JPH0450576B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a silver halide color photographic material suitable for printing. Prior Art and its Problems In silver halide color photographic materials, dye images are usually produced by an aromatic primary amine color developing agent reducing silver halide grains and oxidizing itself, and this oxidized product becomes halogenated. It is obtained by reacting with a coupler previously contained in a silver color photographic material to form a dye. Generally, three dye-forming couplers, yellow, magenta and cyan, are used as couplers to reproduce colors by subtractive color method. Among these three dye-forming couplers, the basic properties required of cyan couplers are that the resulting cyan dye image has fastness to light, heat, moisture, etc., that is, light resistance, heat resistance, and moisture resistance. It is mentioned that the storage stability of dye images containing the dyes is improved in a well-balanced manner, and in particular, it is mentioned that the fading resistance such as heat resistance and moisture resistance is improved. Examples of cyan couplers that meet these requirements include 2,5-diacylaminophenol cyan couplers in which the 2- and 5-positions of the phenol are substituted with acylamino groups;
Specification No. 2895826, Japanese Unexamined Patent Application Publication No. 112038/1983, No. 53-
No. 109630 and No. 55-163537. These 2,5-diacylaminophenol-based cyan couplers have excellent image preservation properties, especially resistance to fading, of the cyan dye images formed, and also have good processing stability, especially good color recovery properties in bleach-fixing processing. It is. In particular, one or both of the 2- and 5-position acylamino groups contain the formula -NR ₁₄
A 2,5-diacylaminophenol cyan coupler bonded with a sulfonamide group represented by SO ₂ R ₁₃ (R ₁₃ represents an alkyl group, aryl group, or amino group, and R ₁₄ represents a hydrogen atom or an alkyl group) is In addition to the above properties, the spectral absorption properties of the cyan dye formed, light resistance, light yellow stain prevention properties,
It also has excellent basic properties such as color development and dispersion stability. Tororo prepares a silver halide photographic emulsion coating solution (hereinafter referred to as coating solution) using the above-mentioned 2,5-diacylaminophenol cyan coupler having a sulfonamide group that has these excellent properties. The sensitivity of silver halide varies significantly between coating on the support immediately after preparation and coating on the support after the coating solution stagnates. In mass production, there was a serious drawback in that it was difficult to mass produce photosensitive materials of consistent quality. Therefore, in order to improve the stagnation after coating the emulsion,
There is a method of adding a sensitizing dye to the coating solution, but this method can be said to be sufficient to improve the stagnation of the coating solution. However, as the amount of the sensitizing dye increases, The drawback was that residual color stains frequently occurred. In addition to the above methods, methods for improving the stagnation of the coating solution include adding azoles, azaindene compounds, etc. known as stabilizers to the coating solution;
For example, a method of adding a reducing agent such as hydroquinones or sulfinic acids, or
As described in Publication No. 111629, there is a method of using a certain copolymer and a fluorescent brightener in combination, but although these methods do not sufficiently improve the stagnation of the coating solution, Not only that, but some of them also have the disadvantage of deteriorating important photographic properties such as gradation and sensitivity. Purpose of the Invention The purpose of the present invention is to prevent light yellow staining, improve the light fastness, heat resistance, and moisture resistance of the formed dye image in a well-balanced manner, and form a dye image with excellent overall image storage stability. A silver halide photographic light-sensitive material that can be stably mass-produced, has excellent image processing stability, especially color recovery properties in bleach-fixing processing, and has good stability over time after emulsion coating during production. Our goal is to provide the following. The above object of the present invention is to provide at least one
In a silver halide photographic light-sensitive material provided with a silver halide emulsion layer, the silver halide emulsion layer contains at least one cyan coupler represented by the following general formula [], and the halogenated This is achieved by spectrally sensitizing the silver halide in the silver emulsion layer with at least one compound from the group of compounds represented by the following general formulas [] and []. General formula [] [In the formula, R ₁ represents an alkyl group or an aryl group. R ₂ is an alkyl group, a cycloalkyl group,
Represents an aryl group or a heterocyclic group. R ₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Further, R ₃ may be combined with R ₁ to form a ring. Z ₁ represents a hydrogen atom or a group capable of being eliminated by reaction with an oxidized product of an aromatic primary amine color developing agent. ] General formula [ ] [In the formula, L ₁ , L ₂ and L ₃ each represent a methine group. Y ₁ and Y ₂ are each an oxygen atom,
Represents a sulfur or selenium atom. R ₄ and
Each R ₅ represents an alkyl group. However, R ₄
and at least one of R ₅ has a sulfo group.
A ₁ , A ₂ , B ₁ , B ₂ , C ₁ , C ₂ , D ₁ and D ₂ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, a cyano group, a nitro group, or an alkoxycarbonyl group. represents. Also A ₁
and B ₁ , B ₁ and C ₁ , C ₁ and D ₁ , A ₂ and B ₂ , B ₂ and C ₂ , and at least one of the combinations of C ₂ and D ₂ are fused to form a benzene ring. Also good. M represents a cation. m represents 0 or 1. ] General formula [ ] [In the formula, Z ₂ represents a group of nonmetallic atoms necessary to constitute a quinoline ring together with the bonded nitrogen atom and carbon atom. Z ₃ is a thiazole ring, a benzothiazole ring, together with the bonding nitrogen atom and carbon atom,
Represents an atomic group necessary to constitute a naphthothiazole ring, benzoxazole ring, naphthoxazole ring, benzoselenazole ring, or naphthoselenazole ring. R ₆ , R ₇ and R ₈ each represent an alkyl group. X represents an acid anion group.
l and n each represent an integer of 0 or 1. ] Detailed Description of the Invention In the present invention, the alkyl group represented by R ₁ in the general formula [] is a linear or branched one, such as a methyl group, an ethyl group, an iso-propyl group,
Butyl group, pentyl group, octyl group, nonyl group,
Examples of the aryl group include a tridecyl group, and examples of the aryl group include a phenyl group and a naphthyl group. These groups represented by R ₁ may have single or multiple substituents, and typical substituents introduced into the phenyl group include halogen atoms (e.g. fluorine, chlorine, bromine). etc.), alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), alkyl sulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (e.g. phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (e.g. butylsulfamoyl group, etc.), arylsulfamoyl group groups (e.g., phenylsulfamoyl group, etc.), alkyloxycarbonyl groups (e.g., methyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g., phenyloxycarbonyl group, etc.), aminosulfonamide groups (e.g., N,N-dimethyl (aminosulfonamide group, etc.), an acylamino group, a carbamoyl group, a sulfonyl group, a sulfinyl group, a sulfoxy group, a sulfo group, an aryloxy group, an alkoxy group, a carboxyl group, an alkylcarbonyl group, an arylcarbonyl group, and the like. Two or more types of these substituents may be introduced into the phenyl group. The halogen atom represented by R ₃ is, for example, fluorine, chlorine, bromine, etc., the alkyl group is, for example, methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc., and the alkoxy group is, for example, Methoxy group, ethoxy group, propyloxy group,
Butoxy group, etc. R ₃ may combine with R ₁ to form a ring. In the present invention, the alkyl group represented by R ₂ in the general formula [] is, for example, a methyl group, an ethyl group, a butyl group, a hexyl group, a tridecyl group, a pentadecyl group, a heptadecyl group, or a so-called polyfluorinated group substituted with fluorine. Such as an alkyl group. The aryl group represented by R ₂ is, for example, a phenyl group or a naphthyl group, and preferably a phenyl group. The heterocyclic group represented by R ₂ is, for example, a pyridyl group or a furan group. The cycloalkyl group represented by R ₂ is, for example, a cyclopropyl group or a cyclohexyl group. These groups represented by R ₂ may have single or multiple substituents. For example, typical substituents introduced into the phenyl group include halogen atoms (e.g. fluorine, chlorine, bromine). etc.), alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group,
Alkoxy groups (e.g. methoxy, ethoxy, etc.), alkylsulfonamide groups (e.g. methylsulfonamide, octylsulfonamide, etc.), arylsulfonamide groups (e.g. phenylsulfonamide, naphthylsulfonamide, etc.), alkyl Sulfamoyl groups (e.g., butylsulfamoyl group, etc.), arylsulfamoyl groups (e.g., phenylsulfamoyl group, etc.), alkyloxycarbonyl groups (e.g., methyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g., methyloxycarbonyl group, etc.). enyloxycarbonyl group, etc.), aminosulfonamide group, acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, sulfooxy group, sulfo group, aryloxy group, alkoxy group, carboxyl group, alkylcarbonyl group,
Examples include arylcarbonyl groups. Two or more types of these substituents may be introduced into the phenyl group. Preferred groups represented by _R2 include a polyfluoroalkyl group, a phenyl group or a halogen atom, an alkyl group, an alkoxy group, an alkylsulfonamide group, an arylsulfonamide group, an alkylfurfamoyl group, an arylsulfamoyl group, and an alkyl group. It is a phenyl group having one or more sulfonyl groups, arylsulfonyl groups, alkylcarbonyl groups, arylcarbonyl groups, or cyano groups as substituents. In the present invention, among the cyan couplers represented by the general formula [], the following general formula []
It is a compound represented by General formula [] In the general formula [], R ₉ represents an alkyl group or a phenyl group. This alkyl group or phenyl group may have a single or multiple substituents, and typical substituents to be introduced include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), alkyl groups ( For example, methyl group, ethyl group,
propyl group, butyl group, octyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.),
Alkylsulfonamide groups (e.g. methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide groups (e.g. phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfonamide groups (e.g. butylsulfamoyl group, etc.) ), arylsulfamoyl groups (e.g., phenylsulfamoyl groups, etc.), alkyloxycarbonyl groups (e.g., methyloxycarbonyl groups, etc.), aryloxycarbonyl groups (e.g., phenyloxycarbonyl groups, etc.). . Two or more of these substituents may be substituted with the phenyl group. Preferred groups represented by R ₉ include polyfluoroalkyl groups, phenyl groups, or halogen atoms (e.g. fluorine,
chlorine, bromine), alkylsulfonamide groups (e.g. o-methylsulfonamide group, p-octylsulfonamide group, o-dodecylsulfonamide group), arylsulfonamide group (e.g. phenylsulfonamide group), alkylsulfamoyl group (e.g. butylsulfamoyl group), arylsulfamoyl group (e.g. phenylsulfamoyl group), alkyl group (e.g. methyl group, trifluoromethyl group), alkoxy group (e.g. methoxy group, ethoxy group), alkyl group oxycarbonyl group,
Aryloxycarbonyl group, acylamino group,
It is a phenyl group having one or more carbamoyl groups, sulfonyl groups, carbonyl groups, or cyano groups as substituents. R ₁₀ is an alkyl group or an aryl group. An alkyl group or an aryl group may have a single or multiple substituents, and typical substituents include halogen atoms (e.g. fluorine,
chlorine, bromine, etc.), hydroxyl group, carboxyl group, alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), aralkyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group) group, ethoxy group), aryloxy group, alkylsulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (e.g. phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfonamide group moyl group (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.) carbonyl group, etc.), aminosulfonamide group (e.g. N, N-
dimethylaminosulfonamide group, etc.), an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, a ureido group, a carbamoyl group, and a sulfinyl group. Two or more types of these substituents may be introduced. Preferred groups represented by R ₁₀ include l=0
When , it is an alkyl group, and when l=1 or more, it is an aryl group. More preferable groups represented by _R10 include, when l=0, an alkyl group having 1 to 22 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a dodecyl group); = 1 or more, a phenyl group, or an alkyl group (e.g. t-butyl group, t-amyl group, octyl group), an alkylsulfonamide group (e.g. butylsulfonamide group, octylsulfonamide group, dodecylsulfonamide group), Arylsulfonamide group (e.g. phenylsulfonamide group), aminosulfonamide group (e.g. N,N-
dimethylaminosulfonamide group) or a phenyl group having one or more alkyloxycarbonyl groups (eg, methyloxycarbonyl group, butyloxycarbonyl group) as a substituent. R ₁₁ represents an alkylene group, preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably a branched alkylene group. R ₁₂ is a hydrogen atom or a halogen atom (fluorine,
chlorine, bromine or iodine). Preferably it is a hydrogen atom. l is 0 or a positive integer, preferably 0 or 1. X is -O-, -CO-, -COO-, -OCO-, -
CONRx′−, −NR′xCO−, −SO ₂ NR′x−, −
NR′xSO ₂ NR″x−, −S−, −SO− or −SO ₂
- Represents a divalent group. Here, R′x, R″X represent an alkyl group, preferably -O-, -S
-, -SO-, _-SO2- groups. Z ₄ represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. In general formulas [] and [], Z ₁ and
The group represented by Z ₄ that can be released by reaction with the oxidized product of an aromatic primary amine color developing agent is well known to those skilled in the art, and can modify the reactivity of the coupler or leave the coupler. Therefore, in the coating layer or other layers containing the coupler in the silver halide color photographic light-sensitive material, it acts advantageously by performing functions such as development inhibition, bleaching inhibition, and color correction. Typical examples include halogen atoms, alkoxy groups, aryloxy groups, arylazo groups, thioether groups, carbamoyloxy groups, acyloxy groups, imido groups, sulfonamide groups, thiocyano groups, and heterocyclic groups (e.g. oxazolyl, diazolyl, triazolyl, tetrazolyl, etc.). Particularly preferably Z ₁ or Z ₄ is a hydrogen atom or a chlorine atom. A more preferred cyan coupler of the present invention has a sulfonamide group ( _{-NR 14 SO 2 R 13 , where R 13} is an alkyl group, an aryl group or _an amino group, R ₁₄ represents a hydrogen atom or an alkyl group). Typical specific examples of the cyan coupler represented by the formula [] are shown below, but the invention is not limited thereto. In the present invention, when the methine group (-CH=) represented by L ₁ , L ₂ and L ₃ in the general formula [] has a substituent, for example, when it is represented by the formula -CR ₂₀ =, this R ₂₀ Examples of substituents include linear or branched alkyl groups having about 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, carboxymethyl group, benzyl group), alkoxy groups (e.g., methoxy group, ethoxy group), and aryl group (e.g. phenyl group,
tolyl group), etc. The alkyl groups represented by R ₄ and R ₅ in the general formula [] are linear or branched, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, etc. , R ₄ and R ₅
When the alkyl group represented by has a substituent, for example, a hydroxylalkyl group (e.g., hydroxymethyl group, hydroxyethyl group, hydroxypropyl group), a sulfoalkyl group (e.g., sulfoethyl group, sulfopropyl group, sulfobutyl group) , 2-hydroxyl-3-sulfopropyl group), carboxyalkyl group (e.g. carboxymethyl group, carboxyethyl group), acetoxyalkyl group (e.g. acetoxyethyl group),
These include aralkyl groups (eg, benzyl group, phenethyl group), alkenyl groups (eg, allyl group, isopropenyl group), and the like. However, at least one of R ₄ and R ₅ is an alkyl group having a sulfo group. A ₁ , A ₂ , B ₁ , B ₂ , C ₁ , C ₂ , D ₁ of general formula []
The alkyl _group represented by The group is a linear or branched alkyloxy group having about 1 to 5 carbon atoms (e.g. methoxy group, ethoxy group), and the halogen atom is fluorine, chlorine,
Bromine or iodine, the phenyl group is, for example, a phenyl group without a substituent, a hydroxyphenyl group, or a carboxyphenyl group, and the alkoxycarbonyl group is, for example, a methoxycarbonyl group or an ethoxycarbonyl group. The cation represented by M in the general formula [] is
Examples include hydrogen ions, sodium ions, potassium ions, triethylammonium ions, pyridinium ions, and N,N-diethyl-N-isopropylammonium ions. When the compound represented by the general formula [] forms an inner salt, m is 0. Specific examples of the compound represented by the general formula [] are shown below, but the compound is not limited thereto. In the present invention, when the quinoline ring having Z ₂ as a constituent in the general formula [] has a substituent, examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a cyano group,
Examples include carboxyl group, alkoxycarbonyl group, alkylamino group, acylmino group, acyl group, phenyl group, and cyclohexyl group. A specific example of a quinoline ring containing Z ₂ as a constituent is 2
-quinoline, 6-chloro-2-quinoline, 6-methyl-2-quinoline, 6-methoxy-2-quinoline, 7-methyl-2-quinoline, 8-methyl-2
-quinoline, 6-hydroxy-2-quinoline, 4
-quinoline, 6-methyl-4-quinoline, 6-ethyl-4-quinoline, 6-methoxy-4-quinoline, 6-ethoxy-4-quinoline, 6-chloro-
4-quinoline, 6-hydroxy-4-quinoline,
6-phenyl-4-quinoline, 7-methyl-4-
Examples include quinoline, 8-methyl-4-quinoline, and the like. Thiazole ring, benzothiazole ring, naphthothiazole ring containing Z ₃ of general formula [] as a constituent component,
benzoxazole ring, naphthoxazole ring,
When the benzoselenazole ring or naphthoselenazole ring has a substituent, the substituent is
Examples include a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a carboxyl group, an alkoxycarbonyl group, an alkylamino group, an acylamino group, an acyl group, a phenyl group, and a cycloalkyl group. Specific examples of thiazole rings containing Z ₃ as a constituent are:
For example, thiazole, 4-phenylthiazole,
4,5-diphenylthiazole, 4-methylthiazole, 5-methylthiazole, 4-chlorothiazole, 4-methoxythiazole, etc., and the benzothiazole ring is benzothiazole, 5-chlorobenzothiazole, 5-phenylbenzo thiazole, 5-methylbenzothiazole, 5-methoxybenzothiazole, etc., and the naphthothiazole ring is α-naphthothiazole, β-naphthothiazole, 5-methoxy-β-naphthothiazole, 5-methoxybenzothiazole, etc.
-methyl-β-naphthothiazole, 8-methoxy-α-naphthothiazole, 8-chloro-α-naphthothiazole, and the like. The benzoxazole ring containing Z ₃ as a constituent is
benzoxazole, 5-chlorobenzoxazole, 5-phenylbenzoxazole, 5-phenylbenzoxazole, 5-methylbenzoxazole, 5-methoxybenzoxazole, etc., and the naphthoxazole ring is α-naphthoxazole, β- Naphthoxazole, 5-methoxy-β-naphthoxazole, 5-methyl-β
-naphthoxazole, 5-methyl-β-naphthoxazole, 8-methoxy-α-naphthoxazole, 8-chloro-α-naphthoxazole, and the like. The benzoselenazole ring containing Z ₃ as a constituent is
benzoselenazole, 5-chlorobenzoselenazole, 5-phenylbenzoselenazole, 5-phenylbenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, etc., and the naphthoselenazole ring is α-naphthoselenazole, β-naphthoselenazole, 5-methoxy-β-naphthoselenazole, 5-methyl-β
-naphthoselenazole, 5-methyl-β-naphthoselenazole, 8-methoxy-α-naphthoselenazole, 8-chloro-α-naphthoselenazole, and the like. The alkyl groups represented by R ₆ , R ₇ and R ₈ in the general formula [] are linear or branched, such as methyl group, ethyl group, n-propyl group, i-
Propyl group, n-butyl group, etc. When the alkyl group represented by R ₄ and R ₅ has a substituent, the alkyl group is, for example, a hydroxylalkyl group (e.g. hydroxymethyl group, hydroxyethyl group, hydroxypropyl group). ), sulfoalkyl groups (e.g. sulfoethyl group, sulfopropyl group, sulfobutyl group, 2-hydroxyl-3-sulfopropyl group), sulfatoalkyl groups (e.g. sulfatepropyl group, sulfatebutyl group), carboxyalkyl groups (e.g. carboxymethyl group, carboxyethyl group), acetoxyalkyl group (e.g. acetoxyethyl group), aralkyl group (e.g. benzyl group, phenethyl group),
These include alkenyl groups (eg, allyl group, isopropenyl group), and the like. The acid anions represented by
These include toluenesulfonate ion, ethylsulfonate ion, methylsulfonate ion, nitrate ion, etc. When the compound represented by the general formula [] forms an inner salt, n is 0. Specific examples of the compound represented by the general formula [] are shown below, but the compound is not limited thereto. The silver halide photographic light-sensitive material of the present invention may be any material provided with at least one silver halide emulsion layer on a support. There are no particular restrictions on the number of layers or the order of the layers. Typical specific examples include color positive or negative film, photographic paper, color slides, and special photosensitive materials for printing, X-rays, high resolution, etc., but it is particularly suitable as color photographic paper. . Usually, most of the silver halide emulsion layer and the non-photosensitive layer are hydrophilic colloid layers containing a hydrophilic binder. Gelatin or a gelatin derivative is used as this hydrophilic binder. The cyan coupler according to the present invention represented by the formula [] (hereinafter referred to as the cyan coupler according to the present invention) can be prepared by the same method used for ordinary cyan dye-forming couplers, and contains the cyan coupler according to the present invention. A silver halide emulsion layer is coated onto a support to form a photographic element. The photographic element may be a single color element or a multicolor element. In the case of multicolor elements, the cyan coupler according to the invention is usually contained in a red-sensitive silver halide emulsion layer, but it may also be contained in a non-sensitized emulsion or an emulsion layer sensitive to the three primary color regions of the spectrum other than red. You can let me. Each structural unit forming a dye image in the present invention is a single emulsion layer or a multilayer emulsion layer that is sensitive to a certain region of the spectrum. In order to incorporate the cyan coupler according to the present invention into an emulsion, a conventionally known method may be followed. for example,
Phthalate esters (dibutyl phthalate, etc.), phosphoric acid esters (tricresyl phosphate, etc.)
or N,N-sialkyl-substituted amides (N,N
The cyan coupler according to the present invention is added to a high boiling point organic solvent such as diethyllaurinamide, etc.) and a low boiling point organic solvent such as butyl acetate or butyl propionate, respectively, or in a mixture of these solvents as necessary. After dissolving each individually or in combination, they are mixed with an aqueous gelatin solution containing a surfactant, and then emulsified and dispersed using a high-speed rotary mixer, colloid mill, or ultrasonic disperser, and then mixed with silver halide. In addition, silver halide emulsions for use in the present invention can be prepared. When the cyan coupler according to the present invention is added to a silver halide emulsion, it is usually added in an amount of about 0.05 to 2 mol, preferably 0.1 to 1 mol, per mol of silver halide. Furthermore, at least one compound of the compound group represented by the general formula [] and the general formula [] (hereinafter referred to as the sensitizing dye according to the present invention) is a silver halide emulsion containing the cyan coupler according to the present invention. In order to add the sensitizing dye according to the present invention to an emulsion containing the cyan coupler according to the present invention,
Conventionally known methods may be followed, and the sensitizing dye may be mixed with a suitable solvent such as methanol, ethanol, N,N-
A solution of dimethylformamide, ethyl acetate, etc., or a mixed solution thereof, during chemical ripening of the emulsion.
Alternatively, the increasing dye solution may be added either before or after the stabilizer and antifoggant are added after chemical ripening. When the sensitizing dye according to the present invention is added to a silver halide emulsion, the amount added is not particularly limited, but is usually about 1×10 -4 to 1×10 ⁻⁴ per mole of silver halide.
It is added in an amount of 1×10 ⁻⁶ mol, preferably 1×10 ⁻⁶ to 5×10 ⁻⁵ mol. The sensitizing dyes according to the present invention can be used alone or in combination. Furthermore, a substance exhibiting a supersensitizing action, a so-called supersensitizer, may be used together with the sensitizing dye, if necessary. A specific example of the method for producing the silver halide photographic material of the present invention is shown below. First, silver halide grains are produced by a known method, and after suitable physical ripening, soluble salts are removed, and then, after suitable chemical ripening, the sensitizing dye solution and stabilizer solution of the present invention are added and chemically aged. A sensitized silver halide emulsion is obtained. On the other hand, the cyan coupler according to the present invention is dissolved in an appropriate high-boiling point solvent and low-boiling point solvent, added to an aqueous gelatin solution containing a surfactant, and then emulsified and dispersed to obtain a cyan coupler dispersion. Next, a cyan coupler dispersion liquid is added to the chemically sensitized silver halide emulsion, and a spreading agent, a hardening agent, etc. are added to prepare a photographic emulsion coating liquid, which is coated on a support and dried. Obtain the sensitive material. When the silver halide color photographic material of the present invention is a multicolor element, the necessary layers of the photographic element, including the layers of the image-forming units described above, may be added in various orders as known in the art. Can be arranged.
In this case, there are layers other than the image-forming structural unit layer, such as non-photosensitive layers such as a filter layer, an intermediate layer, a protective layer, an antihalation layer, and an undercoat layer. Examples of the support according to the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper; transparent support with a reflective layer or a reflective material; glass plate; cellulose acetate, cellulose nitrate, polyethylene terephthalate, etc. Examples include polyester film; polyamide film; polycarbonate film; polystyrene film. These supports are appropriately selected depending on the purpose of use of the silver halide photographic material of the present invention. Various coating methods such as dip coating, air doctor coating, curtain coating, and hopper coating are used for coating the silver halide emulsion layer and non-photosensitive layer used in the present invention. The silver halide used in the silver halide emulsion according to the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc., which are commonly used in silver halide emulsions. Includes anything that These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of [100] planes to [111] planes can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. Furthermore, these silver halides may be produced by any of the neutral method, ammonia method, and acidic method, and may be produced by any of the simultaneous mixing method, forward mixing method, back mixing method, convergence method, etc. Silver halide grains manufactured by can also be applied. The silver halide emulsion according to the present invention contains, in addition to the sensitizing dye according to the present invention, a sulfur sensitizer such as arylthiocarbamide, thiourea, cystine, etc., an active or inactive selenium sensitizer, and a reduction Sensitizers such as stannous salts, polyamines, etc., noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-ourosulfobenzthiazole methyl chloride, etc., or e.g. Chemical sensitization can be carried out using water-soluble salt sensitizers such as ruthenium and iridium, specifically ammonium chlorovaladate, potassium chloroplatinate, and sodium chloroparadide, alone or in combination as appropriate. Further, the silver halide emulsion according to the present invention can contain various known photographic additives.
For example, “Research Disclosure” 1978
A photographic additive such as that described in December, No. 17643. The silver halide emulsion layer and non-photosensitive layer of the silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives. Antifoggants, color stain inhibitors, fluorescent brighteners, antistatic agents, hardeners, plasticizers, wetting agents, antioxidants and ultraviolet absorbers as described in Research Disclosure No. 17643, for example. etc. can be used as appropriate. Specific Uses of the Invention The silver halide photographic material of the present invention thus constructed can be subjected to various photographic processing methods for color development after exposure. A preferred color developing solution used in the present invention is one containing an aromatic primary amine color developing agent as a main component. A typical example of this color developing agent is a P-phenylenediamine type, such as diethyl-p
-phenylenediamine hydrochloride, monomethyl-p-
Phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N
-ethyl-N-dodecylamino)-toluene, 2
-amino-5-(N-ethyl-N-β-methanesulfonamidoethyl)aminotoluene sulfate, 4
-(N-ethyl-N-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N
-β-hydroxyethylamino)aniline, 2-
Amino-5-(N-ethyl-β-methoxyethyl)
These color developing agents, such as aminotoluene, may be used alone or in combination of two or more, and if necessary, in combination with a black and white developing agent such as hydroquinone. Furthermore, color developing solutions generally contain alkaline agents such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfite, etc., and various additives such as alkali metal halides such as potassium bromide, or development modifiers such as hydrazinic acid. It may contain. The silver halide photographic light-sensitive material of the present invention may contain the above color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor. The color developing agent precursor is a compound that can produce a color developing agent under alkaline conditions, and includes a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor,
Examples include a Shugar amine reactant precursor and a urethane type precursor. Precursors for these aromatic primary amine color developing agents are, for example, U.S. Pat.
2695234, British Patent No. 3719492, British Patent No. 803783, Japanese Unexamined Patent Publications No. 53-135628 and 54-79035, Research Disclosure Magazine 15159
No. 12146, No. 13924. These aromatic primary amine color developing agents or their precursors need to be added in amounts that will provide sufficient color development during development. This amount varies considerably depending on the type of photosensitive material and is generally between 0.1 mol and 5 mol, preferably between 0.5 mol and 3 mol, per mol of photosensitive silver halide. These color developing agents or their precursors can be used alone or in combination. In order to incorporate the above compound into a photographic light-sensitive material, it can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc., and added. It can also be added as an emulsified dispersion using a high-boiling organic solvent,
It can also be added by impregnating a latex slimer as described in No. 14850. The silver halide photographic material of the present invention usually includes:
Bleaching and fixing after color development, or bleach-fixing,
Many compounds are used as bleaching agents, including polyvalent metal compounds such as iron (), cobalt (), and tin (), especially complex salts of these polyvalent metal cations and organic acids. , for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and N-hydroxyethylethylenediaminediacetic acid; metal complex salts or ferricyanates such as malonic acid, tartaric acid, malic acid, diglycolic acid, and dithioglycolic acid; Dichromate and the like are used alone or in appropriate combinations. Specific effects of the invention According to the silver halide photographic material of the invention,
A dye image is formed with extremely little light yellowing, and it not only has excellent overall image storage stability including heat resistance, moisture resistance, and fading resistance, but also has excellent color restoration properties during bleach-fixing processing. It has good stability, and the stability of the emulsion coating liquid during production is also good, and specific effects such as stable mass production are exhibited. Specific Examples of the Invention The present invention will be described in more detail below with reference to specific examples, but the embodiments of the present invention are not limited thereto. Example 1 The above exemplary couplers (-8, -14, -43)
Alternatively, each of the comparative couplers (X) below was dissolved in dibutyl phthalate and ethyl acetate, and alkanol XC (sodium alkylnaphthalene sulfonate,
After adding it to an aqueous gelatin solution containing (manufactured by Dupont),
Disperse with a homogenizer to obtain a cyan coupler dispersion. Next, the exemplified compounds (-15, -22, -
Chemical ripening in which the sensitizing dyes shown in 3, -11, -27) or the following comparative sensitizing dyes (A, B, C, D, E) were each added in an amount of 2.0 x 10 ^-5 mol per mol of silver halide. Add the above cyan coupler dispersion per mole of silver halide to 1000μ of finished silver chlorobromide emulsion.
Forty types of photographic coating solutions were prepared by adding each to a content of 0.4 mol. Apply the coating solution prepared as above immediately after preparation.
After being left at 40°C for 3 hours and 6 hours at 40°C, the mixture was coated on polyethylene coated paper and dried to obtain a silver halide photographic material. Comparison sensitizing dye After exposing these samples to light wedge light, they were processed and dried according to the processing method shown below, and then sensitometry was performed using a Sakura color densitometer PDA-60 model (manufactured by Konishiroku Photo Industry KK). Table 1 shows the relative sensitivities of each sample after the coating solution was left standing, with the sensitivity of the immediately applied dry sample being 100. Incidentally, all the development processing conditions were the same as described below. Processing process (32.8℃) Processing time Color development 3 minutes 30 seconds Bleach-fixing 1 minute 30 seconds Washing with water 3 minutes 30 seconds Drying Color developer composition N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4 -aminoaniline sulfate
4.0g Hydroxylamine sulfate 2.0g Potassium carbonate 25.0g Sodium chloride 0.1g Sodium bromide 0.2g Anhydrous sodium sulfite 2.0g Benzyl alcohol 10.0ml Polyethylene glycol (average degree of polymerization 400)
Add 3.0ml water to make 1, and use sodium hydroxide to
Adjust to PH10.0. Bleach-fix composition Ethylenediaminetetraacetic acid iron sodium salt
60.0g Ammonium thiosulfate 100.0g Sodium bisulfite 20.0g Sodium metabisulfite 5.0g Add water to make 1, and adjust to pH 7.0 using sulfuric acid. Redox potential -70mV

【table】

[Table] As shown in Table 1 above, the photographic coating solution of the present invention when the sensitizing dye according to the present invention is used in producing the silver halide photographic light-sensitive material containing the cyan coupler according to the present invention is as follows: A photographic coating other than the present invention that uses a comparative sensitizing dye that exhibits very little loss of sensitivity and is stable even after being aged for a long period of time and has a structure very similar to the sensitizing dye of the present invention. The liquid has a significant decrease in sensitivity and is unstable. That is, the silver halide photographic material of the present invention is
It can be seen that the quality is always constant. Example 2 Cyan colored dye images were formed on the samples No. 1 to 40 prepared in Example-1 by the same method as in Example-1, and the images were left in a dark room at 77°C for 500 hours. A dark fading test was conducted. Then, the dye residual ratio (D/D _{p × 100) of the post-test density D to the pre-test density (D p =} 1.0) was determined using the Sakura color densitometer PDA-
Measured with a 60-inch model using a red filter. The results are shown in Table-2.

【table】

[Table] As shown in Table 2 above, as a result of conducting a fading test on cyan dye images for the above materials No. 1 to No. 40, the photosensitive materials containing the cyan coupler according to the present invention were found to be It can be seen that the fading resistance of the cyan dye image is extremely superior compared to the photosensitive material containing . Furthermore, in conjunction with the results in Table 1, it can be seen that the silver halide photographic material of the present invention has excellent dark fading resistance of cyan color-forming dye images and always has constant quality. I understand. Example 3 The same tests as in Examples 1 and 2 were conducted with different cyan couplers and sensitizing dyes. That is, the exemplary coupler of Example-1 is (-4, -17,
-30, -36, -46) and the comparative coupler was replaced with the following Y, and further sensitizing dyes were added to the illustrative compounds (-8, -14, -29) and the following comparative sensitizing dyes F and G. Instead, 30 types of coating solutions for inochi were prepared in the same manner as in Example-1, and immediately after preparation and at 40°C for 30 minutes.
After being left for an hour and at 40°C for 6 hours, the mixture was applied onto polyethylene coated paper and dried to obtain a silver halide photographic material. Furthermore, tests similar to those in Example-1 and Example-2 were conducted, and the results are shown in Table-3. comparison coupler

[Table] From the results in Table 3, it can be seen that when producing a silver halide photographic material containing a cyan coupler according to the present invention in the same manner as in Example 1, the sensitizing dye according to the present invention was used. The photographic coating solution is stable with very little decrease in sensitivity even after being aged for a long time, and as in Example 2, the silver halide photographic light-sensitive material containing the cyan coupler of the present invention is It can be seen that the cyan dye image has extremely excellent fading resistance. That is, the silver halide photographic material of the present invention is
It can be seen that the cyan dye image has excellent fading resistance and always has a constant quality. Example 4 A front plate was prepared on a support made of polyethylene coated paper.
A coating solution for each layer was prepared so as to have the structure shown in 4, and the layers were sequentially applied from the support side to prepare materials for multilayer silver halide color light-sensitive materials No. 71 to No. 86. Here, each coating liquid for the first layer, third layer, and fifth layer was prepared as follows. 1st layer Yellow coupler Y-1 and stain prevention material AS
-1 was dissolved in dinonyl phthalate and ethyl acetate, mixed with an aqueous gelatin solution containing sodium alkylnaphthalene sulfonate, and emulsified and dispersed using an ultrasonic hogenizer. A coating solution is prepared by adding this to a spectrally sensitized silver chlorobromide emulsion. 3rd layer magenta coupler M-1 and stain inhibitor AS
-1 and anti-fading agents AO-1 and AO-2 were dissolved in dioctyl phthalate and ethyl acetate, mixed with an aqueous gelatin solution containing sodium alkylnaphthalene sulfonate, and dispersed into an emulsion using an ultrasonic homogenizer. A coating solution is prepared by adding the coupler dispersion to a silver chlorobromide emulsion that has been spectrally sensitized with a sensitizing dye. 5th layer cyan coupler-4 and stain inhibitor AS-
1 was dissolved in dioctyl phthalate and ethyl acetate, mixed with an aqueous gelatin solution containing sodium alkylnaphthalene sulfonate, and emulsified and dispersed using an ultrasonic homogenizer. The obtained cyan coupler dispersion was mixed with sensitizing dye-15. Coating solution No. 71 is prepared by adding it to the spectrally sensitized silver chlorobromide emulsion. Similarly, coating solutions No. 72 to No. 86 were prepared using the fifth layer composition conditions (cyan coupler, sensitizing dye) shown in Table 5. In order to examine the effects of the present invention, each of the coating solutions prepared as described above was coated on polyethylene-coated paper immediately after preparation, after being left at 40°C for 3 hours, and after being left at 40°C for 6 hours. Up to seven layers are sequentially applied from the support side as shown in Tables 4 and 5, and dried. Then, tests similar to those in Example-1 and Example-2 were conducted, and the results are shown in Table-5.

【table】

[Table] Yellow coupler Y-1 Magenta coupler M-1 UV absorber UV-1 UV absorber UV-2 Anti-fading agent AO-1 Anti-fading agent AO-2 Sensitizing dye H Sensitizing dye I Stain inhibitor AS-1

【table】

[Table] From the results in Table 5, it can be seen that the silver halide photographic material of the present invention using the cyan coupler of the present invention and the sensitizing dye of the present invention is suitable for producing silver halide photographic materials. It can be seen that even if the photographic coating liquid is aged for a long time, there is very little decrease in sensitivity, and that the sensitivity of the three layers is well balanced and always has a constant quality. Furthermore, the silver halide photographic light-sensitive material of the present invention has extremely excellent fading resistance of cyan dye images, and C, M,
It can be seen that the three layers of Y and Y are well balanced.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having at least one silver halide emulsion layer provided on a support, a cyan coupler represented by the following general formula [] is contained in the silver halide emulsion layer. and the silver halide in the silver halide emulsion layer is spectrally sensitized with at least one compound from the compound group represented by the following general formula [] and general formula []. A silver halide photographic material characterized by: General formula [] [In the formula, R ₁ represents an alkyl group or an aryl group. R ₂ is an alkyl group, a cycloalkyl group,
Represents an aryl group or a heterocyclic group. R ₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Further, R ₃ may be combined with R ₁ to form a ring. Z ₁ represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. ] General formula [ ] [In the formula, L ₁ , L ₂ and L ₃ each represent a methine group. Y ₁ and Y ₂ are each an oxygen atom,
Represents a sulfur or selenium atom. R ₄ and
Each R ₅ represents an alkyl group. However, R ₄
and at least one of R ₅ has a sulfo group.
A ₁ , A ₂ , B ₁ , B ₂ , C ₁ , C ₂ , D ₁ and D ₂ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, a cyano group, a nitro group,
Or represents an alkoxycarbonyl group. Also,
At least one of the combinations of A ₁ and B ₁ , B _{1 and} C 1 , C ₁ and D ₁ , A ₂ and B ₂ , B ₂ and C ₂ , and C ₂ and D ₂ are fused to form a benzene ring You may do so. M represents a cation, and m represents 0 or 1. ] General formula [ ] [In the formula, Z ₂ represents a group of nonmetallic atoms necessary to constitute a quinoline ring together with the bonded nitrogen atom and carbon atom. Z ₃ represents an atomic group necessary to constitute a thiazole ring, benzothiazole ring, naphthothiazole ring, benzoxazole ring, naphthoxazole ring, benzoselenazole ring or naphthoselenazole ring together with the nitrogen atom and carbon atom to which it is bonded. . R ₆ , R ₇ and R ₈ each represent an alkyl group. X represents an acid anion. l
and n each represent an integer of 0 or 1. ]