JPH0833639B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material in which fading of a yellow image is prevented.

[Prior Art] When a silver halide color photographic light-sensitive material is imagewise exposed and color-developed, an oxidized aromatic primary amine type color developing agent reacts with a coupler to give indophenol, indoaniline, indamine. It is well known that dyes, azomethines, phenoxazines, phenazines, and similar dyes are formed to form dye images.

Generally, the quality of these photographic images is not permanent and deteriorates over time. Especially, a color photograph having an image composed of an azomethine dye or an indoaniline dye, when exposed to light for a long period of time or stored under high temperature and high humidity, causes a fading or discoloration of the dye image, and further discoloration of a white background (yellow stain). It also causes the deterioration of the image.

Such deterioration in image quality is a disadvantage that can be fatal to recording materials, and improvement is desired.

In general, cyan, magenta, and yellow dye images are used in color photographs, and studies have been conducted on making each dye image fast. Much research has been done on magenta dye images, but much has not been done on yellow dye image fastness studies, as they are not as fast as magenta dye images. However, as a result of many studies on the fastness of the magenta dye image, the fastness has become high, and fading and discoloration of the yellow dye image have become conspicuous, so that the fastness of the yellow dye image has been desired.

As a method of using an anti-fading agent for improving light and wet heat fastness of a yellow dye image, for example, hindered amine derivatives and phenol derivatives are disclosed in British Patent 1,326,889,
1,354,313, 1,410,846, U.S. Patent 3,336,135,
No. 4,268,593, Japanese Patent Publication No. 48-31256, No. 51-1420, No. 52
-6623, JP-A-58-114036, 59-5426, 61-2151
, EP 246,766, and phosphoric acid esters are suggested in EP 265,196.

These compounds have a slight effect of improving the light and heat fastness to the yellow dye, but sometimes the effect is small or the photographic property is deteriorated.

Further, hydrazine derivatives have been proposed in European Patent 255,722, JP-A-63-229455, JP-A 63-256951, 63-220142 and JP-B-60-47578. However, the compound described in European Patent 255,722 has a very small effect of preventing fading to the dye, and reacts with the developing agent remaining in the color photographic light-sensitive material after the development processing to deteriorate the fading. Is to eliminate. For this reason, the method described in European Patent No. 255,722 has a limit to the fading ability, and the fading prevention effect is very small. In addition, Japanese Examined Sho 60
-47578, JP-A-63-229455, 63-256951, 63-2
The compounds described in 20142 do not have the sufficient effect of improving the fastness, and may deteriorate the photographic properties.

On the other hand, various anti-fading agents have been proposed for fastness to magenta color images, but these compounds certainly show an effect on fastening of magenta color images,
Most of them showed little effect on the yellow dye image, and on the contrary, many of them accelerated fading.

[Problems to be Solved by the Invention] Therefore, a first object of the present invention is to provide a silver halide color photographic light-sensitive material having improved fastness of a yellow dye image.

A second object of the present invention is to include a stabilizer in the photographic layer, which does not cause a change in hue or fog, and has a sufficient effect for improving the fastness of a yellow dye image without causing poor dispersion or crystals. This is to provide a silver halide color photographic light-sensitive material in which the yellow color image is stabilized.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material in which the color balance of the three fading colors is improved by improving the fastness of yellow images to light and heat.

[Means for Solving Problems] As a result of various studies, the present inventors have found that the anti-fading agent represented by the following general formula [I] is added to the yellow coupler-containing layer in an amount of 10 to 200 mol% based on the yellow coupler. The present invention has been completed by finding that the object of the present invention can be achieved by containing the coupler in a proportion and as an emulsified dispersion co-emulsified with the coupler.

General formula [I] [Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a phosphonyl group, a sulfinyl group, an alkylcarbamoyl group. , An arylcarbamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkyloxycarbonyl group and an aryloxycarbonyl group, and Y is 2
Represents a group of non-metal atoms necessary to form a 5-membered heterocycle with nitrogen atoms. However, in the group of non-metal atoms forming Y, there is at least one carbonyl group, which is next to the nitrogen atom, and when 1-phenyl-3-pyrazolidone is formed, the 2-position The substituent is not a hydrogen atom, an acetyl group, or an acyl group substituted with a carboxyl group. ] Of the compounds represented by the above general formula [I], R ₁ and
A compound in which each of R ₂ has 40 or less carbon atoms and the total number of these carbon atoms is 6 to 50 is preferable.

As the yellow coupler used in the yellow dye image forming layer in the silver halide color photographic light-sensitive material of the present invention, any yellow coupler can be used. In particular, the compound represented by the general formula [Y-I] is preferably used. preferable.

General formula [Y-I]: [In the formula, R ¹ represents a substituted or unsubstituted N-phenylcarbamoyl group. R ₂ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted phenyl group. X ¹ represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized developing agent. R ¹ , R ₂ or
X ¹ in it may form a dimer or higher polymer.

The yellow coupler represented by the general formula [Y-I] is described in more detail as follows: R ¹ (N-phenylcarbamoyl group)
As the substituent of the well-known substituent in the yellow coupler, for example, an alkyl group, an alkenyl group, an alkoxy group,
Alkoxycarbonyl group, halogen atom, alkoxycarbamoyl group, aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group, alkyl-substituted succinimide group, aryloxy group,
It represents an aryloxycarbonyl group, an arylcarbamoyl group, an arylamide group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group and the like. Two or more substituents may be attached, in which case they may be the same or different.

Examples of the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms of R ² include a methyl group, a t-butyl group, a t-amyl group,
-Octyl group, 1,1-diethylpropyl group, 1,1-dimethylhexyl group, 1,1,5,5-tetramethylhexyl group, 1
-Methyl-cyclohexyl group, adamantyl group and the like are mentioned as typical examples. As the substituent of the substituted phenyl group of R ^2, the substituent represented by R ¹ is exemplified.

The coupling-off group for X ¹ may be a hydrogen atom, but is preferably a coupling-off group for forming a 2-equivalent yellow coupler, for example, the following general formulas [Y-II] and [Y-
III], [Y-IV] or [YV].

R ¹⁶ represents an optionally substituted aryl group or heterocyclic group.

R ¹⁷ and R ¹⁸ each represent a hydrogen atom, a halogen atom, a carboxylic ester group, an amino group, an alkyl group, an alkylthio group,
It represents an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group or a heterocycle, and these groups may be the same or different.

W ¹ in the formula Together with a non-metallic atom required to form a 4-, 5- or 6-membered ring.

More preferred yellow couplers used in the present invention are represented by the following general formula [Y-VI].

General formula [Y-VI] In the formula, R ³ represents a tertiary alkyl group having 4 to 12 carbon atoms, a phenyl group substituted with a halogen atom, an alkyl group, or an alkoxy group, or an unsubstituted phenyl group. R ⁴ represents a halogen atom or an alkoxy group. R ⁵
Represents a hydrogen atom, a halogen atom or an optionally substituted alkoxy group.

R ⁶ is an optionally substituted acylamino group, alkoxycarbonyl group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonamide group, arylsulfonamide group, alkylureido group, arylureido group, succinimide Represents a group, an alkoxy group, or an aryloxy group.

X ² is represented by the following general formula [Y-VII], [Y-VIII], [Y-I]
X] or [Y-X] is represented.

In the formula, R ⁷ represents a substituted or unsubstituted alkylsulfonyl group, arylsulfonyl group, acyl group, hydroxy group or the substituent represented by R ¹ . l is 2, 3, 4
Or 5 and l is 3 or more, R ⁷ may be the same or different.

In the formula, R ⁸ and R ⁹ each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group. R ¹⁰ , R ¹¹ and R ¹² each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an acyl group. W ² represents an oxygen or sulfur atom.

Particularly preferred yellow couplers used in the present invention are represented by the following general formula [Y-XI].

General formula [XI] In the formula, R ¹³ represents an optionally substituted acylamino group, alkoxycarbonyl group, alkylsulfamoyl group, or alkylsulfonamide group. X ³ represents the following general formula [Y-XII] or the above general formula [Y-VIII], [Y
-IX] or [Y-X] is represented.

In the formula, R ¹⁴ represents a hydrogen atom, a halogen atom, a cyano group, an optionally substituted acylamino group, an alkyl or aryl sulfamoyl group, or an alkyl or aryl sulfonyl group.

R ¹⁵ represents a hydrogen atom, a cyano group, an optionally substituted alkyl or aryl sulfonyl group, an alkyl or aryl sulfamoyl group, an alkyl or aryl sulfonamide group, an acyl group, an alkyl or aryloxycarbonyl group or a carboxy group, And R ¹⁴ , R ¹⁵
Of these, at least one may be substituted alkyl or aryl sulfonyl group, alkyl or aryl sulfamoyl group, alkyl or aryl sulfonamide group, alkyl or aryloxycarbonyl group,
Or a carboxy group.

Specific examples of the yellow coupler represented by the general formula [Y-I] used in the invention are shown below, but the invention is not limited thereto.

The following X and Y ratios are all weight ratios.

These yellow couplers are, for example, Japanese Patent Publication No. 51-10783.
No. 51-33410, No. 52-25733, JP-A-47-26133,
48-73147, 51-102636, 50-130442, 50-6
341, 50-123342, 51-21827, 50-87650,
52-82424, 52-115219, British Patent 1425020, West German Patent 1547868, West German Application Publication No. 2219917, 2261361.
No. 2414006, European Patent Nos. 272041 and 249473, and JP-A No. 63-43144.

In the present invention, the yellow coupler is a silver coupler in the emulsion layer.
2 × 10 ^-3 mole to 5 × 10 ^-1 mole, preferably 1
X 10 ^-2 mol to 5 x 10 ^-1 mol are added.

These yellow couplers may be used alone or 2
You may use together 1 or more types.

Next, the compound represented by formula [I] will be described in more detail. The compound represented by the general formula [I] in the present invention is one whose chemical structure does not substantially change by color development processing (the reducing agent changes its chemical structure by color development processing), and these compounds Are those which are not substantially decomposed by color development processing. R ₁ and
R ₂ is a hydrogen atom, an alkyl group (for example, methyl, butyl, tert-butyl, hexadecyl, phenoxyethyl,
Methoxyethyl), cycloalkyl groups (eg cyclopentyl, cyclohexyl), alkenyl groups (eg 2-
Propenyl, 1,3-butadienyl), cycloalkenyl group (e.g. cyclohexenyl, cyclooctenyl), aryl group (e.g. phenyl, naphthyl, methoxyphenyl), heterocyclic group (e.g. furyl, oxazolyl, thiazolyl), acyl group (e.g. acetyl, Dodecanoyl,
Benzoyl), a sulfonyl group (for example, dodecylsulfonyl, hexadecylsulfonyl, benzenesulfonyl),
A phosphonyl group (eg, butyloctylphosphonyl, octyloxyphosphonyl, aryloxyphosphonyl),
Sulfinyl group (eg octylsulfinyl, benzenesulfinyl), alkylcarbamoyl group (eg N
-Methylcarbamoyl, N-dodecylcarbamoyl, N,
N-dibutylcarbamoyl), arylcarbamoyl group (eg N-phenylcarbamoyl, Np-methoxyphenylcarbamoyl), alkylsulfamoyl group (eg N-methylsulfamoyl, N, N-diethylsulfamoyl), aryl Sulfamoyl group (eg N
-Phenylsulfamoyl, Np-methoxyphenylsulfamoyl), an alkyloxycarbonyl group (for example, methoxycarbonyl, dodecyloxycarbonyl),
And aryloxycarbonyl groups (eg phenyloxycarbonyl, p-methoxyphenoxycarbonyl)
Represents

Y represents a group of non-metal atoms necessary for forming a 5-membered heterocycle (eg, pyrazolidine, pyrazoline) with two nitrogen atoms, and the heterocycle is a substituent (eg, alkyl, alkoxy, alkoxy, carbonyl, alkylcarbamoyl, Alkylsulfamoyl, alkylureido, alkoxycarbonylamino, alkylsulfonyl, acyl, halogen, aryl, aryloxy, aryloxycarbonyl, arylcarbamoyl, arylsulfamoyl, arylureido, aryloxycarbonylamino, arylsulfonyl) May be.

The total carbon number of R ₁ and R ₂ is preferably 6 or more, and particularly preferably 6 to 50. R ₁ or R ₂ is the carbon number
It is preferably 40 or less.

Among the compounds represented by the general formula [I], more preferable compounds are compounds in which R ₁ and R ₂ are not hydrogen atoms at the same time.

The compound represented by the general formula [I] has at least one carbonyl group in the nonmetallic atom group forming Y, and it is adjacent to the nitrogen atom.

Specific examples of the compound of the present invention represented by the general formula [I] are shown below, but the compounds are not necessarily limited to these.

These compounds are disclosed in JP-A-63-95444 and 63-115866.
No., Helv. Chem. Acta., Vol. 36, p. 75 (1953), New Experimental Chemistry Lecture, vol. 14, p. 1220 (1977) Maruzen et al.

Some of the compounds represented by the general formula [I] are
It is similar to the compounds described in JP-A-63-43145, JP-A-63-115866 and JP-B-60-47573, which are known to be effective in preventing fading of magenta couplers. But,
A compound effective for fastening a magenta image is not always effective for fastening a yellow dye image.

When the compound of the present invention represented by the general formula [I] was applied to a dye image of a yellow coupler, it showed a remarkable improving effect on the fastness to heat and light without deteriorating the photographic property.

The compound represented by the general formula [I] in the present invention varies depending on the kind of couplers used in combination, but it is suitable to use in the range of 5 to 400 mol%, preferably 10 to 200 mol% based on the coupler. . If it is less than this range, the anti-fading effect is extremely small and it is not suitable for practical use. On the other hand, if the amount is more than this range, the progress of development may be hindered and the color density may be lowered.

The compound represented by the general formula [I] used in the present invention is particularly excellent in the fading prevention effect when used in the yellow dye image forming layer, and particularly fading when it is present in the high boiling point organic solvent together with the yellow coupler. Excellent prevention effect.

The compound represented by the general formula [I] used in the present invention may be used alone or in combination of two or more kinds.

The color light-sensitive material of the present invention is provided with a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer in this order on the support or in any arrangement thereof. Preferably.

The silver halide used in the present invention includes silver chloride,
Silver bromide, silver salt (iodo) bromide and silver iodobromide can be mentioned. Among them, silver chloride and silver chloro (iodo) bromide are preferable. Further, the halogen composition of the silver halide grains in one emulsion layer is such that 90 mol% or more of the total silver halide constituting the silver halide grains is silver chloride, and substantially no silver iodide is contained. It preferably comprises silver bromide. Here, "contains substantially no silver iodide" means that the silver iodide content is 1.0 mol% or less. A particularly preferred halogen composition of the silver halide grains is silver chlorobromide containing substantially no silver iodide, wherein 95 mol% or more of the total silver halide constituting the silver halide grains is silver chloride.

Furthermore, the silver halide grains according to the present invention preferably have a silver bromide localized phase in a silver bromide content of at least 10 mol% and less than 70 mol%. Such an arrangement of the silver bromide localized phase can be freely selected according to the purpose, and may be inside the silver halide grain, on the surface or subsurface, or divided into the interior and the surface or subsurface. May be. The localized phase may have a layered structure surrounding silver halide grains inside or on the surface, or may have a discontinuous isolated structure. As one preferable specific example of the arrangement of the silver bromide localized phase, the silver bromide content on the surface of the silver halide grains (among others, at the corners of the grains) is at least 10 mol%, more preferably more than 20 mol%. The localized phase is locally epitaxially grown.

The content of silver bromide in the localized phase is preferably more than 20 mol%. However, if the content of silver bromide is too high, desensitization may occur when pressure is applied to the light-sensitive material, or the composition of the processing solution may be reduced. In some cases, characteristics unfavorable for a photographic light-sensitive material, such as a large change in sensitivity and gradation due to fluctuations in the light-sensitive material, may be imparted. Taking these points into consideration, the silver bromide content of the localized phase is preferably in the range of 20 to 60 mol%, and 30 to 50 mol%.
The range of mol% is most preferred. The other silver halide constituting the localized phase is preferably silver chloride. The silver bromide content of the localized phase is described by X-ray diffraction method (for example, described in “Chemical Society of Japan, New Experimental Chemistry Lecture 6, Structural Analysis” Maruzen).
Alternatively, it can be analyzed using the XPS method (for example, described in “Surface Analysis, —IMA, Application of Auger Electron / Photoelectron Spectroscopy—” Kodansha). The localized phase accounts for 0.1 to 20% of the total silver constituting the silver halide grains of the present invention.
Of silver, and more preferably 0.5 to 7% of silver.

The interface between such a silver bromide localized phase and another phase may have a clear phase boundary or may have a short transition region in which the halogen composition changes gradually. The position of the silver bromide localized phase can be confirmed by observation with an electron microscope or the method described in EP-A-273430A2.

Various methods can be used to form such a silver bromide localized phase. For example, a soluble silver salt and a soluble halogen salt can be reacted by a one-sided mixing method or a simultaneous mixing method to form a localized phase. Further, the localized phase can be formed also by using a so-called conversion method including a process of converting already formed silver halide into silver halide having a smaller solubility product. Alternatively, the localized phase can be formed by adding fine silver bromide and recrystallizing it on the surface of the silver chloride grains. These manufacturing methods are described, for example, in the above-mentioned European Patent Application No. 273430A2.

In the localized phase of the silver halide grain of the present invention or its substrate, a metal ion different from silver ion (for example, VI
It is preferable to include a group II metal ion, a group II transition metal ion, a lead ion, a thallium ion) or a complex ion thereof, from the viewpoint of further improving the effects of the present invention.

Iridium ion, rhodium ion, iron ion, etc. are mainly used for the localized phase, and osmium is mainly used for the substrate.
A metal ion selected from iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron and the like or a complex ion thereof can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate.

In order for the metal ion to be contained in the localized phase of silver halide grains and / or other grain portions (substrates),
The metal ion may be added to the preparation liquid before grain formation, during grain formation, or during physical ripening. For example, metal ions can be added to an aqueous gelatin solution, an aqueous silver halide solution, an aqueous silver salt solution, or another aqueous solution to form silver halide grains.

Alternatively, a metal ion can be contained in the silver halide fine grains in advance, this is added to a desired silver halide emulsion, and the fine grain silver halide can be dissolved to introduce the metal ion. This method is particularly effective for introducing metal ions into the silver bromide localized phase on the surface of silver halide grains. The addition method can be appropriately changed depending on where in the silver halide grain the metal ion is present.

In particular, the localized phase is preferably deposited together with at least 50% of the total iridium added when the silver halide grains are prepared.

Here, the term “precipitating the localized phase together with iridium ions” means that the iridium compound is supplied simultaneously with, immediately before, or immediately after the supply of silver and / or halogen for forming the localized phase. Say.

The silver halide grains according to the present invention have (10
It is preferable that the substrate has a (0) plane, a (111) plane, or both, and further includes a higher-order plane. Used.

The shape of the silver halide grains used in the present invention has a regular crystal form such as a cube, a tetradecahedron and an octahedron, and an irregular shape such as a sphere and a plate. Some have a irregular crystal type, or have a complex form of these crystal forms. Further, it can be used even if it is composed of a mixture of particles of various crystal forms, but among them, 50% of the particles having the above-mentioned regular crystal form can be used.
The content is preferably 70% or more, more preferably 90% or more. Silver halide emulsion used in the present invention,
Tabular grains having an average assect ratio (ratio of length / thickness) of 5 or more, particularly preferably 8 or more, account for 50% of the total projected area of the grains.
An emulsion occupying the above may be used.

The size of the silver halide grains according to the present invention may be within the range generally used, but the average grain size is 0.1 μm to 1.5 μm.
m is preferred. The particle size distribution may be polydisperse or monodisperse, but monodisperse is preferable. The particle size distribution representing the degree of the fraction is preferably 20% or less, and 15% or less, in terms of statistical variation coefficient (value S / d obtained by dividing the standard deviation S when the projected area is approximated by a circle by the diameter d). Is more preferable.

Further, two or more of such tabular grain emulsions and monodispersed emulsions may be mixed. When the emulsions are mixed, at least one of them preferably has the coefficient of variation described above, and more preferably the coefficient of variation of the mixed emulsion satisfies the above range of values.

The so-called substrate portion other than the localized phase of the silver halide grains used in the present invention may have a different phase between the inside and the surface layer, or may have a uniform phase.

The silver halide emulsion used in the present invention is usually one subjected to physical ripening, chemical ripening and spectral sensitization. Regarding the chemical sensitizer used for chemical ripening, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column, and for the spectral sensitizer, Those described in the upper right column of page 22 to page 38 of the same publication are preferably used.

Further, as the antifoggant or stabilizer used during the production or storage of the silver halide emulsion used in the present invention, those described in the right-hand column on pages 39 to 72 of the same publication are preferably used.

Examples of the magenta coupler used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color-forming dye, and typical examples thereof are U.S. Patent Nos. 2,311,082 and 2,343,703.
No. 2,600,788, No. 2,908,573, No. 3,062,65
No. 3, No. 3,152,896 and No. 3,936,015. As a leaving group for a 2-equivalent 5-pyrazolone-based coupler, a nitrogen atom leaving group described in US Pat. No. 4,310,619 or US Pat. No. 4,351,897, International Publication No. W
The arylthio groups described in O88-0479 are preferred. In addition, 5-having a ballast group described in European Patent No. 73,636.
The pyrazolone-based coupler provides high color density.

As the pyrazoloazole-based coupler, US Patent No. 2,
Pyrazolobenzimidazoles described in US Pat. No. 369,879, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure 24220 (June 1984). Pyrazolotetrazole described and Research Disclosure 24
The pyrazolopyrazoles described in 230 (June 1984) can be mentioned. Any of the couplers mentioned above may be polymeric couplers.

These compounds are specifically represented by the following general formula (M-
1), (M-2) or (M-3).

Here, R ³¹ represents a diffusion-resistant group having a total carbon number of 8 to ³² , and R ³² represents a phenyl group or a substituted phenyl group. R ³³ represents a hydrogen atom or a substituent. z represents a group of non-metal atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring).

X ² represents a hydrogen atom or a leaving group. Column 2, line 41 - column 8 of substituents and for more substituents azole ring, for example, US Patent 4,540,654 Pat of R ³³ 27
Are listed in a row.

Among the pyrazoloazole-based couplers, U.S. Pat.No. 4, in terms of low yellow sub-absorption of the coloring dye and light fastness.
The imidazo [1,2-b] pyrazoles described in 500,630 are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in U.S. Pat. No. 4,540,654 are particularly preferred.

In addition, a pyrazolotriazole coupler in which a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2,3 or 6-position of a pyrazolotriazole ring, JP-A-61-652.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A No. 46, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and European It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in Japanese Patent No. 226,849.

 Specific examples of these couplers are listed below.

The most representative cyan couplers are phenol cyan couplers and naphthol cyan couplers.

U.S. Pat.
369.929, 4,518,687, 4,511,647 and 3,772,0
As described in No. 02 and the like, there are those having an acylamino group at the 2-position of the phenol nucleus and an alkyl group at the 5-position (including polymer couplers). Typical examples thereof include:
The coupler of Example 2 described in Canadian Patent 625,822, the compound (1) described in US Pat. No. 3,772,002, 4,564,590.
(I-4) and (I-5) described in JP-A-61-3
Compounds (1), (2), (3) and (2
4) and the compound (C-2) described in JP-A-62-70846.

U.S. patents for phenolic cyan couplers
2,772,162, 2,895,826, 4,334,011, 4,50
There are 2,5-diacylaminophenol couplers described in JP-A No. 0,653 and JP-A-59-164555, and typical examples thereof include the compound (V) described in US Pat. No. 2,895,826,
Compound (17) described in JP-A-4,557,999, compounds (2) and (12) described in JP-A-4,565,777, compound (4) described in JP-A-4,124,396, and compound (I-1) described in JP-A-4,613,564.
9) etc. can be mentioned.

U.S. patents for phenolic cyan couplers
No. 4,372,173, No. 4,564,586, No. 4,430,423, JP-A-6
1-390441 and Japanese Patent Application No. 61-100222 include those in which a nitrogen-containing heterocycle is condensed with a phenol nucleus, and typical examples thereof include the coupler (1) described in U.S. Pat. No. 4,327,173. (3), the compound (3) described in No. 4,564,586
And (16), the compounds (1) and (3) described in 4,430,423, and the following compounds.

In addition to the cyan couplers of the above-mentioned type, diphenylimidazole-based cyan couplers described in EP 0,249,453A2 may be used.

Other phenolic cyan couplers include U.S. Patents 4,333,999, 4,451,559, 4,444,872, and 4,4.
Uleide couplers described in, for example, 27,767, 4,579,813, and European Patent (EP) 067,689B1, and typical examples thereof include couplers (7) described in U.S. Pat. No. 4,333,999 and 4,451,559. Couplers (1), 4,4
44,872 couplers (14), 4,427,767 couplers (3), 4,609,619 couplers (6) and (24), 4,579,813 couplers (1) and (11) The couplers (45) and (50) described in European Patent (EP) 067,689B1 and the coupler (3) described in JP-A No. 61-42658 can be mentioned.

The naphthol type cyan coupler has an N-alkyl-N-arylcarbamoyl group at the 2-position of the naphthol nucleus (for example, US Pat. No. 2,313,586) and an alkylcarbamoyl group at the 2-position (for example, US Pat. No. 2,474,293). No. 4,282,312), which has an arylcarbamoyl group at the 2-position (for example, Japanese Examined Patent Publication No. 50-14523),
Those having a carbonamide or sulfonamide group at the 5-position (for example, JP-A-60-237448, JP-A-61-145557, JP-A-61-1)
53640), those having an aryloxy leaving group (for example, US Pat. No. 3,476,563), those having a substituted alkoxy leaving group (for example, US Pat. No. 4,296,199), those having a glycolic acid leaving group (for example, JP-B-60-). No. 39217) etc.

These couplers can be contained in the emulsion layer dispersed together with at least one high boiling point organic solvent.
Preferably, a high boiling point organic solvent represented by the following formulas (A) to (E) is used.

Formula (A) Formula (B) W ¹ -COO-W ² Formula (C) Formula (D) Formula (E) W ¹ —O—W ² (In the formula, W ¹ , W ² , and W ³ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, W ⁴ represents W ¹ , OW ¹ or S-W ¹ , n is a number from 1 to 5, and n is 2
In the above case, W ⁴ may be the same as or different from each other, and in the general formula (E), W ¹ and W ² may form a condensed ring). It can be impregnated with a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence or absence of a solvent, or dissolved in a water-insoluble and organic solvent-soluble polymer to be emulsified and dispersed in an aqueous hydrophilic colloid solution. . The homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO88 / 00723 are preferably used, and the use of an acrylamide polymer is particularly preferable in terms of color image stabilization and the like.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, as an organic anti-fading agent for cyan, magenta and / or yellow images, hydroquinones,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical examples are hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating and alkylating the phenolic hydroxyl groups of these compounds. Can be mentioned. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of organic anti-fading agents are described in the specifications of the following patents.

Hydroquinones are U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
728,659, 2,732,300, 2,735,765, and
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No. 2, U.S. Patent Nos. 2,710,801 and 2,816,028,
6-hydroxychromans, 5-hydroxycoumarans and spirochromans are described in U.S. Pat. No. 3,432,300
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP-A-52-152225 and the like, spiroindanes in U.S. Pat.No. 4,360,589, p-alkoxyphenols in U.S. Pat. British Patent No. 2,06
6,975, JP-A-59-10539, JP-B-57-19765, etc., hindered phenols are described in U.S. Pat.
No. 5, JP-A-52-72224, U.S. Pat.No. 4,228,235, Japanese Patent Publication No. 52-6623, etc., gallic acid derivatives, methylenedioxybenzenes, aminophenols U.S. Pat.Nos. 3,457,079 and 4,332,886, respectively. , Japanese Patent Publication No. 56-21144, hindered amines are U.S. Pat. No. 3,336,135,
No. 4,268,593, British Patent No. 1,326,889, No. 1,354,
No. 313, No. 1,410,846, Japanese Patent Publication No. 51-1420, Japanese Patent Laid-Open No. 58-
114036, 59-53846, 59-78344 and the like, the metal complex, U.S. Pat.Nos. 4,245,018, 4,684,603, 4,
050,938, 4,241,155, British Patent 2,027,731
(A) and the like, respectively. These compounds can achieve their purpose by adding 5 to 100% by weight, based on the corresponding color coupler, to the photosensitive layer, usually by co-emulsifying the coupler with the coupler. In order to prevent the cyan dye image from deteriorating due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into both layers adjacent to the cyan coloring layer.

The photosensitive material prepared using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat.No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat.Nos. 3,314,794 and 3,352,681), benzophenone compounds (for example, Kaisho
46-2784), cinnamic acid ester compounds (for example, those described in US Pat. Nos. 3,705,805 and 3,707,375), butadiene compounds (for example, US Pat. No. 4,045,
229) or a benzooxide compound (eg, as described in US Pat. No. 3,700,455)
Can be used. An ultraviolet absorbing coupler (for example, an α-naphthol-based cyan dye forming coupler), an ultraviolet absorbing polymer, or the like may be used. These ultraviolet absorbers may be mordanted to a specific layer.

The photosensitive material prepared according to the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As a binder or protective colloid which can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin may be lime-treated,
It may be either treated with an acid or not. Details of the method for producing gelatin are described in Arthur Weiss, The Macromolecular Chemistry of Gelatin, (Academic Press, 1964).

As the support used in the present invention, a transparent film such as a cellulose nightlace film or polyethylene terephthalate, which is generally used in a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of reflective supports is more preferred.

The "reflective support" used in the present invention means one which enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clear. Examples include those coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light-reflecting substance dispersed therein as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or in combination with a reflective material, such as a glass plate, polyethylene terephthalate, polyester film of cellulose triacetate or cellulose nitrate, polyamide There are films, polycarbonate films, polystyrene films, vinyl chloride resins, etc.
These supports can be appropriately selected depending on the purpose of use.

As the light-reflecting substance, a white pigment should be sufficiently kneaded in the presence of a surfactant, and the surface of the pigment particles should not be mixed.
It is preferable to use one treated with a tetrahydric alcohol.

The occupying area ratio (%) of the white pigment fine particles per limited unit area is projected on the unit area of the most typically observed area by dividing the observed area into adjacent 6 μm × 6 μm unit areas. The occupied area ratio (%) of fine particles (R _i can be obtained by measuring. The variation coefficient of the occupied area ratio (%) is the ratio of the standard deviation s of R _{i to} the average value of R _i s /
Can be sought by. The number (n) of the target unit areas is preferably 6 or more. Therefore, the coefficient of variation s / is Can be sought by.

In the present invention, the occupied area ratio (%) of the fine particles of the pigment
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, the dispersibility of particles can be said to be “uniform”.

The color photographic light-sensitive material of the present invention is preferably subjected to a coloring phenomenon, bleach-fixing, and washing treatment (or stabilizing treatment). Bleaching and fixing may be performed separately instead of the one bath as described above.

In the case of continuous processing, it is desirable that the replenishment amount of the developer is as small as possible from the viewpoint of resource saving and low pollution.

The preferred amount of replenishing color developer is 1 m ^{2 of} light-sensitive material
It is less than 200 ml. More preferably, it is 120 ml or less.
More preferably, the volume is 100 ml or less. However, the replenishing amount here indicates the amount of replenishment of the so-called color developing replenisher, and the amount of an additive or the like for correcting deterioration with time or concentration is outside the replenishing amount. Here, the additive refers to, for example, water for diluting concentration, a preservative which is susceptible to deterioration with time, or an alkali agent for increasing pH.

The color developing solution applied to the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3
-Methyl-4-amino-N, N-diethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p
-Toluenesulfonate and the like. Two or more of these compounds can be used in combination depending on the purpose.

Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazites, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Preservatives, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines, dye-forming couplers, competitive couplers, sodium boron hydride and the like. Fogging agent, auxiliary developing agent such as 1-phenyl-3-pyrazolidone, viscosity-imparting agent, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ,ethylene Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexane diamine tetraacetic acid, hydroxyethyliminodiacetic Gino acetate, 1-hydroxyethylidene-1,1
Representatives of diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof Examples can be given.

When the reversal process is performed, color development is usually performed after black-and-white development. This black-and-white developer contains dihydroxybenzenes such as hydroquinone and 1-phenyl-3.
Known black-and-white developing agents such as 3-pyrazolidones such as -pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishment amount of these developing solutions is generally 3 liters or less per 1 square meter of the light-sensitive material though it depends on the aller photographic light-sensitive material to be processed, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the treatment layer with air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
Fixing before bleach-fixing or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Examples of the bleaching agent include iron (III) and cobalt (II
Compounds of polyvalent metals such as I), chromium (VI), and copper (II), peracids, quinones, and nitro compounds are used.
Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. . Among them, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salt and persulfate are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution containing these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: U.S. Patent No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,
988, JP-A-53-32736, JP-A-53-57831, and JP-A-53-37418
No. 53, No. 53-72623, No. 53-95630, No. 53-95631, No. 53
-104232, 53-124424, 53-141623, 53-2842
No. 6, Research Disclosure No. 17,129 (1978
Compounds having a mercapto group or a disulfide group described in JP-A No. 50-140129; JP-B-45-8506; JP-A-52-20832;
No. 53-32735, thiourea derivatives described in U.S. Pat. Oxyethylene compounds; JP-B-45-8836
Polyamine compounds described in JP-A-49-42434,
No. 49-59644, No. 53-94927, No. 54-35727, No. 55-265
Compounds described in No. 06 and No. 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect,
Especially U.S. Patent No. 3,893,858, West German Patent No. 1,290,812,
The compounds described in JP-A-53-95630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodide salts, and the use of thiosulfates is common.
In particular, ammonium thiosulfate can be used most widely.
As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and
Television Engineers Volume 64, pp.248-253 (May 1955)
Monthly issue) can be obtained by the method described in.

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in Japanese Patent Application No. 131632/1986 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemical fungicide chemistry", The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Techniques" edited by the Sanitary Technology Association, and "Encyclopedia of Antibacterial and Antifungal Agents" by the Japan Society for Antibacterial and Antifungal Agents can be used.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to
9, preferably 5 to 9. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilizing process, the method disclosed in
All known methods described in Nos. 57-8543, 58-14834, and 60-220345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and as an example thereof, it is used as a final bath of a color light-sensitive material for photographing. Examples include a stabilizing bath containing formalin and a surfactant. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, U.S. Patent No. 3,342,597
No. 3,342,599, indoaniline compounds described in No.
Research Disclosure No. 14,850 and 15,159
Examples thereof include the Schiff base type compounds described in JP-A No. 13924/1983, the aldol compounds described in JP-A-13924, the metal salt complexes described in US Pat. No. 3,719,492, and the urethane compounds described in JP-A-53-135628.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.
No. etc.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

In order to fully exhibit the excellent characteristics of the silver halide photographic light-sensitive material of the present invention, 2 minutes and 30 seconds in a color developer containing substantially no benzyl alcohol and containing bromine ions in an amount of 0.002 mol / l or less. It is preferable to perform processing in the following developing time.

"Substantially free of benzyl alcohol" as described above
Means 2 ml or less, preferably 0.5 ml or less, and most preferably none at all per color developer.

EXAMPLES Hereinafter, the present invention will be described based on specific examples, but the present invention is not limited thereto.

[Example 1] Silver halide emulsion (1) of blue-sensitive silver halide emulsion layer
Was prepared as follows.

(1st solution) H ₂ O 1000 ml NaCl 8.8 g Gelatin 25 g (2nd solution) Sulfuric acid (1N) 20 ml (3rd solution) The following compound (1%) 3 ml (4 solutions) KBr 14.01g NaCl 1.72g H ₂ O added 130 ml (5 solutions) AgNO ₃ 25 g H ₂ O added 130 ml (6 solutions) KBr 56.03g NaCl 6.88g K ₂ IrCl ₆ (0.001) %) 1.0 ml H ₂ O was added to 285 ml (7 solution) AgNO ₃ 100 g NH ₄ NO ₃ (50%) 2 ml H ₂ O was added to 285 ml (1 solution) to 75 ° C., and ( (Part 2) and (Part 3) were added. Then, (4 solution) and (5 solution) were added simultaneously spending 40 minutes. After a further 10 minutes, (6 solution) and (7 solution) were added simultaneously spending 25 minutes. Five minutes after the addition, the temperature was lowered and the mixture was desalted. Add water and dispersed gelatin, adjust pH to 6.2, average particle size 1.01 μm, coefficient of variation (standard deviation divided by average particle size; s / d) 0.08 Monodisperse cubic salt of 80 mol% silver bromide A silver bromide emulsion (1) was obtained. This emulsion was optimally chemically sensitized with triethylthiourea.

A silver halide emulsion (2) in a blue-sensitive halogenated emulsion layer,
Further, for the silver halide emulsions (3) and (4) of the green-sensitive silver halide emulsion layer and the silver halide emulsions (5) and (6) of the red-sensitive silver halide emulsion layer, the chemical amount, It was prepared by changing the temperature and the addition time.

The shapes, average grain sizes, halogen compositions and variation coefficients of the silver halide emulsions (1) to (6) are as shown below.

On a paper support laminated on both sides with polyethylene,
A multilayer color photographic light-sensitive material having the layer structure shown below was produced. The coating liquid was prepared as follows.

Preparation of 1st layer coating solution 19.1 g of yellow coupler (Y-15) and 0.46 g of antifoggant (Cpd-2) were added to 27.2 cc of ethyl acetate and solvent (So.
lv-1) 3.8cc and solvent (Solv-2) 3.8cc are added and dissolved,
Add this solution to 10% sodium dodecylbenzene sulfonate.
It was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc.
On the other hand, silver halide emulsion (1) and silver halide emulsion (2)
A blue-sensitizing sensitizing dye shown below was added to the 6: 4 mixed emulsion of 5.0 × 10 ⁻⁴ mol per mol of silver to prepare a mixture. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating liquid for the first layer having the composition shown below.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a gelatin hardening agent for each layer, 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dye in each layer.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1.2 × 10 ^-2 mol and 1.1 × 10 1 mol per mol of silver halide, respectively.
^-2 mol was added.

Further, to the green-sensitive emulsion layer, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added at 1.0 × 10 ⁻³ mol per mol of silver halide.

Further, to the red-sensitive emulsion layer, 2-amino-5-mercapto-1,3,4-thiadiazole was added in an amount of 3.0 × 10 ^-4 mol per mol of silver halide.

The following dyes were used as the anti-irradiation dye.

The composition of each layer is shown below. The numbers indicate the application amount (g / m ² )
The silver halide emulsion represents the coating amount in terms of silver.

(Layer structure) Support Paper support laminated on both sides with polyethylene [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue-sensitive layer) Silver halide emulsion (1) + (2) 0.26 Gelatin 1.20 Yellow coupler (Y-15) 0.66 Antifoggant (Cpd-2) 0.02 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13 Second layer (color mixing prevention layer) Gelatin 1.34 Anti-color mixing agent (Cpd-3) 0.04 Solvent (Solv-3) 0.10 Solvent (Solv-4) 0.10 Third layer (green sensitive layer) Silver halide emulsion (3) + (4) 0.14 Gelatin 1.30 Magenta coupler (ExM ) 0.27 Color image stabilizer (Cpd-5) 0.16 Anti-stain agent (Cpd-8) 0.025 Anti-stain agent (Cpd-9) 0.032 Solvent (Solv-3) 0.21 Solvent (Solv-5) 0.33 Fourth layer (UV absorption) Layer) Gelatin 1.44 UV absorber (UV-1) 0.53 Color mixture inhibitor (Cpd-2) 0.05 Solvent (Solv-2) 0.26 Fifth layer (red sensitive layer) Silver halide emulsion (5) + (6) 0.20 Gelatin 0.89 Cyan coupler (ExC-1) 0.13 Cyan coupler (ExC-2) 0.16 Color image stabilizer ( Cpd-1) 0.27 Color image stabilizer (Cpd-6) 0.07 Antifoggant (Cpd-2) 0.01 Solvent (Solv-1) 0.19 Sixth layer (UV absorbing layer) Gelatin 0.47 UV absorber (UV-1) 0.17 Solvent (Solv-2) 0.08 Seventh layer (protective layer) Gelatin 1.25 Polyvinyl alcohol acrylic 0.05 Modified copolymer (Modification degree 17%) Liquid paraffin 0.02 (Solv-2) solvent _{O = PO-C 9 H 19} -iso) 3 The above photosensitive material was exposed through an optical wedge and processed in the following steps.

Processing process temperature Time Color development 37 ° C 3 minutes 30 seconds Bleach fixing 33 ° C 1 minute 30 seconds Water washing 24-34 ° C 3 minutes Drying 70-80 ° C 1 minute The composition of each processing solution is as follows.

Color developer Water 800 ml Diethylenetriaminepentaacetic acid 1.0 g Nitrilotriacetic acid 2.0 g Benzyl alcohol 15 ml Diethylene glycol 10 ml Sodium sulfite 2.0 g Potassium bromide 1.0 g Potassium carbonate 30 g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulphate 4.5g Hydroxylamine sulphate 3.0g Fluorescent brightener (WHITEX4B, Sumitomo Chemical Co., Ltd.) 1.0g Add water 1000ml pH (25 ℃) 10.25 Bleach fixer Water 400ml Ammonium thiosulfate (70%) 150ml Sodium sulfite 18g Ethylenediaminetetraacetate iron (III) ammonium 55g Disodium ethylenediaminetetraacetate 5g Water was added to 1000ml pH (25 ℃) 6.70 The sample thus obtained was designated as 1A and the yellow of the first layer Samples except that the coupler and additives [color image stabilizer] (50 mol% based on the coupler) were combined as shown in Table 1.
Other samples were made in the same manner as 1A.

Each sample on which a dye image was formed in this manner was exposed for 200 hours with a xenon tester (illuminance: 200,000 lux), and the density residual rate at an initial density of 1.0 was shown as a percentage.

In order to examine the heat resistance, the percentage of the residual dye at the initial yellow density of 1.0 when stored at 100 ° C for 400 hours is shown. The results obtained are shown in Table 1. The measurement was performed with a Macbeth densitometer RD-514 type (status, AA filter).

From these results, it is understood that the compound of the present invention is extremely effective in preventing the photobleaching of the color image as compared with the comparative compound.
Not only that, but it also has an excellent effect on preventing thermal fading.

[Example 2] Silver halide emulsion (1) of blue-sensitive silver halide emulsion layer
Was prepared as follows.

(1 liquid) H ₂ O 1000cc NaCl 5.8g Gelatin 25g (2 liquid) Sulfuric acid (1N) 20cc (3 liquid) The following compound (1%) 3cc (4 solution) KBr 0.18g NaCl 8.51g H ₂ O added 130cc (5 solution) AgNO ₃ 25g H ₂ O added 130cc (6 solution) KBr 0.70g NaCl 34.05g K ₂ IrCl ₆ (0.001%) 2cc H ₂ O was added and 285 cc (7 liquid) AgNO ₃ 100 g H ₂ O was added and 285 cc (1 liquid) was heated to 60 ° C., and (2 liquid) and (3 liquid) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 60 minutes. 10 minutes after the addition of (liquid 4) and (liquid 5),
(Sixth solution) and (Sixth solution) were simultaneously added over 25 minutes. Five minutes after the addition, the temperature was lowered and the mixture was desalted. Add water and dispersed gelatin, adjust pH to 6.0, average particle size 1.0 μm, coefficient of variation (standard deviation divided by average particle size; s / d) 0.
11. A monodisperse cubic silver chlorobromide emulsion containing 1 mol% of silver bromide was obtained. Triethylthiourea was added to this emulsion for optimum chemical sensitization. After that, the following spectral sensitizing dye (Sen-1) was added at 7 × 10 ⁻⁴ per mol of silver halide emulsion.
Mole was added.

Silver halide emulsion in green-sensitive silver halide emulsion layer (2)
Also, the silver halide emulsion (3) in the red-sensitive silver halide emulsion layer was prepared in the same manner by changing the chemical amount, temperature and addition time.

For the silver halide emulsion (2), a spectral sensitizing dye (Sen
-2) was added in an amount of 5 × 10 ^-4 mol per mol of the emulsion, and a spectral sensitizing dye (Sen-3) was added to the silver halide emulsion (3).
^Was added in an amount of 0.9 × 10 ^-4 mol per mol of the emulsion.

The shapes, average grain sizes, halogen compositions and variation coefficients of the silver halide emulsions (1) to (3) are as shown below.

Using the prepared silver halide emulsions (1) to (3),
A multilayer color photographic light-sensitive material having the layer structure shown below was produced. The coating liquid was prepared as follows.

1st layer coating liquid preparation Yellow coupler (Y-15) 19.1g to ethyl acetate 27.2c
c and 3.8 cc of solvent (Solv-1) were added and dissolved, and this solution was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, a blue-sensitive sensitizing dye (Sen-1) was added to the silver halide emulsion (1) in an amount of 5.0 × 10 ^-4 mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating liquid for the first layer having the composition shown below.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a gelatin hardening agent for each layer, 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used.

The following compounds were added to the red-sensitive emulsion layer in an amount of 1.9 × 10 ⁻³ mol per mol of silver halide.

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer in an amount of 1.0 × 10 ^-2 mol per mol of silver halide.

For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 1-
(5-methylureidophenyl) -5-mercaptotetrazole was added at 1.0 × 10 ⁻³ mol per mol of silver halide;
1.5 × 10 ⁻³ mol was added.

Further, to the red-sensitive emulsion layer, 2-amino-5-mercapto-1,3,4-thiadiazole was added in an amount of 2.5 × 10 ^-4 mol per mol of silver halide.

The composition of each layer is shown below. The abbreviations and structural formulas of the respective compounds are the same as in Example 1.

(Layer constitution) Support Paper support laminated on both sides with polyethylene [White pigment (TiO ₂ ) on the polyethylene of the first layer (2.7 g
/ m ² ) and bluish dye (ultraviolet)] First layer (blue sensitive layer) Silver halide emulsion (1) 0.26 Gelatin 1.13 Yellow coupler (Y-15) 0.66 Solvent (Solv-4) 0.28 Second layer (Anti-color mixing layer) Gelatin 0.89 Anti-color mixing agent (Cpd-3) 0.08 Solvent (Solv-4) 0.20 Solvent (Solv-3) 0.20 Dye (T-1) 0.005 Third layer (Green-sensitive layer) Silver halide emulsion ( 2) 0.15 Gelatin 0.51 Magenta coupler (ExM) 0.27 Color image stabilizer (Cpd-5) 0.10 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Solvent (Solv-3) 0.19 Solvent ( Solv-5) 0.15 Fourth layer (UV absorbing layer) Gelatin 1.42 UV absorber (UV-1) 0.52 Color mixture inhibitor (Cpd-3) 0.06 Solvent (Solv-2) 0.26 Dye (T-2) 0.015 Fifth layer (Red-sensitive layer) Silver halide emulsion (3) 0.22 Gelatin 1.06 Cyan coupler (ExC-3) 0.37 Color image stabilizer (Cpd-1) 0.32 Image Stabilizer (Cpd-6) 0.18 Solvent (Solv-2) 0.10 Solvent (Solv-7) 0.10 Solvent (Solv-6) 0.11 Sixth Layer (UV Absorbing Layer) Gelatin 0.48 UV Absorbing Agent (UV-1) 0.18 Solvent (Solv-2) 0.08 Dye (T-2) 0.005 Seventh layer (protective layer) Gelatin 1.33 Polyvinyl alcohol acrylic 0.05 Modified copolymer (Modification degree 17%) Liquid paraffin 0.03 The above photosensitive material was exposed through an optical wedge and processed in the following steps.

Processing process temperature Time Color development 35 ℃ 45 seconds Bleach fixing 35 ℃ 45 seconds Water wash 35 ℃ 30 seconds Water wash 35 ℃ 30 seconds Water wash 35 ℃ 30 seconds Dry 75 ℃ 60 seconds Color developer water 800ml Ethylenediamine-N, N, N ', N'-Tetramethylenephosphonic acid 3.0g Triethanolamine 8.0g Sodium chloride 1.4g Potassium carbonate 25g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.0g N, N-bis (carboxymethyl) hydrazine 5.0g Optical brightener (WHITEX4, Sumitomo Chemical Co., Ltd.) 1.0g Water added 1000 ml pH (25 ° C) 10.05 Bleach-fixing solution Water 700 ml Ammonium thiosulfate solution (700 g / l) 100 ml Ammonium sulfite 18 g Ethylenediaminetetraacetic acid ferric ammonium dihydrate 55 g Ethylenediaminetetraacetic acid disodium salt 3 g Ammonium bromide 40 g Glacial acetic acid 8 g Water is added 1000 ml pH (25 5.5) Water washing solution Tap water was treated with ion exchange resin to reduce calcium and magnesium to 3 ppm or less, respectively (conductivity at 25 ° C was 5 µs / cm).

The sample thus obtained was designated as sample 2A, and was the same as sample 2A except that the yellow coupler and the additive [color image stabilizer] (100 mol% based on the coupler) of the first layer were combined as shown in Table 2. Then, another sample was prepared.

Each sample thus formed with a dye image was exposed to a fluorescent lamp fading device (illuminance: 15,000 lux) for 4 weeks to perform a fading test, and the density residual ratio at an initial yellow density of 1.0 was shown as a percentage.

Further, the maximum reflection density (Dmax) of the yellow density is measured, and the ratio to the value when the density of the color image stabilizer-free level is 100 is shown in Table 2 together with the results of the fading test.

From these results, it can be seen that the compound of the present invention does not deteriorate the coupler's color developing property as compared with the comparative compound and is extremely effective in preventing photofading.

Example 3 The yellow couplers of the samples 2A, 2B, 2C, 2D, 2E, 2K, 2L, 2N and 2O of Example 2 were replaced with Y-5, Y-13, Y-14 and Y.
When the same treatment and fading test as in Example 2 were carried out in place of −20 and Y-27, the compound of the present invention showed an extremely excellent fading prevention effect.

[Effect of the Invention] The silver halide color photographic light-sensitive material of the present invention comprises the compound represented by the general formula [I] in at least one layer of the yellow dye image forming layer and its adjacent layer. Image quality preservation is extremely excellent.

The silver halide color photographic light-sensitive material of the present invention does not exhibit the color developability of the yellow coupler, and the obtained yellow dye image shows remarkably high fastness to light, heat or humidity.

Claims (1)

[Claims] 1. An anti-fading agent represented by the following general formula [I] is incorporated in a yellow coupler-containing layer on a support in an amount of 10 to 200 mol% based on the yellow coupler and coemulsified with the coupler. A silver halide color photographic light-sensitive material characterized by being contained as an emulsion dispersion. General formula [I] [In the formula, R ₁ and R ₂ are a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a phosphonyl group, a sulfinyl group, an alkylcarbamoyl group, Represents an arylcarbamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkyloxycarbonyl group or an aryloxycarbonyl group, and Y represents a non-membered group which is necessary for forming a 5-membered heterocyclic ring with 2 nitrogen atoms. Represents a group of metal atoms. However, in the non-metal atom group forming Y, there is at least one carbonyl group, and it is adjacent to a nitrogen atom, and when 1-phenyl-3-pyrazolidone is formed, the 2-position The substituent is a hydrogen atom,
It is not an acyl group substituted with an acetyl group or a carboxyl group.