0.003 g / m ² ) of ultramarine blue as a bluing dye (the chromaticity of the surface of the support is L 88 in the ^* , a ^* , and b ^* systems.
It was 0, -0.20, -0.75. ).

(Photosensitive layer composition) The components and coating amount (g /
m ² unit). However, the addition amount of the sensitizing dye is shown in mol per mol of silver. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer is Emulsion E described below.
It was made by changing the particle size by changing the temperature according to the manufacturing method of M-1. However, as the emulsion for the 11th layer, a Lippmann emulsion which was not surface-chemically sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver 0.10 Color Mixing Inhibitor (Cpd-7) 0.05 Color Mixing Inhibitor Solvent (Solv-4, 5 Equivalents) 0.12 Gelatin 0.70

Second Layer (Intermediate Layer) Gelatin 0.70 Dye (Cpd-32) 0.005

Third Layer (Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3 equivalents 5.4 × 10 ^{−4 in} total) (average grain size 0 40 μ, particle size distribution 10%, octahedron) 0.25 gelatin 0.70 cyan coupler (ExC-1, 2, 3 1: 1: 0.2) 0.30 anti-fading agent (Cpd-1, 2) 3, 4, 30 each equivalent) 0.18 Anti-staining agent (Cpd-5, 15 each equivalent) 0.003 Coupler dispersion medium (Cpd-6) 0.30 Coupler solvent (Solv-1, 3, 5) Each equivalent) 0.12

Fourth Layer (Intermediate Layer) Gelatin 1.00 Color Mixing Inhibitor (Cpd-7) 0.07 Color Mixing Inhibitor Solvent (Solv-4, 5 Equivalent Amount) 0.16 Polymer Latex (Cpd-8) 0 .10

Fifth Layer (Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4 2.6 × 10 ⁻⁴ ) (average particle size 0.40 μ, particle size distribution 10%, Octahedron) 0.20 Gelatin 1.00 Magenta coupler (ExM-1, 2 each equivalent) 0.11 Yellow coupler (ExY-1) 0.03 Anti-fading agent (Cpd-9, 26, 30, 31 etc.) Amount) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 in 10: 7: 7: 1 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6 each equivalent) 0.15

6th layer (intermediate layer) Same as 4th layer

Seventh Layer (Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6 equivalence of 3.4 × 10 ^{−4 in} total) (average grain size 0.58 μ, Particle size distribution 10%, octahedron) 0.32 Gelatin 0.82 Yellow coupler (ExY-2, 3 each equivalent) 0.36 Antifading agent (Cpd-14) 0.10 Antifading agent (Cpd-30) 0.05 Comparative compound (A) 0.025 Anti-staining agent (Cpd-5, 15 in 1: 5 ratio) 0.002 Coupler dispersion medium (Cpd-6) 0.06 Coupler solvent (Solv-2) 0. 11

Eighth Layer (UV Absorber-Containing Layer) Gelatin 0.60 UV Absorber (Equivalent for Cpd-2, 4, 16) 0.40 Anti-Color Mixing Agent (Equivalent for Cpd-7, 17) 03 Dispersion medium (Cpd-6) 0.02 UV absorber solvent (Solv-2, 7 each equivalent) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 10:10: 13:15:20 ratio) 0.05

Ninth Layer (Protective Layer) Fine grain silver iodobromide (99 mol% silver bromide, average size 0.05 μ) 0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight 50,000) 0.01 Poly Methyl methacrylate particles (average particle size 2.4μ) and silicon oxide (average particle size 5μ) Equivalent 0.05 Gelatin 0.05 Gelatin hardening agent (Equivalent for each of H-1 and H-2) 0.18

10th layer (back layer) Gelatin 2.50 Ultraviolet absorber (Equivalent amount for each Cpd-2, 4, 16) 0.50 Dye (Equivalent amount for each Cpd-18, 19, 20, 21, 27) 0 .06

Eleventh Layer (Back Layer Protective Layer) Polymethylmethacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent 0.05 gelatin 2.00 Gelatin hardener (H- 1, H-2 equivalent) 0.14

Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 65 ° C. over 15 minutes with vigorous stirring,
Octahedral silver bromide grains having an average grain size of 0.23 μm were obtained. At this time, 0.3 g of 3,4-dimethyl-1,3 per mol of silver was used.
-Thiazolin-2-thione was added. 1 silver in this emulsion
Chemical sensitization was carried out by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol and heating at 75 ° C. for 80 minutes. Using the particles thus obtained as a core, the particles are further grown in the same precipitation environment as the first time,
Finally, an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.4 μ was obtained. Coefficient of variation of particle size is about 10%
Met. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver.
The mixture was heated at 0 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

ExZK-1 is used as a nucleating agent in each photosensitive layer.
And ExZK-2 are 10 ^-3 for silver halide,
10 ^-2 % by weight, Cpd-22, 28 as a nucleation accelerator,
29 were used at 10 ^-2 wt% each. Further, for each layer, alkanol XC (Du Pont) and sodium alkylbenzene sulfonate were used as emulsification / dispersion aids, and succinate and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. In the silver halide and colloidal silver-containing layer, (Cpd-23, 24 and 25 equivalent amounts) was used as a stabilizer. This sample was designated as sample number 501. The compounds used in the examples are shown below.

[0147]

[Chemical 38]

[0148]

[Chemical Formula 39]

[0149]

[Chemical 40]

[0150]

[Chemical 41]

[0151]

[Chemical 42]

[0152]

[Chemical 43]

[0153]

[Chemical 44]

[0154]

[Chemical formula 45]

[0155]

[Chemical formula 46]

[0156]

[Chemical 47]

[0157]

[Chemical 48]

Solv-1 Di (2-ethylhexyl) sebacate Solv-2 Trinonyl Phosphate Solv-3 Di (3-methylhexyl) Phthalate Solv-4 Tricresyl Phosphate Solv-5 Dibutyl Phthalate Solv-6 Trioctyl Phosphate Solv- 7 Di (2-ethylhexyl) phthalate

H-1 1,2-bis (vinylsulfonylacetamido) ethane H-2 4,6-dichloro-2-hydroxy-1,3
5-triazine Na salt

ExZK-1 7- (3-ethoxythiocarbonylaminobenzamido) -9-methyl-10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3- {3- [5-
{3- [2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenylcarbamoyl] -4
-Hydroxy-1-naphthylthio} tetrazole-1-
Ill] phenyl} ureido] benzenesulfonamide}
Phenyl] -1-formylhydrazine

Preparation of Samples 502 to 504 Sample 5 was prepared in the same manner as in Sample 501 except that the seventh layer was replaced with an equimolar compound shown in Table 10 instead of Comparative Compound A.
It was prepared in the same manner as 01.

Evaluation of Color Fog A sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) was applied to the sample prepared as described above.
Was subjected to gradation exposure, and development processing was carried out in processing step 2 described below. The density of the developed sample was measured, and color fog was evaluated by the fog density value (yellow density). Evaluation of storability A sample which had been left for 5 days under conditions of 50 ° C. and 60% Rh and was subjected to a aging test was subjected to exposure, development treatment and density measurement in the same manner as above to determine the maximum density value (yellow density). The storability was evaluated by the maximum concentration value before and after the aging test (value after aging test-value before aging test). The above results are summarized in Table 10.

[0163]

[Table 10]

[Processing Step 5] After the silver halide color photographic light-sensitive material prepared as described above is imagewise exposed, the cumulative replenishment amount of the solution is determined by the method described below using an automatic processor. It processed until it became 3 times the volume. Treatment process time Temperature Tank capacity Replenishment amount Color development 135 seconds 38 ℃ 28 liters 240 ml / m ² Bleach fixing 40 seconds 35 ℃ 11 liters 320 ml / m ² Water washing (1) 40 seconds 35 ℃ 7 liters-water washing (2) 40 S 35 ℃ 7 liter 320 ml / m ² dry 30 s 80 ℃ Wash water replenishment method is to replenish the wash bath (2) with the wash bath (2)
The so-called countercurrent replenishment system was used in which the overflow liquid of (1) was introduced into the washing bath (1). At this time, the carry-out amount of each processing solution by the light-sensitive material was 35 ml / m ² .

The composition of each treatment liquid was as follows. [Color developer] [Tank solution] [Replenisher] D-Sorbit 0.15g 0.20g Sodium naphthalenesulfonate / formalin condensate 0.15g 0.20g Nitrilotris (methylenephosphonic acid) pentasodium salt 1.8g 1.8g Diethylenetriaminepentaacetic acid 0.5 g 0.5 g 1-hydroxyethylidene-1,1-diphosphonic acid 0.15 g 0.15 g diethylene glycol 12.0 ml 16.0 ml benzyl alcohol 13.5 ml 18.0 ml potassium bromide 0.70 g-benzotriazole 0.003 g 0.004 g sodium sulfite 2.8 g 3.7 g hydroxylamine 1/2 sulphate 3.0 g 4.0 g triethanolamine 6.0 g 8.0 g 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfuric acid ½ hydrate 4.2 g 5.6 g potassium carbonate 30.0 g 25.0g Optical brightener (diaminostill Adding emission system) 1.3 g 1.7 g Water 1000 ml 1000 ml pH (25 ℃) (pH adjusted with KOH or sulfuric acid) 10.35 10.93

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Ethylenediaminetetraacetic acid / 2 sodium / dihydrate 4.0 g Same as tank solution Ethylenediaminetetraacetic acid / Fe (III) / Ammonium / dihydrate 55.0 g Thio Ammonium sulfate (750 g / liter) 168 ml Sodium p-toluenesulfinate 30.0 g Ammonium sulfite 35.0 g 5-Mercapto-1,3,4-triazole 0.5 g Ammonium nitrate 10.0 g Water added 1000 ml pH (25 ° C) (ammonia PH adjustment with water or acetic acid) 6.20

[Washing Water] [Both tank solution and replenisher] Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

From Table 10, as compared with the sample to which the comparative compound A is added, the sample to which the comparative compound B is added has a certain effect of improving the color fog, but the photographic property change with time is large. It can be seen that the sample to which the compound of the present invention is added improves color fog without increasing the change in photographic properties with time.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 13, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] In the formula, R represents a non-metal atom group necessary for forming a heterocycle together with -C (= N-)-, and Y and Z are a hydrogen atom, an aliphatic residue, an aromatic residue or a hetero residue, respectively. Represents a ring residue, and X represents a diffusion resistant group which is released when the compound represented by the general formula (I) reacts with an oxidized product of a color developing agent to form a efflux dye.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

In the formula, R represents a group of non-metal atoms necessary for forming a heterocycle together with -C (= N-)-, and Y and Z are a hydrogen atom, an aliphatic residue and an aromatic residue, respectively. Represents a group or a heterocyclic residue, and X represents a diffusion-resistant group which is released when the compound represented by the general formula (I) reacts with an oxidized product of a color developing agent to form a efflux dye. . As a result of intensive studies by the inventors, the silver halide emulsion was not adversely affected, the coupling reaction with the oxidized product of the developing agent was fast,
In addition, the produced dye reaches a group of compounds having a property of quickly flowing out from the emulsion layer.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

[0016]

[Chemical 5]

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

[0022]

[Chemical 7]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

[0028]

[Chemical 12]

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

25.0 g (200 mmol) of compound (1-a) is dissolved in 100 ml of methanol, and 43.0 g (220 mmol) of compound (1-b) is added with stirring. After stirring at room temperature for 3 hours, the mixture is poured into water, extracted with ethyl acetate, the organic layer is washed with water, dehydrated and concentrated under reduced pressure. Compound (1-c) (41.8 g, 200 mmol) was added thereto, and the pressure was reduced by an aspirator at 170 ° C.
Stir for 4 hours. After cooling to 100 ° C., it was dissolved in 30 ml of N, N-dimethylformamide (DMF), allowed to cool to room temperature, and 200 ml of ethyl acetate was added.
Precipitate crystals. The crystals are collected by filtration and washed with ethyl acetate to obtain the compound (1-d) (17.0 g, 22%). 9 g (23.4 mmol) of compound (1-d) was dissolved in 30 ml of N, N-dimethylacetamide (DMAc),
3.16 g (23.4 mol mol) of sulfuryl chloride was added to 20
Drip over a period of minutes. After stirring at room temperature for 1 hour, the mixture is poured into water, extracted with ethyl acetate, the organic layer is washed with water, dehydrated and concentrated under reduced pressure. Dissolve this in 20 ml DMAc,
12.1 g (28.1 mmol) of compound (1-e) was added to 4
It was dissolved in 0 ml of DMAc, 8.55 g (56.2 mmol) of 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) was added, and the mixture was added dropwise while stirring. The reaction solution is stirred at 60 ° C. for 3 hours, poured into hydrochloric acid water, and extracted with ethyl acetate. After washing the organic layer with water,
After dehydration, concentration under reduced pressure, and purification by silica gel column, compound (1-f) (12.0 g, 63%) is obtained as a solid. Compound (1-f) (4.0 g, 4.92 mmol) was dissolved in isopropyl alcohol (20 ml), sodium hydroxide (760 mg, 17.7 mmol) was dissolved in water (2 ml), and the mixture was stirred for 1 hour. Pour and extract with ethyl acetate. The organic layer is washed with water, dried, concentrated under reduced pressure, and purified with a silica gel column to obtain the exemplary compound (1) (2.78 g, 72%) as a solid.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material containing a compound represented by the following general formula (I) which forms a efflux dye by a coupling reaction with an oxidant of a color developing agent. General formula (I) In the formula, R represents a non-metal atom group necessary for forming a heterocycle together with -C (= N-)-, and Y and Z are a hydrogen atom, an aliphatic residue, an aromatic residue or a hetero residue, respectively. X represents a ring residue, and X represents a diffusion-resistant group which is released when the compound represented by the general formula (I) reacts with an oxidant of a color developing agent to form a efflux dye.