JPH06342198A - Color image forming method and color photographic sensitive material used therefor - Google Patents

Abstract

PURPOSE:To provide a color image forming method and a color photographic sensitive material, with which good color development properties and color reproducibility can be obtained and image preservable properties can be improved and also the variation of color balance does not occur over a long period by adding a combinaion of specific cyan color image forming couplers to a silver halide emulsion layer. CONSTITUTION:The color photographic sensitive material which has a silver halide emulsion layer contg. at least one of cyan color image forming couplers represented by the formula I and at least one of those represented by the formula II on the substrate is processed with a color developer having <=5ml/l of benzylalcohol concn. after exposure of the sensitive material. In the formulas, each of R<1>, R<2> and R<4> is an aliphatic, aryl or heterocyclic group optionally having substituents; R<3> and R<5> is a hydrogen atom or an alkyl group, etc., wherein optionally R<3> is a nonmetallic atomic group forming a five to six membered nitrogen heterocycle together with R<2>; R<6> is an aliphatic group; each of R<7> and R<8> is a hydrogen atom or an alkyl group same as or different from each other; each of Z<1> and Z<2> is a hydrogen atom or an eliminable group at the time of subjecting the couplers to coupling reaction with the oxidized body in the developing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color photographic light-sensitive material which forms a color photographic image having excellent storability, and more specifically, a combination of two cyan color image-forming couplers (hereinafter referred to as cyan couplers). Due to photobleaching,
The present invention relates to a silver halide color photographic light-sensitive material capable of forming a color image which is less susceptible to thermal fading and is less likely to lose color balance even after long-term storage, and a color image forming method used therefor.

[0002]

2. Description of the Related Art In order to form a color photographic image,
Photosensitive couplers of three colors of yellow, magenta and cyan are contained in a photosensitive layer (blue-sensitive, green-sensitive and red-sensitive photosensitive layers), and the exposed photosensitive material is color-developed with a so-called color developing agent. The oxidation product of the aromatic primary amine reacts with each of the above-mentioned couplers to give a coloring dye. In this case, the color forming dye is a vivid cyan, magenta or yellow dye having little secondary absorption, and it is basically important to provide a color photographic image with good color reproducibility. However, on the other hand, the problem of the storability of the color photographic image is also extremely important, and the formed color photographic image is required to have good storability under various conditions. In order to improve storage stability, not only the fading or discoloring speed of coloring dyes of different hues should be slow, but also the fading speed should be as uniform as possible over the entire image density, and the color balance of the residual dye image should not change. is necessary.
However, in conventional light-sensitive materials, especially color papers, the cyan dye image is largely deteriorated due to long-term dark fading due to the influence of humidity and heat, and therefore the color balance is apt to change, and improvement is strongly desired. Further, conventionally, a color-forming dye that is difficult to dark fade has a strong hue, and has a strong reciprocal tendency that it gives only a cyan dye image that is easily photobleached and photobleached.Development of a color photographic light-sensitive material that overcomes this problem Is required. In order to partially solve such a problem, a specific combination of couplers has been conventionally proposed, for example, Japanese Patent Publication No. 52-7344, Japanese Patent Publication No. 57-200037, and Japanese Patent Application No. 59-57238. An example thereof is described in JP-A-58-35178. However, with these combinations, the resulting color developability is insufficient, or the hue of the color forming dye is poor,
The color balance of the residual dye image changes due to adverse effects on color reproduction or deterioration due to light or heat, and improvement is desired.

[0003]

The present invention overcomes the above-mentioned drawbacks of the conventional color photographic light-sensitive materials, and its object is to combine a specific cyan color image-forming coupler in a silver halide emulsion layer. By containing it, the color reproducibility and the color reproducibility of the obtained color photographic image are good, and the image storability is improved, and in particular, the color balance does not fluctuate either under exposure to light or in the dark for a long period of time.
It is to provide a color image forming method. Further, an object of the present invention is to provide a silver halide color which has good image storability even when stored for a long time in an atmosphere of at least one of high temperature and high humidity, and which does not lose color balance not only in the high color-developing portion but also in the gradation portion. To provide a photographic light-sensitive material.
Furthermore, the object of the present invention is to improve storage stability and
It is intended to provide a silver halide color photographic light-sensitive material having improved light fastness.

[0004]

That is, the present invention is as follows.
(1) A color photographic light-sensitive material characterized by having an emulsion layer containing at least one cyan image forming coupler represented by the following general formulas [I] and [II] on a support is exposed. A method for forming a color image, which comprises processing with a color developing solution having a concentration of benzyl alcohol of 5 ml / l or less.

[0005]

[Chemical 3]

(In the formula, R ¹ , R ² and R ⁴ represent an aliphatic group, an aryl group or a heterocyclic group which may have a substituent, and R ³ and R ⁵ represent a hydrogen atom or a halogen atom. ,
An alkyl group or an acylamino group, and R ³ is R ²
It may also be a non-metal atom group forming a nitrogen-containing 5- or 6-membered ring. R ⁶ represents an aliphatic group, R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a lower alkyl group. Z ¹ and Z ² represent a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. (2) After exposing the color photographic light-sensitive material with a color developer having a benzyl alcohol concentration of 5 ml / l or less,
In addition, the color image forming method according to the item (1), in which the replenishing solution is 100 ml or less per 1 m ^{2 of the} processing area, and (3) the color image is formed on the support by the following general formulas [I] and [II]. Color photograph characterized by having a silver halide emulsion layer containing at least one cyan color image-forming coupler and a silver halide emulsion layer containing at least one pyrazoloazole-based magenta color image-forming coupler. Photosensitive material,

[0007]

[Chemical 4]

(In the formula, R ¹ , R ² and R ⁴ represent an aliphatic group, an aryl group or a heterocyclic group which may have a substituent, and R ³ and R ⁵ represent a hydrogen atom or a halogen atom. ,
An alkyl group or an acylamino group, and R ³ is R ²
It may also be a non-metal atom group forming a nitrogen-containing 5- or 6-membered ring. R ⁶ represents an aliphatic group, R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a lower alkyl group. Z ¹ and Z ² represent a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. ) Is provided.

In the present specification, the "aliphatic group" may be linear, branched or cyclic and includes saturated and unsaturated groups such as alkyl, alkenyl and alkynyl groups. The cyan coupler represented by the general formula [I] or [II] used in the present invention will be described in more detail. The above general formulas [I] and [II]
In the formula, R ¹ , R ² and R ⁴ are each an aliphatic group having 1 to 31 carbon atoms (eg, methyl group, butyl group, octyl group, tridecyl group, iso-hexadecyl group, cyclohexyl group, etc.), aryl group (eg, phenyl group). Group, naphthyl group, 2-pyridyl group, 2-thiazolyl group, 2-imidazolyl group, 2-furyl group, 6-quinolyl group, etc., and these are alkyl group, aryl group, heterocyclic group, alkoxy group ( For example, an aryloxy group such as a methoxy group, a 2-methoxyethoxy group, a tetradecyloxy group (eg, 2,4-di-tert-amylphenoxy group, 2
-Chlorophenoxy group, 4-cyanophenoxy group, 4-
Butanesulfonamide phenoxy group etc.), acyl group (eg acetyl group, benzoyl group etc.), ester group (eg ethoxycarbonyl group, 2,4-di-ter)
t-amylphenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (for example, acetylamino group, butanesulfonamide group, dodecylbenzenesulfonamide group, dipropylsulfamoylamino) Group), carbamoyl group (eg, dimethylcarbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group (eg, butylsulfamoyl group), imide group (eg, succinimide group, hydantonyl group, etc.), ureido group (eg, phenylureido group). Group, dimethylureido group, etc.), sulfonyl group (eg, methanesulfonyl group, carboxymethanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (eg, butylthio group, phenylphenyl group) And thio group), a hydroxyl group,
It may be substituted with a group selected from a cyano group, a carboxyl group, a nitro group, a sulfo group, a halogen atom and the like. When having two or more substituents, they may be the same or different from each other.

In the above general formula [I], R ³ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acylamino group or a nonmetallic atom group forming a nitrogen-containing 5- or 6-membered ring together with R ^2. Represent. The general formula [II]
In, R ⁵ represents a hydrogen atom, a halogen atom, a lower alkyl group, an aryl group (eg, a phenyl group) or an acylamino group (eg, an acetylamino group).
Examples of the aliphatic group represented by R ⁶ in the general formula [II] include a methyl group, an ethyl group, a cyclohexyl group and a tetradecyl group. R ⁷ and R ⁸ each represent a hydrogen atom or a lower alkyl group. The above general formula [I]
Z ¹ and Z ² in the general formula [II] are
Represents a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkoxy group (eg, ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, Carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy group (eg, 4
-Chlorophenoxy group, 4-methoxyphenoxy group, 4
-Carboxyphenoxy group etc.), acyloxy group (e.g. acetoxy group, tetradecanoyloxy group, benzoyloxy group etc.), sulfonyloxy group (e.g.
Methanesulfonyloxy group, toluenesulfonyloxy group etc.), amide group (eg dichloroacetylamino group, heptafluorobutyrylamino group, methanesulfonylamino group, toluenesulfonylamino group etc.), alkoxycarbonyloxy group (eg ethoxycarbonyloxy) Group, benzyloxycarbonyloxy group etc.), aryloxycarbonyloxy group (eg phenoxycarbonyloxy group etc.), aliphatic or aromatic thio group (eg ethylthio group, phenylthio group, tetrazolylthio group etc.), imide group (eg Succinimide group, hytantoinyl group, etc.), aromatic azo group (eg, phenylazo group, etc.), and the like. These leaving groups may include photographically useful groups. Further, preferable examples of the cyan coupler represented by the above general formula [I] or [II] are as follows.

In the general formula [I], R ¹ is preferably an aryl group or a heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group; an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group. More preferably, it is an aryl group substituted with a group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group. In the general formula [I], when R ³ and R ² do not form a ring, R ² is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group, R 2
³ is preferably a hydrogen atom. In the general formula [II], R ⁶ is preferably a substituted or unsubstituted alkyl group, and particularly preferably a substituted aryloxy-substituted alkyl group. In the general formula [II], R ⁶ is preferably an alkyl group having 1 to 14 carbon atoms, and particularly preferably 1 carbon atom.
~ 3 alkyl groups. Each of R ⁷ and R ⁸ is preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.

Preferred R ⁵ in the general formula [II] is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. In the general formula [II], it is particularly preferable that R ⁵ is a chlorine atom, R ⁶ is an alkyl group having 1 to 14 carbon atoms, and R ⁷ and R ⁸ are both hydrogen atoms. In the general formulas [I] and [II], Z ¹ and Z ² are each a hydrogen atom, a halogen atom, an alkoxy group which may have a substituent, an aryloxy group or a sulfonamide group. In formula [II], Z ² is preferably a halogen atom, and particularly preferably a chlorine atom and a fluorine atom. In formula [I], Z ¹ is more preferably a halogen atom, and particularly preferably a chlorine atom and a fluorine atom. Below, the above general formulas [I] and [I
Specific examples of the cyan coupler compound represented by I] are listed below, but the present invention is not limited thereto.

[0013]

[Chemical 5]

[0014]

[Chemical 6]

[0015]

[Chemical 7]

[0016]

[Chemical 8]

[0017]

[Chemical 9]

[0018]

[Chemical 10]

[0019]

[Chemical 11]

[0020]

[Chemical 12]

[0021]

[Chemical 13]

[0022]

[Chemical 14]

[0023]

[Chemical 15]

[0024]

[Chemical 16]

[0025]

[Chemical 17]

[0026]

[Chemical 18]

[0027]

[Chemical 19]

[0028]

[Chemical 20]

[0029]

[Chemical 21]

[0030]

[Chemical formula 22]

In the color photographic light-sensitive material of the present invention, by using one or more of the compounds represented by the following general formulas [III] and [IV] (UV absorber and antioxidant (anti-fading agent)) in combination, It is possible to improve the storability of a color image, particularly a cyan image.

[0032]

[Chemical formula 23]

In the formula, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² may be the same or different and may have a hydrogen atom, a halogen atom, a nitro group, a cyano group or a substituent. It represents a good alkyl group, alkoxy group, aryl group, aryloxy group, acylamino group or alkoxycarbonyl group. R ¹³ and R ¹⁴ may be the same or different and represent a hydrogen atom or an alkyl group which may have a substituent, and are not hydrogen atoms at the same time. R ¹⁵ represents an m-valent organic group, and m represents an integer.
Typical compounds represented by the general formula [III] or [IV] are shown below.

[0034]

[Chemical formula 24]

[0035]

[Chemical 25]

[0036]

[Chemical formula 26]

[0037]

[Chemical 27]

[0038]

[Chemical 28]

[0039]

[Chemical 29]

[0040]

[Chemical 30]

[0041]

[Chemical 31]

[0042]

[Chemical 32]

[0043]

[Chemical 33]

[0044]

[Chemical 34]

A method for synthesizing the compound represented by the above general formula [III] or other compound examples is described in JP-B-44-29.
620, JP-A-50-151149, JP-A-54-
95233, US Pat. No. 3,766,205, US Pat. No. 3,761,272, EP0057160,
Research Disclosure 22519 (1983, No. 2
25) and the like. In addition, JP-A-58-11
1942, Japanese Patent Application Nos. 57-61937 and 57-6360.
2, ibid. 57-129780 and ibid. 57-133371.
It is also possible to use the high molecular weight UV absorbers described in 1., and it is also possible to use low molecular weight and high molecular weight UV absorbers in combination. The synthetic method of the compound represented by the general formula [IV] or other examples of the compound is described in US Pat. No. 3,112,3.
No. 38, No. 3,168,492, No. 3,206,41
No. 3, etc. The compounds represented by the general formulas [III] and [IV] are dissolved in a high-boiling organic solvent and a low-boiling organic solvent alone or in a mixed solvent as in the coupler, and dispersed in the hydrophilic colloid. You may coemulsify with the cyan coupler used together. In the present invention, a yellow image-forming coupler (hereinafter, yellow coupler)
There is no particular limitation with respect to, and those conventionally used can be used. The magenta color image-forming coupler (hereinafter, magenta coupler) is preferably a pyrazoloazole-based coupler, but other ones may be used. As the yellow coupler, for example, those represented by the general formula [V] can be used.

[0046]

[Chemical 35]

(In the formula, R ¹⁶ represents a substituted or unsubstituted N-phenylcarbamoyl group, Z ³ represents a hydrogen atom or a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent, and Z ³ represents 2 It may form a multimer or more.) In the general formula [V], the substituent of the fail group of the N-phenylcarbamoyl group R ¹⁶ is a substituent acceptable for R ¹ . It can be arbitrarily selected from the group, and when there are two or more substituents, they may be the same or different. Preferred R ¹⁶ includes the following general formula [VA].

[0048]

[Chemical 36]

(In the formula, G ₁ represents a halogen atom or an alkoxy group, and G ₂ represents a hydrogen atom, a halogen atom or an alkoxy group which may have a substituent. R ¹⁷
Represents an alkyl group which may have a substituent. As the substituent of G ₂ and R ¹⁷ in the general formula [VA], for example, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a dialkylamino group, a heterocyclic group (for example, an N-morpholino group, (N-piperidino group, 2-furyl group, etc.), halogen atom, nitro group, hydroxy group, carboxyl group, sulfo group, alkoxycarbonyl group, etc. Next, regarding the magenta coupler, what can be used in the present invention is, for example, a so-called two-equivalent magenta in which a substituent is introduced into the coupling active position of a pyrazolone type magenta coupler and the substituent is split-off in the color development step. Couplers, eg US Pat. No. 3,311,47
6, U.S. Pat. No. 3,419,391, U.S. Pat. No. 3,617,291, U.S. Pat. No. 3,926,631.
No., etc. Further, a magenta coupler having a substituent group continuous with a sulfur atom at the coupling active position of the magenta coupler can be used. Examples thereof include couplers having a thiocyano group described in US Pat. No. 3,214,437, and US Pat.
A coupler having an acylthio group or a thioacylthio group described in US Pat. No. 3,227,55.
4, No. 3,701,783, and further, couplers having an arylthio group and a heterocyclic thio group described in Japanese Patent Publication No. 53-34044, West German Published Patent No. 29.
Examples thereof include couplers having an alkylthio group described in No. 44601. Also, Japanese Patent Laid-Open Publication No. 57-3
Examples include magenta couplers which release an arylthio group described in No. 5858. In the present invention, Japanese Patent Application No. 58-23434 (Japanese Patent Laid-Open No. 59-16254).
8), Japanese Patent Application No. 58-151354 (JP-A-60-436)
59), Japanese Patent Publication No. 47-27411, Japanese Patent Application No. 58-45.
5, 59-27745 (JP-A-60-17298).
2), Japanese Patent Application No. 58-142801 (Japanese Patent Laid-Open No. 60-335)
The couplers of pyrazoloazole compounds described in 52) and the like are preferable. References that describe the couplers used in the present invention, other exemplified compounds, or synthetic methods are given. Magenta couplers are disclosed in Japanese Patent Laid-Open No. 49-1116, in addition to the above-mentioned documents.
31, 56-126833 and U.S. Pat. No. 4,35.
1,897, etc., yellow coupler compounds are disclosed in
4-48541, JP-B-58-10739, U.S. Pat. No. 4,326,024, Research Disclosure 18053 and the like, respectively. Also,
JP-A-58-42045, Japanese Patent Application Nos. 58-88940, 58-52923, 58-52924 and 58-
The highly colorable ballast group described in 52927 and the like can be linked to any of the coupler compounds used in the present invention.

The cyan, yellow or magenta coupler used in the present invention is usually contained in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 0.1 mol per mol of silver halide.
It is contained in an amount of 1.0 mol, preferably 0.1 to 0.5 mol. The amount ratio between cyan, magenta and yellow couplers is usually about 1: 0.2 to 1.5: 0.5 by molar ratio.
The range is often in the range of 1.5, but the photosensitive material can be designed outside this range. In the present invention, the cyan coupler is based on 1 mol of the coupler represented by the general formula [I].
The coupler represented by the general formula [II] is usually 0.1 to
10 mol, preferably 0.2 to 5 mol is used. In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protect method. For example, dibutyl phthalate, dioctyl phthalate and other phthalate esters, and tricresyl phosphate, trinonyl phosphate and other phosphate esters and the like can be added. After dissolving in a boiling point organic solvent or a low boiling point organic solvent such as ethyl acetate alone or in a mixed solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by the so-called Fisher dispersion method. The low boiling point organic solvent may be removed from the coupler dispersion by a method such as distillation, washing with noodles or ultrafiltration, and then mixed with a photographic emulsion.

If desired, the color photographic light-sensitive material of the present invention may contain a special coupler other than the above-mentioned couplers. For example, a colored magenta coupler can be contained in the green-sensitive emulsion layer to have a masking effect. Further, a development inhibitor releasing coupler (DIR coupler), a development inhibitor releasing hydroquinone and the like can be used in combination in each color-sensitive emulsion layer or in a layer adjacent thereto. The development inhibitor released from these compounds upon development brings about an interlayer superimposing effect such as improvement of image sharpness, image fineness or monochromatic saturation. In the photographic emulsion layer of the color photographic light-sensitive material of the present invention or a layer adjacent to the photographic emulsion layer, a coupler which releases a development accelerator or a nucleating agent with silver development is added to improve photographic sensitivity and graininess of color image. It is also possible to obtain effects such as improvement and increasing gradation. In the present invention, the compounds represented by the general formulas [III] and [IV] (ultraviolet absorbers and antioxidants) can be added to any layer. Preferably, it is contained in the compound-containing layer represented by the general formula [I] or [II] or in the adjacent layer. Similar to the coupler, the ultraviolet absorber is dissolved in a high boiling organic solvent and a low boiling organic solvent alone or in a mixed solvent and dispersed in a hydrophilic colloid. The amounts of the high-boiling organic solvent and the ultraviolet absorber are not particularly limited, but the high-boiling organic solvent is usually used in the range of 0% to 300% based on the weight of the ultraviolet absorber. The compounds which are liquid at room temperature are preferably used alone or in combination.

When the ultraviolet absorber of the above-mentioned general formula [III] is used in combination with the combination of the couplers of the present invention, a colored dye image,
In particular, the storability of a cyan image, especially the light fastness can be improved. The coating amount of the ultraviolet absorber may be an amount sufficient to impart light stability to the cyan dye image, but if it is used in an excessively large amount, it is unexposed portion (white background portion) of the color photographic light-sensitive material.
Since it may cause yellowing, it is usually preferably 1 ×.
10 ⁻⁴ mol / m ² to 2 × 10 ⁻³ mol / m ² , especially 5 × 1
It is set in the range of 0 ⁻⁴ mol / m ^{2 to} 1.5 × 10 ⁻³ mol / m ² . In the layer structure of a light-sensitive material of a normal color paper, an ultraviolet absorber is contained in either one of the layers adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When the ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with the color mixing inhibitor. When the ultraviolet absorber is added to the protective layer, another protective layer may be coated as the outermost layer. The protective layer may contain a matting agent having an arbitrary particle size.

The compounds represented by the general formula [IV] may be used in combination of two or more kinds, and may be used in combination with a conventionally known anti-fading agent in a yellow coupler or a magenta coupler. Various silver halides can be used in the silver halide emulsion layer of the color photographic light-sensitive material according to the present invention. Examples thereof include silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide. Silver iodobromide containing 2 to 20 mol% silver iodide and silver chlorobromide containing 10 to 50 mol% silver bromide are preferred. The crystal form, crystal structure, grain size, grain size distribution, etc. of the silver halide grains are not limited. The crystal of silver halide may be a normal crystal or a twin crystal, and may be any of a hexahedron, an octahedron and a tetrahedron. It may be a tabular grain having a thickness of 0.5 micron or less, a diameter of at least 0.6 micron and an average aspect ratio of 5 or more as described in Research Disclosure 22534. Even if the crystal structure is uniform,
The inside and outside may have different compositions, may have a layered structure, or may have silver halides having different compositions joined by epitaxial joining, and are composed of a mixture of grains of various crystal forms. May be. Further, the latent image may be formed mainly on the surface of the particle or may be formed inside. The grain size of silver halide may be fine grains of 0.1 micron or less, large grains having a projected area diameter of 3 microns, monodisperse emulsion having a narrow distribution,
Alternatively, a polydisperse emulsion having a wide distribution may be used. These silver halide grains can be produced by a known method commonly used in the art.

The above-mentioned silver halide emulsion can be sensitized by a conventional chemical sensitization, that is, a sulfur sensitization method, a noble metal sensitization method, or a combination thereof. Further, the silver halide emulsion according to the present invention can impart color sensitivity to a desired light-sensitive wavelength region by using a sensitizing dye. Examples of dyes that are advantageously used in the present invention include methine dyes such as cyanine, hemicyanine, rhodacyanine, merocyanine, oxonol, and hemioxonol, which are described in detail later, and styryl dyes, and one kind or a combination of two or more kinds is used. You can The support used in the present invention may be either a transparent support such as polyethylene terephthalate or cellulose triacetate or a reflective support described below. A reflective support is more preferred, for example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer, or used in combination with a reflective material, such as a glass plate, polyethylene terephthalate, cellulose triacetate or Polyester film such as cellulose nitrate, polyamide film, polycarbonate film,
There are polystyrene films and the like, and these supports can be appropriately selected depending on the purpose of use. Each of the blue-sensitive, green-sensitive and red-sensitive emulsions of the present invention is spectrally sensitized with a methine dye or the like so as to have color sensitivity. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

The color photographic light-sensitive material of the present invention may be provided with auxiliary layers such as an undercoat layer, an intermediate layer and a protective layer in addition to the above-mentioned constituent layers. A second ultraviolet absorbing layer may be provided between the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer, if necessary. It is preferable to use the above-mentioned ultraviolet absorber for the ultraviolet absorbing layer, but other known ultraviolet absorbers may be used. As the binder or protective colloid of the photographic emulsion, it is advantageous to use gelatin,
Other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose,
Cellulose derivatives such as cellulose sulfates,
Sodium alginate, sugar derivatives such as starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. Various kinds of synthetic hydrophilic polymer substances can be used.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Phot. Japan.
No. 16, page 30 (1966), an enzyme-treated gelatin may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may be used. In the light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightening agent. These may be water-soluble, or a water-insoluble whitening agent may be used in the form of a dispersion. Specific examples of the fluorescent whitening agent are U.S. Pat. Nos. 2,632,701, 3,269,840, 3,359,102, British Patents 852,075, 1,319,763, and Research. Disclosure 176, 17643 (issued in December 1978), page 24, left column 9-
It is described in the description of Brighteners on the 36th line.
In the light-sensitive material of the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like. For example, British Patent 685,475 and US Patent 2,675,
316, 2,839,401, 2,882,1
No. 56, No. 3,048, 487, No. 3, 184, 30
No. 9, No. 3,445,231, West German patent application (OL
S) 1,914,362, JP-A-50-47624.
Nos. 50-71332 and the like can be used.

The light-sensitive material of the present invention contains a hydroquinone derivative, an aminophenol derivative,
It may contain a gallic acid derivative, an ascorbic acid derivative and the like, and specific examples thereof include US Pat. No. 2,360,290.
No. 2,336,327, No. 2,403,721
Issue 2, Issue 2,418,613, Issue 2,675,314
No. 2,701,197, No. 2,704,713
Issue 2, Issue 2,728,659, Issue 2,732,300
No. 2,735,765, JP-A-50-92988.
No. 50-92989, No. 50-93928, No. 50-110337, No. 52-146235, and Japanese Patent Publication No. 50-23813. In the color photographic light-sensitive material of the present invention, in addition to the above, various photographic additives known in the art, such as stabilizers, antifoggants, surfactants, couplers other than the present invention, filter dyes and anti-irradiation dyes. , Developing agents can be added as required, examples of which are Research Disclosure 1
7643. Further, in some cases, a fine grain silver halide emulsion having substantially no photosensitivity in the silver halide emulsion layer or other hydrophilic colloid layer (for example, silver chloride, silver bromide, chloroodor having an average grain size of 0.20 μm or less). Silver halide emulsion) may be added. The color developing solution that can be used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As a color developing agent, 4-amino-N, N-diethylaniline, 3-methyl-4-N, N-diethylaniline, 4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfone Amidoethylaniline,
A typical example is 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline.

The color developer is an alkali metal sulfite,
It may contain a pH buffer such as carbonate, borate and phosphate, a development inhibitor such as bromide, iodide and an organic antifoggant, or an antifoggant. If necessary, a water softener, a preservative such as hydroxylamine, an organic solvent such as benzyl alcohol and diethylene glycol, a polyethylene glycol, a quaternary ammonium salt, a development accelerator such as amines, a dye-forming coupler,
Competitive couplers, antifoggants such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, polycarboxylic acid type chelating agents described in US Pat. No. 4,083,723, published by West Germany ( OL
S) The antioxidant described in 2,622,950 may be included. The photographic emulsifier layer of the color developer is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. Examples of bleaching agents include iron (III), cobalt (III), chromium (IV), copper (II)
Compounds of polyvalent metals such as, peracids, quinones, and nitroso compounds are used. For example, ferricyanide, dichromate, iron (III) or cobalt (III) organic complex salts, for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propanoltetraacetic acid. Or citric acid, tartaric acid,
Complex salts of organic acids such as malic acid; persulfates, permanganates, nitrosophenol and the like can be used. Of these, potassium ferricyanide, sodium iron (III) ethylenediaminetetraacetate, and ammonium iron (III) ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron (III) complex salt, even in a separate bleach,
It is also useful in a one-bath bleach-fix solution.

You may wash with water after color development or bleach-fixing treatment. Color development can be carried out at any temperature between 18 ° C and 55 ° C. Color development is preferably carried out at 30 ° C. or higher, particularly preferably at 35 ° C. or higher. The development time is preferably as short as about 3 and a half minutes to about 1 minute. For continuous development processing, a solution of 100 cc or less per square meter of processing area is replenished. 5 ml of benzyl alcohol in the developer
/ L or less. Bleach-fixing can be carried out at any temperature from 18 ° C to 50 ° C, but preferably 30 ° C or higher. When the temperature is 35 ° C. or higher, the processing time can be reduced to 1 minute or less, and the liquid replenishment amount can be reduced. The time required for washing with water after color development or bleach-fixing is usually within 3 minutes.
It can be washed with water within minutes. The colored pigment deteriorates and fades due to mold during storage as well as deterioration by light, heat or temperature. Especially, the cyan image is greatly deteriorated by mold, so that it is preferable to use an antifungal agent. Specific examples of the fungicide include 2-thiazolylbenzimidazoles as described in JP-A-57-157244. The antifungal agent may be incorporated in the light-sensitive material, added externally in the development processing step, or added in any step so long as it coexists in the processed light-sensitive material.

[0060]

INDUSTRIAL APPLICABILITY The silver halide color photographic light-sensitive material of the present invention is excellent in color forming property and color reproducibility of the color photographic image obtained, and has improved image storability, especially under long-time exposure to light and dark place. The color balance does not change in either case. Further, the light-sensitive material of the present invention has excellent image storability even when stored for a long time in an atmosphere of at least one of high temperature and high humidity, and has an excellent effect that the color balance of not only the high-coloring portion but also the gradation portion is not deteriorated. Play. Furthermore, the light-sensitive material of the present invention can be improved not only in storability but also in light fastness.

[0061]

The present invention will be described in more detail based on the following examples. Actual Reference 1 As described in Table 1 and Table 2, a double-sided polyethylene laminated paper was coated with the first layer (lowermost layer) to the seventh layer (uppermost layer) to prepare a color photographic light-sensitive material. (Samples A to T) The coating liquid for the first layer was prepared as follows. That is, the yellow coupler 10 shown in Table 1
0 g was dissolved in a mixed solution of 166.7 ml of dibutyl phthalate (DBP) and 200 ml of ethyl acetate, and this solution was added to a 1% sodium dodecylbenzenesulfonate aqueous solution 80
A 10% aqueous solution containing gelatin was emulsified and dispersed in 800 g of an aqueous gelatin solution. Next, the total amount of this emulsified dispersion was mixed with 1450 g of a blue-sensitive silver chlorobromide emulsion (Br80%) (containing 66.7 g of Ag) to prepare a coating solution. Coating solutions were prepared for the other layers by the same method. As a hardener for each layer, 2,4-dichloro-6-hydroxy-S-triazine sodium salt was used. The following were used as the spectral sensitizer for each emulsion.

Blue-sensitive emulsion layer: 3,3'-di- (γ-sulfopropyl) -selenacyanine sodium salt (2 × 10 ^-4 mol per mol of silver halide) Green-sensitive emulsion layer: 3,3'- Di- (γ-sulfopropyl)
-5,5'-Diphenyl-9-ethyloxacarbocyanine sodium salt (2.5 x 1 per mol of silver halide)
^0-4 mol) Red-sensitive emulsion layer; 3,3'-di- (γ-sulfopropyl)
-9-Methyl-thiadicarbocyanine sodium salt (2.5 × 10 ^-4 mol per mol of silver halide) The following dye was used as the anti-irradiation dye in each emulsion layer.

[0063]

[Chemical 37]

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

In Table 1, DBP is dibutyl phthalate, T
OP represents tri (n-octyl phthalate), and * a
The chemical structures of the compounds * to * d are as follows.

[0068]

[Chemical 38]

[0069]

[Chemical Formula 39]

These samples were subjected to gradation exposure with a Fuji Color Head 690 enlarger (manufactured by Fuji Photo Film Co., Ltd.) (exposure was carried out so that a portion where the color density after development became 1.0 in gray was included). After that, development processing was performed by the following processing steps.

Processing step temperature Time Current image solution 33 ° C. 3 minutes 30 seconds Bleach-fixing solution 33 ° C. 1 minute 30 seconds Water washing 28-35 ° C. 3 minutes The processing solution used has the following formulation.

Developer Benzyl alcohol 15 ml Diethylene glycol 8 ml Ethylenediamine tetraacetic acid disodium salt 5 g Sodium sulfite 2 g Hydroxylamine sulfate 3 g 4-Amino-N-ethyl-N- (β-methanesulfonamidoethyl) -m-toluidine.2 / 3 Sulfate / Monohydrate 5g Add water to adjust to 1000ml pH 10.20

Bleach-fixing solution Ethylenediaminetetraacetic acid ・ 2 sodium salt 2 g Ethylenediaminetetraacetic acid ferric salt 40 g Sodium sulfite 5 g Ammonium thiosulfate 70 g Water was added to adjust the pH to 1,000 ml 6.80.

After the development processing, each sample was subjected to a discoloration / fading test under the following conditions. Irradiate with xenon tester (illuminance 130,000 lux) for 6 days. Store at 80 ° C for 4 weeks. 60 ° C-
Stored at 70% RH for 8 weeks. Macbeth RD-514 was used for each sample after the discoloration / fading test at a concentration of 1.0 before the test
The density was measured using a type densitometer. The results are shown in Table 4.

[0075]

[Table 4]

The following can be seen from Table 4. Samples B and E were yellow in both photobleaching and dark heat fading.
Compared to the decrease in the density of magenta, the decrease in the density of cyan is large, and the color balance after fading is lost, and the image looks reddish. Samples A and C to D have little dark heat fading and the color balance is maintained, but the photofading causes a large decrease in cyan density as compared with yellow magenta, and the color balance is reddish. On the other hand, the color balance of Samples F to T is maintained in both the light fading and the thermal fading. In particular, a sample L containing a compound of the general formula [III] or [IV]
O has further improved light fastness.

Example 1 The surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated to give Multi-layer color photographic papers (Samples A to K) having the layer structure shown in Table 1 were prepared. The coating liquid was prepared as follows.

Preparation of coating solution for fifth layer 165.0 g of cyan coupler, ultraviolet absorber (UV-
2) 90.0 g, color image stabilizer (Cpd-1) 165.0
g, color image stabilizer (Cpd-6) 5.0 g, color image stabilizer (Cpd-8) 5.0 g, color image stabilizer (Cpd-9)
5.0 g, color image stabilizer (Cpd-10) 5.0 g, color image stabilizer (Cpd-11) 5.0 g as a solvent (Solv-
6) 60 g, (Solv-8) 60 g and ethyl acetate 2
This was dissolved in 50 cc, and this solution was emulsified and dispersed in 1000 g of a 10% gelatin aqueous solution containing 60 cc of 10% sodium dodecylbenzenesulfonate and 10 g of citric acid to prepare an emulsified dispersion C. On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion A having a grain size of 0.41 μm (silver molar ratio). The variation coefficient of grain size distribution is , 0.0 each
9, 0.11, silver bromide 0.8 mol% for each size emulsion
Was locally contained in a part of the surface of the grain based on silver chloride) was prepared. In this emulsion, the red sensitizing dye E shown below is added to the large size emulsion C per mol of silver,
9.0 × 10 ⁻⁵ mol, and for small size emulsion C,
1.1 × 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 C and this silver chlorobromide emulsion C were mixed and dissolved to prepare a coating solution for the fifth layer having the composition shown below. The emulsion coating amount indicates a coating amount equivalent to silver.

Coating solutions for the first to seventh layers other than the fifth layer 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. In addition, Cp for each layer
The total amount of d-14 and Cpd-15 is 25.0 mg / m 2, respectively.
² and 50.0 mg / m ² were added. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0080]

[Chemical 40]

(2.0 × 10 ⁻⁴ mol each for large size emulsion and 2.5 × 10 ⁻⁴ mol each for small size emulsion per mol of silver halide) Green-sensitive emulsion layer

[0082]

[Chemical 41]

(Per mol of silver halide, 4.0 × 10 ^-4 mol for large-sized emulsion and 5.6 × 10 ^-4 mol for small-sized emulsion) and

[0084]

[Chemical 42]

(7.0 × 10 ⁻⁴ mol for large-sized emulsion and 1.0 × 10 ⁻⁴ mol for small-sized emulsion per mol of silver halide) Red-sensitive emulsion layer

[0086]

[Chemical 43]

(0.9 × 10 ⁻⁴ mol for large size emulsion and 1.1 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide)

Further, the following compounds were added in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0089]

[Chemical 44]

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

[0091]

[Chemical formula 45]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)]

First Layer (Blue-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large size emulsion A having an average grain size of 0.88 μm and small size emulsion A of 0.70 μm (silver mol) The coefficient of variation of the grain size distribution is 0.08 and 0.10, respectively. For each size emulsion, 0.3 mol% of silver bromide is locally contained in a part of the grain surface based on silver chloride. 0.27 Gelatin 1.36 Yellow coupler (see Table 5) 0.70 Color image stabilizer (Cpd-1) 0.04 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-) 3) 0.04 solvent (Solv-1) 0.13 solvent (Solv-2) 0.13

Second Layer (Color Mixing Prevention Layer) Gelatin 1.00 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25 Solvent (Solv-7) 0.03

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B of 0.39 μm (Ag mol The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface based on silver chloride in each size emulsion) 0 .13 Gelatin 1.45 Magenta coupler (see Table 5) 0.18 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-5) 0.08 Color image stabilizer (Cpd-6) 0 .01 color image stabilizer (Cpd-7) 0.01 color image stabilizer (Cpd-8) 0.05 solvent (Solv-3) 0.50 solvent (Solv-4) 0.15 solvent (Solv-5) 0.15

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.04 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.02

Fifth Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C of 0.41 μm (Ag mol The ratio of variation of the grain size distribution is 0.09 and 0.11, and 0.8 mol% of AgBr was locally contained in a part of the grain surface based on silver chloride for each size emulsion). 20 Gelatin 0.85 Cyan coupler (see Table 5) 0.33 Ultraviolet absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.01 Solvent ( Solv-6) 0.12 Solvent (Solv-8) 0.12

Sixth Layer (UV Absorbing Layer) Gelatin 0.66 UV Absorber (UV-1) 0.45 Color Image Stabilizer (Cpd-5) 0.03 Color Image Stabilizer (Cpd-12) 0.20

Seventh Layer (Protective Layer) Gelatin 1.13 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.05 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

[0100]

[Chemical formula 46]

[0101]

[Chemical 47]

[0102]

[Chemical 48]

[0103]

[Chemical 49]

[0104]

[Chemical 50]

[0105]

[Chemical 51]

[0106]

[Chemical 52]

[0107]

[Table 5]

The above light-sensitive material was processed into a roll having a width of 127 mm, imagewise exposure was carried out by using a printer processor PP1820V manufactured by Fuji Photo Film Co., Ltd., and continuous in the following processing steps until the tank capacity for color development was doubled. Processed. Treatment process Temperature Time Replenishment amount ^* Color development 38.5 ° C. 45 seconds 73 ml Bleach fixing 35 ° C. 45 seconds 60 ml ^** Rinse (1) 35 ° C. 30 seconds − Rinse (2) 35 ° C. 30 seconds − Rinse (3) 35 ℃ 30 seconds 360 ml Dry 80 ℃ 60 seconds * Replenishment amount per 1 m ^{2 of} light-sensitive material ** In addition to the above 60 ml, light-sensitive material 1 m from rinse (1)
120 ml per ² was poured. (The three-tank countercurrent system from rinse (3) to (1) was used.)

The composition of each processing liquid is as follows. [Color developer] [Tank solution] [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 (sulfonate ethyl) hydroxylamine 5.0 g 10.0 g Triisopropylnaphthalene (β) sodium sulfonate 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamide) Ethyl) -3-methyl-4-aminoaniline ・ 3/2 sulfuric acid ・ monohydrate 5 0.0 g 11.5 g Water was added 1000 ml 1000 ml pH (25 ° C./adjusted with potassium hydroxide and sulfuric acid) 10.00 11.00

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Water 600 ml 150 ml Ammonium thiosulfate (750 g / l) 93 ml 230 ml Sodium sulfite 40 g 100 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g 135 g Ethylenediaminetetraacetic acid 5 g 12.5 g Nitric acid (67%) 30 g 65 g Water was added to 1000 ml 1000 ml pH (adjusted with 25 ° C./acetic acid and aqueous ammonia) 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 Samples A to K treated Cyan under 6 conditions,
A storability test of magenta and yellow colored images was conducted. The degree of storability was evaluated at the initial density of 1.0 of each color image. The obtained results are shown in Table 6.

[0112]

[Table 6]

As is clear from the results shown in Table 6, the combined use of the two cyan couplers according to the present invention and the pyrazoloazole-based magenta coupler allows for long-term exposure to light and storage in the dark. However, it is understood that the fastness of yellow, magenta and cyan is excellent, and the fading balance of the three colors is excellent.

Claims (3)

[Claims] 1. A color photographic light-sensitive material comprising a support and an emulsion layer containing at least one cyan image forming coupler represented by the following general formulas [I] and [II]. After the exposure, a color image forming method is characterized by treating with a color developing solution having a benzyl alcohol concentration of 5 ml / l or less. [Chemical 1] (In the formula, R ¹ , R ² and R ⁴ represent an aliphatic group, an aryl group or a heterocyclic group which may have a substituent;
³ and R ⁵ are a hydrogen atom, a halogen atom, an alkyl group,
It may be an acylamino group, and R ³ may be a nonmetallic atom group forming a nitrogen-containing 5- or 6-membered ring with R ² .
R ⁶ represents an aliphatic group, R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a lower alkyl group. Z ¹ and Z ² represent a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. ) 2. A color photographic light-sensitive material is subjected to continuous color development processing after exposure with a color developing solution having a benzyl alcohol concentration of 5 ml / l or less and a replenisher solution of 100 ml or less per 1 m ^{2 of the} processing area. The color image forming method according to claim 1. 3. A silver halide emulsion layer containing at least one of cyan color image forming couplers represented by the following general formulas [I] and [II] and a pyrazoloazole type magenta color image forming on a support. A color photographic light-sensitive material comprising a silver halide emulsion layer containing at least one coupler. [Chemical 2] (In the formula, R ¹ , R ² and R ⁴ represent an aliphatic group, an aryl group or a heterocyclic group which may have a substituent;
³ and R ⁵ are a hydrogen atom, a halogen atom, an alkyl group,
It may be an acylamino group, and R ³ may be a nonmetallic atom group forming a nitrogen-containing 5- or 6-membered ring with R ² .
R ⁶ represents an aliphatic group, R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a lower alkyl group. Z ¹ and Z ² represent a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. )