JPH0466341B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material with excellent image storage stability, and more specifically, to a silver halide photographic material with excellent storage stability that prevents loss of color balance from low density to high density during storage. Regarding photographic materials. [Background of the Invention] Generally, silver halide color photographic light-sensitive materials consist of three types of photographic silver halide emulsions on a support that are selectively spectrally sensitized to have sensitivity to blue light, green light, and red light. The layers are coated. for example,
In silver halide photographic materials for color negatives, generally a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are coated in this order from the exposed side. A bleachable yellow filter layer is provided between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer to absorb blue light that passes through the blue-sensitive silver halide emulsion layer. ing. Further, each emulsion layer is provided with other intermediate layers for various special purposes, and a protective layer as the outermost layer. Furthermore, for example, in a silver halide photographic light-sensitive material for color photographic paper, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer are generally arranged in this order from the exposed side. Similar to silver halide photographic materials for color negatives, intermediate layers such as an ultraviolet absorbing layer and protective layers are provided for special purposes. It is also known that each of these silver halide emulsion layers is provided in a different arrangement from the above, and furthermore, each silver halide emulsion layer is sensitive to substantially the same wavelength range for each color light. It is also known to use a photosensitive silver halide emulsion layer consisting of two layers. In these silver halide color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with the dye-forming coupler. In this method, phenolic or naphthol cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indazolone or cyano couplers are typically used to form cyan, magenta and yellow dye images, respectively. An acetyl magenta coupler and an acylacetamide yellow coupler are used. Generally, the selection of couplers is determined by the rate at which they form a dye through a coupling reaction with the oxidation product of the color developing agent when developing with a color developing solution containing a color developing agent such as a p-phenylenediamine derivative as a main component. The coupling speed must be as high as possible, the dye formed must have good hue and stability against light, heat, moisture, etc., and various photographic materials such as sensitizing dyes that coexist in silver halide photographic materials must be used. This is done based on requirements such as not deteriorating photographic properties due to interaction with additives, good storage stability, and ease of coupler synthesis at low cost. However, it is extremely difficult to select a coupler that satisfies all of these requirements, and some relatively good couplers have been found within the range of individual light-sensitive emulsion layers containing yellow couplers, magenta couplers, and cyan couplers. It is extremely difficult to find a material that satisfies the overall requirements for a silver halide color photographic light-sensitive material arranged in combination with other light-sensitive emulsion layers. Color photographic materials for printing generally include a blue-sensitive silver halide emulsion layer containing a yellow coupler, a non-light-sensitive first intermediate layer, and a green-sensitive silver halide emulsion layer containing a magenta coupler on a reflective support. an emulsion layer, a non-light-sensitive second intermediate layer, a red-sensitive silver halide emulsion layer containing a cyan coupler;
It is formed by sequentially applying a non-photosensitive protective layer. In order to particularly suppress fading of the dye image due to light, an ultraviolet absorber is added to the first intermediate layer and/or the second intermediate layer. However, such conventional photographic materials for printing are still insufficient in terms of image storage stability, particularly light resistance, and have the disadvantage that dye images are significantly faded by light. In particular, among the dye images formed from each coupler, the fading speed increases in the order of cyan, yellow, and magenta, and the difference between them is extremely large, resulting in a drawback that the color balance is greatly disrupted by light irradiation. This is true for the British Journal.
British Journal of Photography
Photography) 128 (6329) 1170-1171 (1981), etc. Furthermore, conventional color photosensitive materials for printing have the disadvantage that they are not stable even at high temperatures, and even if they are stored in an album, their color will fade significantly over a long period of time. The rate of color fading during long-term storage in a dark place increases in the order of magenta, yellow, and cyan, and because the difference in the rate of fading is large, the color balance is impaired. A combination of a yellow coupler, a magenta coupler, and a cyan coupler that reduces the color balance is disclosed in JP-A-60-117249. Although some of the combinations disclosed in the above-mentioned publications improve the color balance loss to some extent during storage, they are still insufficient and further improvements are required. [Object of the Invention] Accordingly, the first object of the present invention is to provide a silver halide photographic light-sensitive material that has excellent image storage stability against light and moist heat. A second object of the present invention is to provide a silver halide photosensitive material which has excellent storage stability and is resistant to loss of color balance from low density to high density during long-term storage. [Structure of the Invention] The above object of the present invention is to provide at least the following on a support:
In a silver halide photographic material having a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer, the red-sensitive silver halide emulsion layer contains a cyan coupler represented by the following general formula [I]; The green-sensitive silver halide emulsion layer has the following general formula []
This was achieved by providing a silver halide photographic material containing a magenta coupler represented by: General formula [I] [In the formula, R ₁ represents an alkyl group having 2 to 4 carbon atoms, and R ₂ represents a halogen atom, a hydroxy group, a cyano group, an alkyl group, an acylamino group, a sulfonamide group, or an acyl group. J represents an alkylene group, and X represents a halogen atom, an alkoxy group or an aryloxy group. n represents an integer from 0 to 3. When n is 2 or 3, R ₂ may be the same group or different groups. ] General formula [] [In the formula, R ₅ represents a substituent, and R ₆ and R ₇ each represent a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, or an aryl group. However, at least one of R ₆ and R ₇ represents an alkoxy group. Ar represents an aryl group, and Y represents a halogen atom or an alkoxy group. l,
Each K represents an integer from 0 to 4. When l is 2 to 4, R ₅ may be the same group or different groups, and when K is 2 to 4,
R ₇ may be the same group or different groups. ] [Specific structure of the invention] The cyan coupler represented by the general formula [I] will be explained. In the general formula [I], the number of carbon atoms in the alkyl group is the number of carbon atoms excluding the substituent when these alkyl groups have a substituent. Examples of the alkyl group having 2 to 4 carbon atoms represented by R ₁ include ethyl group, propyl group,
Examples include iso-propyl group, butyl group, t-butyl group, and ethyl group is preferred. R ₂ is a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a hydroxy group, a cyano group, an alkyl group (including those with substituents; for example, an ethyl group, a propyl group, a butyl group, an octyl group, a pentadecyl group, etc.) , acylamino groups (including those with substituents; for example, acetylamino groups, butyrylamino groups, benzoylamino groups, etc.), sulfonamide groups (including those with substituents; for example, alkylsulfonamides such as methanesulfonamide groups) groups, arylsulfonamide groups such as benzenesulfonamide groups) or acyl groups (including those with substituents; for example, acetyl groups,
propionyl group, butyryl group, benzoyl group, etc.)
represents. When n is 2 or 3, R ₂ may be the same group or different groups. Examples of the alkylene group represented by J include -CH ₂ CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -,

【formula】

[Formula] etc. But especially

[Formula] is preferred. Here, R' represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a t-butyl group. R' is preferably a hydrogen atom.
Further, R'' represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, and the alkyl group is preferably an alkyl group having 2 to 12 carbon atoms, such as an ethyl group, a butyl group, a t-butyl group, a pentyl group,
Examples include octyl group, decyl group, dodecyl group, and the like. In addition, the alkyl groups represented by R ₁ , R′ and R″ each include those having a substituent. or represents an alkoxy group, among which halogen atoms include, for example, chlorine atom, bromine atom,
Examples include fluorine atoms, but chlorine atoms are preferred. Examples of the alkoxy group include methoxy group,
Examples of the aryloxy group include an ethoxy group and a β-methoxyethylcarbamoylmethoxy group, and examples of the aryloxy group include a phenoxy group and a p-methoxyphenoxy group. Next, typical examples of the coupler represented by the general formula [I] will be shown, but the present invention is not limited thereto. The cyan coupler of the general formula [I] used in the present invention is, for example, Japanese Patent Application No. 59-67033, Japanese Patent Application Laid-open No. 60-60
It can be synthesized according to the method described in No. 55340. Next, the magenta coupler represented by the general formula [] will be explained. In the general formula [],
Examples of the substituent represented by R ₅ include a halogen atom (specifically, a chlorine atom, a bromine atom, etc.), an alkyl group (specifically, a methyl group, a t-butyl group,
(tetradedyl group, trifluoromethyl group, etc.), alkoxy group (specifically, methoxy group, ethoxy group,
tetradecyloxy group, etc.), acylamino group [specifically, acetamido group, benzamide group, butanamide group, α-(2,4-di-t-amylphenoxy)acetamide group, α-(2,4-di-t-t)
-amylphenoxy)butylamide group, etc.], sulfonamide group (specifically methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.), sulfamoyl group (specifically N-methylsulfamoyl group, N-hexadecylsulfamoyl group, N-methyl-N-tetradecylsulfamoyl group, etc.), carbamoyl group (specifically N-methylcarbamoyl group, N-octadecylcarbamoyl group, N-methyl-N-tetra decylcarbamoyl group, etc.), diacylamino group (specifically N-succinimide group, N-phthalimide group, 2,5-dioxo-1-oxazolidinyl group, 3-dodecyl-2,5-dioxo-1
-hydantoinyl group, etc.), alkoxycarbonyl group (specifically, methoxycarbonyl group, tetradecyloxycarbonyl group, etc.), alkoxysulfonyl group (specifically, methoxysulfonyl group, tetradecyloxysulfonyl group, etc.), aryloxysulfonyl group (specifically phenoxysulfonyl group, 2,4-di-t-amylphenoxysulfonyl group, etc.), alkylsulfonyl group (specifically methylsulfonyl group, octylsulfonyl group, hexadecanesulfonyl group, etc.), Arylsulfonyl group (specifically, benzenesulfonyl group, etc.), alkylthio group (specifically, ethylthio group, hexylthio group, tetradecylthio group, etc.), arylthio group (specifically, phenylthio group, etc.), alkoxycarbonylamino group (specifically ethoxycarbonylamino group, hexadecyloxycarbonylamino group, etc.), alkylureido group (specifically N-methylureido group, N-methyl-N-dodecylureido group, N,N-dioctadecylureido group) etc.), an acyl group (specifically an aticel group, a benzoyl group, etc.), a nitro group, a carboxy group, etc. The halogen atom represented by R ₆ and R ₇ includes, for example, a chlorine atom, a bromine atom, etc., and the alkyl group is preferably an alkyl group having 1 to 22 carbon atoms, such as a methyl group, an ethyl group, a t-
Examples include butyl group, 1,1,3,3-tetramethylbutyl group, etc., and the alkoxy group is preferably an alkoxy group having 1 to 22 carbon atoms, such as methoxy group, butoxy group, hexadecyloxy group, etc. Examples of the aryl group include a phenyl group and a p-methylphenyl group. However, at least one of R ₆ and R ₇ is an alkoxy group. The aryl group represented by Ar includes, for example, a phenyl group, and in particular, a halogen atom (for example, a chlorine atom, etc.), an alkyl group (for example, a methyl group,
A phenyl group substituted with a t-butyl group, etc.) or an alkoxy group (eg, a methoxy group, an octyloxy group, etc.) is preferred, and a phenyl group substituted with a chlorine atom at the 2, 4, and 6 positions is most preferred. Examples of the halogen atom represented by Y include chlorine atom, bromine atom, fluorine atom, etc.
The alkoxy group is preferably an alkoxy group having 1 to 22 carbon atoms, such as a methoxy group or a dodecyloxy group. Typical specific examples of the magenta coupler represented by the general formula [] of the present invention are shown below, but the present invention is not limited thereto. The magenta coupler of general formula [] used in the present invention can be synthesized, for example, by the method described in JP-A-57-35858. The silver halide photographic material of the present invention has at least a red-sensitive silver halide emulsion layer containing a cyan coupler of general formula [I] and a green-sensitive silver halide emulsion layer containing a magenta coupler of general formula [] on a support. It is sufficient to have an emulsion layer, and may also have other layers. As a cyan coupler in the red-sensitive silver halide emulsion layer, a cyan coupler other than the general formula [I] may be used in combination, but the cyan coupler of the general formula [I] is the cyan coupler used in the layer.
It is preferable that it is 50% or more. The total amount of cyan coupler used in the layer is from 2.times.10.sup. ^-3 to 5.times.10.sup. ^-1 mol per mole of silver halide. As a magenta coupler in the green-sensitive silver halide emulsion layer, a magenta coupler other than the general formula [] may be used in combination, but the magenta coupler of the general formula [] is the magenta coupler used in the layer.
It is preferable that it is 50% or more. The total amount of magenta coupler used in the layer is from 2.times.10.sup. ^-3 to 5.times.10.sup. ^-1 mol per mole of silver halide. The magenta coupler and cyan coupler used in the present invention can be added to silver halide photographic materials in the same manner as the general methods of adding hydrophobic compounds, such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion. The dispersion can be carried out using various methods such as the above method, and this method can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water emulsion dispersion method can be applied by dispersing hydrophobic compounds such as couplers, and usually has a boiling point of about 150.
It is dissolved in a high-boiling point organic solvent of ℃ or above, combined with a low-boiling point and/or water-soluble organic solvent if necessary, and then mixed with a hydrophilic binder such as an aqueous gelatin solution using a surfactant, using a stirrer, homogenizer, or colloid mill. After being emulsified and dispersed using a dispersing means such as a flow jet mixer, an ultrasonic device, etc., it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion. Examples of high-boiling organic solvents include phenol derivatives, phthalates, phosphates, citric esters, benzoic esters, alkylamides, fatty acid esters, which do not react with the oxidized form of the developing agent;
An organic solvent with a boiling point of 150°C or higher, such as trimesic acid ester, is used. High boiling point organic solvents that can be preferably used in the present invention include compounds with a dielectric constant of 6.0 or less, such as esters such as phthalates and phosphates, organic acid amides, and ketones with a dielectric constant of 6.0 or less. , hydrocarbon compounds, etc.
Preferably, it is a high boiling point organic solvent having a dielectric constant of 6.0 or less and 1.9 or more and a vapor pressure of 0.5 mmHg or less at 100°C. Even more preferred are phthalic esters or phosphoric esters in the high-boiling organic solvent. Furthermore, the high boiling point organic solvent may be a mixture of two or more kinds. Note that the dielectric constant in the present invention refers to the dielectric constant at 30°C. The photosensitive material according to the present invention can be applied to, for example, color negative and positive films, color photographic paper, etc., but the effects of the present invention are particularly effective when applied to color photographic paper used for direct viewing. Demonstrated. The photosensitive material according to the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide color photographic materials, in order to perform subtractive color reproduction, silver halide emulsion layers containing magenta, yellow, and cyan couplers as photographic couplers and non-silver halide emulsion layers are usually used. Although the photosensitive layer has a structure in which the photosensitive layer is laminated on a support in an appropriate number and order of layers, the number and order of layers may be changed as appropriate depending on the important performance and purpose of use. The silver halide emulsion used in the light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used can be used. The silver halide grains used in the silver halide emulsion may be obtained by any one of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different. In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. Further, while taking into consideration the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the PH and pAg in the mixing pot. After growth, using the convergence method,
The halogen composition of the particles may be changed. By using a silver halide solvent as necessary during the production of a silver halide emulsion, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled. Silver halide grains used in silver halide emulsions are produced by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Metal ions can be added to the inside of the particles and/or on the surface of the particles using complex salts, etc., and by placing them in an appropriate reducing atmosphere, reduction can be increased inside the particles and/or on the surface of the particles. It can give you a feeling of emotion. Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left as they are contained. When removing such salts, research disclosure
This can be done based on the method described in No. 17643. The silver halide grains used in the silver halide emulsion may consist of uniform layers inside and on the surface, or may consist of different layers. The silver halide grains used in the silver halide emulsion may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains. The silver halide grains used in the silver halide emulsion may have a regular crystal shape or may have an irregular crystal shape such as a spherical or plate shape. In these particles, {100} plane and {111}
Any surface ratio can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. The silver halide emulsion may be a mixture of two or more silver halide emulsions formed separately. The silver halide emulsion is chemically sensitized by conventional methods. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensing methods can be used alone or in combination. Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good. Silver halide emulsions are used in the manufacturing process of photosensitive materials,
For the purpose of preventing fog during storage or photographic processing and/or keeping photographic performance stable, silver halide emulsions are used during and/or at the end of chemical ripening, and/or after the end of chemical ripening. Compounds known in the photographic industry as antifoggants or stabilizers can be added prior to coating. As a binder (or protective colloid) for silver halide emulsions, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymer substances such as copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material according to the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution. A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material according to the present invention. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability. In the emulsion layer of the light-sensitive material according to the present invention, a dye is produced by a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, a p-phenylenediamine derivative or an aminophenol derivative) during color development processing. A dye-forming coupler is used. The dye-forming couplers are typically selected such that for each emulsion layer a dye is formed that absorbs light in the light sensitive spectrum of the emulsion layer, with a yellow coupler in the blue light sensitive emulsion layer. A magenta coupler is used in the green light-sensitive emulsion layer, and a cyan coupler is used in the red light-sensitive emulsion layer. In the present invention, it is preferable from the viewpoint of color balance that the yellow coupler is represented by the following general formula [] and is combined with the cyan coupler and magenta coupler of the present invention. General formula [] In the formula, R ₈ is −NHCOR ₁₁ , −NHSO ₂ R ₁₁ , −
COOR ₁₁ or _-SO2N - _R12 - _R11 ( _R11 and _R12 each represent an alkyl group). R ₉ represents an alkyl group, and R ₁₀ represents an alkyl group. The alkyl group represented by R ₉ includes those having substituents, such as methyl group, ethyl group, iso-propyl group, butyl group, t-butyl group,
Examples include a benzyl group and a phenethyl group, but an alkyl group without a substituent is preferable. The alkyl group represented by R ₁₀ includes those having substituents, such as methyl group, ethyl group, iso-propyl group, butyl group, t-butyl group,
Examples include benzyl group and phenethyl group, and particularly preferred are alkyl groups substituted with phenyl groups such as benzyl group and phenethyl group. Examples of the alkyl groups represented by R ₁₁ and R ₁₂ include ethyl group, iso-propyl group,
Examples include butyl group, t-butyl group, and hexyl group, but these alkyl groups also include those having substituents. Examples of this substituent include aryloxy groups (specifically, phenoxy groups, etc.), alkoxycarbonyl groups (specifically, methoxycarbonyl groups, etc.), alkylsulfonyl groups (specifically, ethylsulfonyl groups, etc.), sulfonic acid groups, etc. group, an aryl group (specifically, a phenyl group, etc.), an alkylamide group (specifically, a diethylamide group, etc.), and the like. Specific examples of the yellow coupler represented by the general formula [] are shown below, but the present invention is not limited thereto.

【table】

[Table] Between the emulsion layers of the light-sensitive material according to the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity or sharpness. Color antifogging agents are used to prevent deterioration in quality and noticeable graininess. The color antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers. In the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material according to the present invention, an ultraviolet absorber is added to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain. The layer structure of the silver halide photographic material according to the present invention may have any number of layers and any order of layers, but preferably a yellow coupler-containing silver halide emulsion layer, a magenta coupler-containing silver halide emulsion layer, and a cyan coupler are provided on the support. The containing silver halide emulsion layers are coated in the order of - from the support side, an intermediate layer is provided between and and a non-photosensitive layer is provided on the side farther away from the support side, and an intermediate layer between the above and It is preferable to contain an ultraviolet absorber in the non-photosensitive layer adjacent to and, and when the non-photosensitive layer adjacent to the above contains an ultraviolet absorber, a protective layer is further applied adjacent to the layer. It is preferable that the The photosensitive material according to the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer, if necessary. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development. A matting agent is added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material according to the present invention with the aim of reducing the gloss of the light-sensitive material, increasing the ease of writing, and preventing mutual scratching of the light-sensitive materials. I can do it. A lubricant can be added to reduce the sliding friction of the photosensitive material according to the present invention. An antistatic agent for the purpose of preventing static electricity can be added to the photosensitive material according to the present invention. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer. The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material according to the present invention may be used to improve coating properties, prevent static electricity, improve slipperiness, emulsification and dispersion, prevent adhesion, and (promote development, increase contrast, increase sensitization, etc.). ) Various surfactants are used for the purpose of improving photographic properties. The photographic emulsion layer and other layers of the light-sensitive material according to the present invention are a baryta layer or a flexible reflective support such as paper laminated with α-olephne polymer, synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, polychloride, etc. It can be applied to films made of semi-synthetic or synthetic polymers such as vinyl, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics. The photosensitive material according to the present invention can be produced by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, and then directly or It may be applied via one or more subbing layers (to improve abrasion, hardness, antihalation, frictional properties and/or other properties). When coating the photographic material according to the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously. The photosensitive material according to the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the photosensitive material according to the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps,
Emitted from phosphors excited by mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser beams, light emitting diode light, electron beams, X-rays, γ-rays, α-rays, etc. Any known light source can be used. The exposure time is not only 1 millisecond to 1 second, which is normally used with a camera, but also an exposure shorter than 1 microsecond, for example, an exposure of 100 microseconds to 1 microsecond using a cathode ray tube or xenon arc lamp. Exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently. The photosensitive material according to the present invention can form a color image by performing color development as known in the art. The aromatic primary amine color developing agent used in the color developing solution in the present invention includes known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Further, these compounds are generally used in a concentration of about 0.1 g to about 30 g per color developer 1, preferably about 1 g per color developer 1.
Use at a concentration of ~15g. As the aminophenol developer, for example, o
-aminophenol, p-aminophenol, 5
-amino-2-oxytoluene, 2-amino-3
-oxytoluene, 2-oxy-3-amino-
Includes 1,4-dimethylbenzene and the like. A particularly useful primary aromatic amine color developer is an N,N'-dialkyl-p-phenylenediamine compound, in which the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, and N,N'-dimethyl-p-phenylenediamine hydrochloride. salt, 2-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,
N'-diethylaniline, 4-amino-N-(2-
(methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate and the like. In addition to the above-mentioned aromatic primary amine color developer, the color developer used in the process of the present invention further contains various components normally added to color developers, such as sodium hydroxide and sodium carbonate. , an alkali agent such as potassium carbonate, an alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener and a thickening agent. The pH value of this color developer is usually 7 or more, most commonly about 10 to about 13. In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. As the bleaching agent used in the bleaching process, a metal complex salt of an organic acid is used, and the metal complex salt is
It has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. Its composition is aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. Coordinated with metal ions such as iron, cobalt, and copper. The most preferred organic acids used to form such metal complexes of organic acids include:
Mention may be made of polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetranitrium salt [7] Nitrilotriacetic acid sodium salt The bleaching agent used contains a metal complex salt of an organic acid as described above as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.
In addition, PH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions may be added as appropriate. . Furthermore, the fixing solution and bleach-fixing solution contain sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, and borax. , sodium hydroxide, potassium hydroxide,
It may contain one or more PH buffers consisting of various salts such as sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, or appropriate oxidation Agents such as hydrogen peroxide, bromates, persulfates, etc. may be added as appropriate. [Examples] Examples of the present invention will be described in detail below, but the present invention is not limited to these embodiments. Example 1 Samples Nos. 1 to 8 of multicolor silver halide photographic materials were prepared by sequentially coating the following layers on a support made of polyethylene-coated paper from the support side. 1st layer: Blue-sensitive silver halide emulsion layer As the yellow coupler, the above-mentioned coupler Y-
1 at 8 mg/dm ² , blue-sensitive silver chlorobromide emulsion at 3 mg/dm ² in terms of silver, dinonyl phthalate at 3 mg/d
m ² and gelatin were coated at a coating amount of 16 mg/dm ² . 2nd layer: Intermediate layer Gelatin was coated at a coating amount of 4 mg/dm ² . 3rd layer: green-sensitive silver chlorobromide emulsion layer containing 4 mg/g of the above exemplary magenta coupler (Table 1)
dm ² , the following anti-fading agents A-1 and A-2 were added to 3
mg/dm ² , green-sensitive silver chlorobromide emulsion converted to silver 2
mg/dm ² , 4 mg/dm ² of dioctyl phthalate, and 16 mg/dm ² of gelatin. 4th layer: Intermediate layer UV absorber 2-(2'-hydroxy-3',5'-di-amylphenol)-benzotriazole
mg/dm ² , 2-(2'-hydroxy-3',5'-di-t
-butylphenol)-benzotriazole 3
mg/dm ² , 4 mg/dm ² of dioctyl phthalate, and 14 mg/dm ² of gelatin. 5th layer: Red-sensitive silver chlorobromide emulsion layer: 4 mg/d of the exemplified cyan coupler (Table 1)
² mg/dm ² of dioctyl phthalate and 3 mg/dm ² of red-sensitive silver chlorobromide emulsion in terms of silver. 6th layer: Intermediate layer 3 mg/dm ² of ultraviolet absorber 2-(2'-hydroxy-3',5'-di-t-amylphenol)-benzotriazole, 2-(2'-hydroxy-3', 2 mg/dm ² of 5'-di-t-butylphenol)-benzotriazole and 2 mg/d of dioctyl phthalate.
m ² and gelatin were coated at a coating amount of 6 mg/dm ² . 7th layer: Protective layer Gelatin was coated at a coating amount of 9 mg/dm ² . The obtained samples 1 to 8 were subjected to optical wedge exposure with white light using a sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd., model KS-7), and then subjected to the following processing steps. Processing process (1) Color development 38℃ 3 minutes 30 seconds (2) Bleach-fixing 33℃ 1 minute 30 seconds (3) Washing with water 25-30℃ 3 minutes (4) Drying 75-80℃ approx. 2 minutes Processing solution composition (Color developer) Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 4.1g Polyphosphoric acid (TPPS) 2.5g 3-Methyl-4-amino-N-ethyl-N-
(β-Methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to bring the total amount to 1, pH 10.20 Adjust to. (Bleach-fix solution) Ferric ethylenediaminetetraacetic acid Ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to PH7.1 with potassium carbonate or glacial acetic acid,
Add water to bring the total volume to 1. Image density obtained by the above processing, and image density after exposing the sample obtained by this processing to sunlight for 400 hours using an underglass outdoor exposure table, under conditions of relative humidity 40% and temperature 77°C. After 15 days of aging, the density of each image was measured using a microdensitometer POM-5, and the results are shown in Table 1.
It was shown to. However, in Table 1, G is the density for green light, and R is the density for red light.

【table】 From the results in Table 1, samples No. 1 and 2 using comparative magenta coupler and comparative cyan coupler.
In particular, the color balance deteriorates significantly after storage over time. Furthermore, although the color balance of sample No. 3 using the mazen coupler of the present invention and the comparative cyan coupler was considerably improved compared to samples No. 1 and 2 after storage over time, the color balance after exposure to sunlight was It will collapse slightly. On the other hand, samples Nos. 4 to 8 using the magenta coupler of the present invention and the cyan coupler of the present invention showed very little deterioration in color balance even after exposure to sunlight and after storage over time; This holds true in all regions from high concentration to high concentration.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having at least a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer on a support, the red-sensitive silver halide emulsion layer has the following general formula: A silver halide photographic material comprising a cyan coupler represented by [I] and a magenta coupler represented by the following general formula [] in the green-sensitive silver halide emulsion layer. General formula [I] [In the formula, R ₁ represents an alkyl group having 2 to 4 carbon atoms, and R ₂ represents a halogen atom, a hydroxy group, a cyano group, an alkyl group, an acylamino group, a sulfonamide group, or an acyl group. J represents an alkylene group, and X represents a halogen atom, an alkoxy group or an aryloxy group. n represents an integer from 0 to 3. When n is 2 or 3, R ₂ may be the same group or different groups. ] General formula [] [In the formula, R ₅ represents a substituent, and R ₆ and R ₇ each represent a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, or an aryl group. However, at least one of R ₆ and R ₇ represents an alkoxy group. Ar represents an aryl group, and Y represents a halogen atom or an alkoxy group. l,
Each K represents an integer from 0 to 4. When l is 2 to 4, R ₅ may be the same group or different groups, and when K is 2 to 4,
R ₇ may be the same group or different groups. ]