JPH0414334B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide color photographic light-sensitive material with improved photographic performance, and more specifically to a novel halogen-based color photographic material that prevents fogging due to high temperature and high humidity storage and also prevents coupler deactivation due to long storage. This invention relates to silver chemical color photographic materials. Generally, after a silver halide color photographic material (hereinafter simply referred to as a color photographic material) is imagewise exposed, it is developed with a color developing solution to form an oxidation product of an aromatic primary amine developing agent and a coupler. It is well known that various dyes such as indophenol, indoaniline, indamine, azomethine, phenoxazine, and phenazine are produced by a coupling reaction, and an image-like dye image is formed. In the field of ordinary color photography, color reproduction is performed based on the principle of the dechromic method, so the above color light-sensitive materials have a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer. It has a silver emulsion layer, and each layer contains a yellow coupler, a magenta coupler, and a cyan coupler, respectively. Conventionally, these couplers include 4-equivalent couplers, which require 4 moles of silver halide to produce 1 mole of dye, and 2-equivalent couplers, which require only 2 moles of silver halide.
Equivalent couplers are known. For example, in the magenta coupler, 2
Equivalent couplers are described in U.S. Pat. No. 3,214,437 and U.S. Pat. No. 3,253,924, and U.S. Pat. Displaced coupler, West German patent no. 2414006,
JP-A-49-53436 and JP-A-50-13041 describe couplers substituted with a substituent having a nitrogen atom. However, when the above-mentioned known couplers are used, they may cause significant color fogging, may not have appropriate reaction activity, or may develop color during long-term storage due to the couplers being chemically unstable. However, it has been extremely difficult to put it into practical use because it sometimes changes into a substance that does not exist. Also, apart from these couplers, U.S. Patent No.
Two-equivalent couplers in which the 4-position of a 5-pyrazolone is substituted with an alkylthio group, an arylthio group, or a heterocyclic thio group are also known, as described in No. 3,227,554. However, many of these compounds have inadequate reaction activity with the oxidation products of aromatic primary amine developing agents, and furthermore, due to the strong photographic effects of the mercapto compounds formed as a result of the coupling reaction, they are not commonly used. There were difficulties in applying it to color photosensitive materials, and the chemical stability of the coupler was not sufficient. Furthermore, in response to the recent technical issue of increasing the sensitivity of color photosensitive materials, the coloring sensitivity of the above-mentioned 2-equivalent magenta coupler is not necessarily sufficient, and the development of technology to increase the sensitivity of the magenta dye image forming layer is required. It was strongly desired. Furthermore, U.S. Pat. No. 3,419,391 also discloses couplers substituted with aryloxy groups,
No. 55-172509 and No. 55-172510 disclose couplers substituted with an aralkyloxy group, a heterocyclic oxy group, or the like. These couplers have particularly high activity and color development, are highly resistant to formalin gas, and are attracting attention as they do not change into inert substances when stored for long periods of time. When stored under humid conditions (hereinafter referred to as high temperature and high humidity conditions), it has the disadvantage of being extremely prone to fogging. Therefore, for the purpose of improving the long-term storage stability at low temperatures of the above-mentioned active site substituted magenta couplers, a technique using a compound having an imino group and a ketone group in the heterocycle has been proposed, for example, as disclosed in JP-A-53-52422.
No. 54-130928, these compounds are effective in preventing coupler deactivation, but have the disadvantage of being ineffective in preventing fogging under high temperature and high humidity conditions. There is. Furthermore, recently, a technique has been disclosed, for example, in JP-A-56-85749, in which a non-diffusible 1-phenyl-3-pyrazolidone derivative is used in combination with a magenta coupler in which the active site is substituted with an alkylthio group. There is. However, the technology related to this combination is intended to improve the coloring efficiency of the coupler, and has no antifogging effect at all under high temperature and high humidity conditions, and on the contrary, it even has the effect of accelerating fogging. Therefore, the first object of the present invention is to provide a color photosensitive material that has good color development and is prevented from fogging due to couplers under high temperature and high humidity conditions, and the second object is to provide a color photosensitive material that can be stored for a long time The object of the present invention is to provide a color light-sensitive material in which deactivation of couplers is prevented during processing, and the storage stability of dye images under light, high temperature, and high humidity conditions is improved.
The purpose of this invention is to provide a color photosensitive material with excellent desilvering properties during bleaching. As a result of various investigations into the above-mentioned problem, the present inventors have found that a silver halide emulsion layer containing at least one type of 2-equivalent magenta coupler represented by the following general formula () and/or adjacent to the emulsion layer. It has been found that the above object can be achieved by a silver halide color photographic material containing a non-diffusible 1-phenyl-3-pyrazolidone derivative represented by the following general formula () in a hydrophilic colloid layer. General formula () Cp-OR (wherein, Cp represents a magenta color image-forming coupler residue, OR represents a group capable of coupling off with the oxidation product of an aromatic primary amine developing agent, and here R represents a substituted or unsubstituted aryl group or aralkyl group.) General formula () (In the formula, R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, an alkenyl group, a hydroxy group, an alkoxy group, an alkylthio group, an amino group, an allylamino group, or a sulfonamide group, and R ₂ to R ₅ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkoxy group, or aryloxy group, and at least one of the above substituents represented by R ₂ to R ₅ is a carbon atom. In other words, according to the combined effect of the present invention, the increase in fog under high temperature and high humidity conditions is clearly small, and the inactivation of the coupler during long-term storage at low temperatures is reduced. This is an unexpected effect. These surprising effects are due to the fact that a special substituent is introduced into the 4- or 5-position of the 3-pyrazolidone derivative to make it non-diffusible, thereby preventing diffusion to other layers, and by changing the reducing power. It is thought that this has a unique effect on the coupler represented by the above general formula (). The present invention will be explained in more detail below. Preferred compounds of the magenta color image-forming coupler according to the present invention having a group capable of being separated by a coupling reaction with the oxidation product of the aromatic primary amine developing agent represented by the general formula () include pyrazolone-based compounds, respectively. compounds, pyrazolotriazole compounds, and pyrazolobenzimidazole compounds, which can be represented by the following general formulas (), (), or (). General formula () General formula () General formula () In the formula, R ₆ is a hydrogen atom, a linear or branched alkyl group having 1 to 35 carbon atoms, preferably 1 to 22 carbon atoms (e.g., methyl, isopropyl, tert-butyl, etc.), an alkenyl group (e.g., allyl group, etc.), It represents a cyclic alkyl group (e.g., cyclopentyl, norbornyl group, etc.), an aralkyl group (e.g., benzyl group, etc.), a cyclic alkenyl group (e.g., cyclopentenyl group, etc.), and these groups include a halogen atom, nitro, cyano, aryl, Alkoxy, aryloxy, carboxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, acyloxy, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, thioureido, urethane, thiourethane, sulfonamide, arylsulfonyloxy, alkyl Sulfonyloxy, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylsulfinyl, arylsulfinyl, alkylamino, dialkylamino, anilino, N-arylanilino, N-alkylanilino, N-acylanilino, hydroxy and mercapto It may be substituted with a substituent selected from the group. Furthermore, R ₆ represents an aryl group (eg, phenyl, naphthyl group, etc.) and an aryl group having one or more substituents. Examples of this substituent include alkyl groups (e.g., methyl, isopropyl, tert-butyl, etc.), alkenyl groups (e.g., allyl group, etc.),
Cyclic alkyl groups (e.g., cyclopentyl, norbornyl groups, etc.), aralkyl groups (e.g., benzyl groups, etc.), cyclic alkenyl groups (e.g., cyclopentenyl groups, etc.), halogen atoms, nitro,
Cyano, aryl, alkoxy, aryloxy, carboxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, acyloxy, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, thioureido, urethane,
Thiourethane, sulfonamide, heterocycle, arylsulfonyloxy, alkylsulfonyloxy, arylsulfonyl, alkylsulfonyl,
Allurthio, alkylthio, alkylsulfinyl, arylsulfinyl, alkylamino,
selected from dialkylamino, anilino, N-arylanilino, N-alkylanilino, N-acylanilino, hydroxy and mercapto groups. Further, R ₆ is more preferably a phenyl group in which at least one ortho position is substituted with an alkyl group, an alkoxy group, a halogen atom, etc. The coupler remains in the film and is less likely to be printed out by light or heat. It is useful. Furthermore, R ₆ is a heterocyclic group (for example, a 5- or 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, a fused heterocyclic group, pyridyl,
quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, naphthoxazolyl, etc.) and a heterocyclic group substituted with a substituent listed for the above-mentioned aryl group. Furthermore, R ₆ represents an acyl, thioacyl, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, carbamoyl, and thiocarbamoyl group. Next, in the formula, R ₇ represents a hydrogen atom, a straight chain or branched alkyl, alkenyl, cyclic alkyl, aralkyl, or cyclic alkenyl group having 1 to 35 carbon atoms, preferably 1 to 22 carbon atoms, and these represent the above R ₆ It may also have the listed substituents. Moreover, R ₇ represents an aryl or a heterocyclic group,
These may have the substituents listed for R ₆ above. Furthermore, R ₇ is alkoxycarbonyl (e.g.
methoxycarbonyl, ethoxycarbonyl, stearyloxycarbonyl, etc.), aryloxycarbonyl (e.g., phenoxycarbonyl,
α- to β-naphthoxycarbonyl group, etc.),
Aralkyloxycarbonyl (e.g. penzyloxycarbonyl group, etc.), alkoxy (e.g. methoxy, ethoxy, decyloxy group, etc.), aryloxy (e.g. phenoxy, tolyloxy group, etc.), alkylthio (e.g. ethylthio, dodecylthio group, etc.), arylthio (e.g. phenylthio, α-naphthylthio group, etc.), carboxy,
Acylamino (e.g. acetylamide, 3-
{(2,4-di-tert-amylphenoxy)acetamido}benzamide group, etc.), diacylamino,
N-alkylacylamino (for example, N-methylpropionamide group, etc.), N-arylacylamino (for example, N-phenylacetamide group, etc.),
ureido (e.g. ureido, N-aryl ureido, N-alkyl ureido groups, etc.), thioureido (e.g. thioureido, N-aryl thioureido, N-alkyl thioureido groups, etc.), urethane, thiourethane, anilino (e.g. phenylamino, N-alkyl Anilino, N-arylanilino, N-acylanilino, 2-chloro-5-
(tetradecanamide anilino group, etc.), alkylamino (e.g. n-butylamino, N-N-dialkylamino, cycloalkylamino group, etc.),
Cycloamino (e.g. piperazino, pyrrolidino group, etc.), alkylcarbonyl (e.g. methylcarbonyl group, etc.), arylcarbonyl (e.g. phenylcarbonyl group, etc.), sulfonamide (e.g. alkylsulfonamide, arylsulfonamide group, etc.), carbamoyl (e.g. N-alkylcarbamoyl, N,N-dialkylcarbamoyl, N-alkyl-N-arylcarbamoyl, N-arylcarbamoyl, N,N-diarylcarbamoyl group, etc.), sulfamoyl (e.g. N-alkylsulfamoyl, N,N - dialkylsulfamoyl, N-arylsulfamoyl, N-alkyl-N-arylsulfamoyl, N-N-diarylsulfamoyl group, etc.),
Guanidino (e.g. N-alkylguanidino, N
-arylguanidino group, etc.), cyano, acyloxy (eg, tetradecyloxy group, etc.), sulfonyloxy (eg, benzenesulfonyloxy group, etc.), hydroxy, mercapto, halogen atom, and sulfo group. In the formula, _R8 is a hydrogen atom, a straight or branched alkyl group having 1 to 35 carbon atoms, preferably 1 to 22 carbon atoms,
alkenyl group, cyclic alkyl group, aralkyl group,
Represents a cyclic alkenyl group, which may have the substituents listed for R ₆ above. In addition, R ₈ represents an aryl or a heterocyclic group,
These may have the substituents exemplified for R ₆ above. Furthermore, R ₈ is cyano, halogen atom, alkoxy, aryloxy, carboxy, acyloxy, alkylcarbonyl, alkylthiocarbonyl, arylthiocarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, acyloxy, sulfamoyl, carbamoyl, acylamino, diacyl Amino, ureido, thioureido, urethane, thiourethane, sulfonamino, alkylsulfonyloxy, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylsulfinyl, arylsulfinyl, alkylamino, dialkylamino, anilino, N-arylani Represents lino, N-alkylanilino, N-acylanilino, hydroxy and mercapto groups. In the formula, R ₉ represents an aralkyl group (such as a benzyl group), and these groups include a halogen atom, nitro, cyano, aryl, alkoxy,
Aryloxy, carboxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, acyloxy, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, thioureido, urethane, thiourethane, sulfonamide,
Heterocycle, aryl, sulfonyloxy, alkylsulfonyloxy, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylsulfinyl, arylsulfinyl, substituted amino group (e.g. alkylamino, dialkylamino group, etc.), etc. It's okay. Furthermore, the aryl group of R ₉ is phenyl, naphthyl,
It represents a polycyclic aryl group such as substituted phenyl and substituted naphthyl, and these represent one or more alkyl, aralkyl, alkenyl, cyclic alkyl,
Cyclic alkenyl, halogen atom, nitro, cyano, aryl, alkoxy, aryloxy, carboxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, acyloxysulfamoyl, N,N-dialkylsulfamoyl, N- Alkyl-N-arylsulfamoyl, N-alkylsulfamoyl, N-arylsulfamoyl, carbamoyl, N-alkylcarbamoyl,
N,N-dialkylcarbamoyl, N-alkyl-N-arylcarbamoyl, N-arylcarbamoyl, acylamino, diacylaminoureido, thioureidosulfonamide, urethane, thiourethane heterocycle (e.g. pyridyl, quinolyl,
furyl, piperidyl group, etc.), alkylsulfonyl, arylsulfonyl, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, substituted amino group (e.g. N,N-dialkylamino, anilino, N-acylanilino, N-
represents a substituted aryl group which may be substituted with an arylanilino group, etc.). The present invention also includes a pyrazole coupler in which the 5-position of 5-pyrazolone represented by the general formula () is substituted with a carbonyloxy group or a sulfonyloxy group. Next, specific examples of the 2-equivalent magenta coupler represented by the general formula () of the present invention will be described, but the present invention is not limited thereto. The above-mentioned two-equivalent coupler of the present invention represented by the general formula ( can do. Next, in the general formula () of the present invention, examples of the substituent for the alkyl group having 1 to 5 carbon atoms represented by R ₁ include an alkoxy group and a hydroxy group. In the above general formula (), substituents for the alkyl group and aryl group represented by R ₂ to _{R 5} include a halogen atom, an alkyl group, an aryl group,
Aralkyl group, alkoxy group, aryloxy group, arylthio group, alkylthio group, acylamino group, nitro group, sulfonamide group, cyano group, hydroxy group, sulfo group, heterocyclic group, alkoxy group, alkoxycarbonyl group, aryloxycarbonyl group etc. can be mentioned. Specific compound examples of the non-diffusible 1-phenyl-3-pyrazolidone derivative (hereinafter referred to as phenidone derivative) of the present invention represented by the general formula () are described below, but the present invention is not limited thereby. It's not a thing. (Compound example) The phenidone derivatives of the present invention represented by the general formula () are disclosed in, for example, US Pat.
It can be synthesized according to the synthesis methods described in No. 2843598, JP-A-56-64339, and the like. In the present invention, a silver halide emulsion layer containing the 2-equivalent magenta coupler according to the present invention and a hydrophilic colloid layer adjacent to the emulsion layer to be contained in combination with the phenidone derivative according to the present invention, The photosensitive layer contains a silver halide such as silver bromide or silver iodobromide, which is made sensitive to a specific wavelength range by a sensitizing dye, as well as a colloidal silver-containing layer and a filter layer (ultraviolet absorbing layer). layer, mordant dyed layer, colored layer containing dye, etc.),
Refers to non-photosensitive layers such as gelatin intermediate layers and protective layers. A preferred adjacent layer is a gelatin intermediate layer containing no silver halide. The two-equivalent magenta couplers according to the present invention can be used alone or in combination of two or more. Further, if necessary, a colorless or colored 2-equivalent or 4-equivalent magenta coupler other than the above magenta coupler may be used in combination. Examples of such couplers include ordinary magenta couplers, magenta couplers, so-called development-inhibiting compound-releasing couplers (DIR couplers), monothio couplers, and O-
Aminophenylazo couplers, hydroquinones that release compounds that inhibit development during development,
There are compounds selected from each group of compounds that do not form a dye through a coupling reaction with a color developing agent, unlike DIR couplers. In order to satisfy the characteristics required of a color photosensitive material, two or more of the couplers mentioned above can be used in the same layer, or the same compound can be added to two or more different layers. The amount of magenta coupler added according to the present invention is
Usually, preferred results are obtained with 0.01 to 5 mol/mol of silver halide. Further, the timing of addition is usually preferably after the completion of chemical ripening. In the silver halide color photographic light-sensitive material of the present invention, a 5- or 6-membered ring nucleus containing an imino group and a carbonyl group is incorporated as a ring constituent unit in the emulsion layer containing the magenta coupler or in the hydrophilic colloid layer adjacent thereto. Heterocyclic compounds (hereinafter referred to as self-release desensitization inhibitors) having the following properties can be added alone or in combination of two or more. A compound useful as this self-release desensitization inhibitor is one in which the nitrogen atom of the imino group and the carbon atom of the carbonyl group are directly bonded. In addition, as specific compounds of the self-release desensitization inhibitor that can be used in the present invention, JP-A-53-
Examples include those described in Publication No. 52422. The phenidone derivatives according to the present invention can be used alone or in combination of two or more. The amount added is usually about 0.005 mol to 10 mol per mol of the 2-equivalent magenta coupler, whether it is added to an emulsion layer containing the magenta coupler according to the present invention or to a layer adjacent to the emulsion layer. Moles are appropriate.
A particularly preferable addition amount for the present invention is 0.01 mol to 2 mol per mol of the 2-equivalent magenta coupler. The emulsion layer or hydrophilic colloid layer containing the above phenidone derivative may contain reducing agents or antioxidants such as sulfites (sodium sulfite, potassium sulfite, etc.), bisulfites (sodium bisulfite, potassium bisulfite, etc.), hydroxyl Amines (hydroxylamine, N-methylhydroxylamine,
N-phenylhydroxylamine, etc.), sulfinic acids (sodium phenylsulfinate, etc.),
Hydrazines (N,N'-dimethylhydrazine, etc.), reductones (ascorbic acid, etc.), aromatic hydrocarbons having one or more hydroxyl groups (p-
It may be preferable to use aminophenol, gallic acid, catechol, pyrogallol, resordin, 2,3-dihydroxynaphthalene, etc. in combination in order to fully exhibit the effects of phenidone derivatives. Furthermore, adding one or more types of alkyl-substituted hydroquinones, bishydroquinones, polymeric hydroquinones, etc. to the emulsion layer containing the magenta coupler according to the present invention or its adjacent layer can fully exhibit the effects of the phenidone derivative. It is useful for Furthermore, in order to improve the light fastness of a magenta color image formed from the magenta coupler according to the present invention, p-alkoxyphenols and phenolic compounds can be added to the emulsion layer or a layer adjacent thereto. The magenta couplers and phenidone derivatives mentioned above can be used in either high-boiling water-immiscible organic solvents, low-boiling point organic solvents or water-soluble organic solvents, or in high-boiling water-immiscible organic solvents and/or low-boiling point and/or water-immiscible organic solvents. Alternatively, it is advantageously mixed into a solvent dispersion by dissolving it in a water-soluble organic solvent. Useful solvents among high-boiling water-immiscible organic solvents include, for example, di-n-butyl phthalate, benzyl phthalate, triphenyl phosphate, tri-o-cresyl phosphate, diphenyl mono-o-chlorophenyl phosphate. , monophenyl-di-o-chlorophenyl phosphate, dioctyl phthalate, dibutyl sepacate, acetyl tributyl citrate, tri-t-octyl trimellitate, n-nonylphenol, dioctyl phosphate, N,N'-diethyl laurylamide , 3-pentadecyl phenyl ethyl ether, 2,5-di-Bec-amyl phenyl butyl ether, and the like. Low boiling or water-soluble solvents that can be used in place of or in conjunction with high boiling solvents include the following. (1) Low-boiling organic solvents substantially insoluble in water, such as methyl, ethyl, propyl, isopropyl and butyl acetate, ethylformate, butylformate, ethylpropionate, chloroform, carbon tetrachloride, Nitromethane, nitroethane, sec-butyl alcohol, etc. (2) Water-soluble organic solvents, such as methyl isobutyl ketone, β-ethoxyethyl acetate, diethylene glycol monoacetate, methoxy triglycol acetate, acetylacetone, diacetone alcohol, methyl carbitol, butyl carbitol, methyl cellosolve, ethylene glycol, diethylene glycol, Acetone, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, etc. Emulsifying homogenizers, ultrasonic emulsifiers, colloid mills, and the like are useful for dispersing lipophilic couplers. Diffusion-resistant couplers that have a ballast group and a sulfonate group or a carboxyl group in one molecule are soluble in a neutral to weakly alkaline aqueous solution, and by adding the aqueous solution to a silver halide emulsion, the coupler can be added to a silver halide emulsion layer. can be incorporated into the The above magenta coupler and phenidone derivative may be mixed with a silver halide emulsion as an independent solution or dispersion, or a solution or dispersion containing two or more of these may be mixed with a halogen emulsion. It may be mixed with a silveride emulsion. The layer structure of the color photosensitive material of the present invention may be made by a normal subtractive color method, and in principle, a yellow coupler is used to form a yellow dye in the blue-sensitive photosensitive layer, and a magenta dye is formed in the green-sensitive photosensitive layer. (and the magenta coupler according to the present invention is advantageously used as the magenta coupler), and a cyan coupler for forming a cyan dye in the red-sensitive photosensitive layer. The three layers are the basic layer structure, and any or all of these layers can be made into double or triple layers to improve color development properties,
By using a variety of couplers with different color pigment granularity, the color development characteristics, color reproducibility,
Various photographic properties such as color pigment granularity can be improved. In particular, one or more of the magenta couplers according to the present invention may be used in a single layer or in a multilayer in a green-sensitive photosensitive layer, and a phenidone derivative may be contained in the photosensitive layer and/or its adjacent layer. As a result, it is possible to obtain a multilayer color photosensitive material with excellent color reproducibility and excellent color density, stability, fog, etc. over time. In addition to these basic emulsion layers, layers such as a protective layer on the top layer, an intermediate layer and a filter layer between the layers, and an undercoat layer and an antihalation layer on the bottom layer are appropriately used to protect and prevent color contamination. It is possible to measure the prevention, graininess improvement, white reproduction improvement, film adhesion improvement, etc. The silver halide used in the color light-sensitive material of the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide, etc. Any silver halide used is included. The amount of silver halide used in the present invention is preferably in the range of 0.1 to 0.5 mol/emulsion. Even if these silver halide grains are coarse grains,
It may be fine particles, and the particle 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 [1.0.0] planes to [1.1.1] 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. 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. These silver halide grains can be prepared by known and conventional methods. It is preferable that soluble salts be removed from the silver halide emulsion used in the present invention, but those in which soluble salts have not been removed can also be used. It is also possible to use a mixture of two or more silver halide emulsions prepared separately. The above silver halide emulsion can be sensitized using a known chemical sensitizer. As the chemical sensitizer, noble metal sensitizers, sulfur sensitizers, selenium sensitizers, and reduction sensitizers can be used alone or in combination. Binders used for silver halide include gelatin, colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, and methyl cellulose, or synthetic binders. For example, polyvinyl alcohol, partially saponified polyvinyl acetate, polyacrylamide, poly-N,N-dimethylacrylamide, poly-N-vinylpyrrolidone, water-soluble polymers, phenylcarbamylated gelatin, acylated gelatin, phthalated gelatin, etc. gelatin derivatives, acrylic acid (ester), methacrylic acid (ester),
Examples include those obtained by graft copolymerizing gelatin with a monomer having a polymerizable ethylene group such as acrylonitrile. These binders can be used as a compatible mixture of two or more if desired. Furthermore, the silver halide emulsion used in the present invention may be spectral-enhanced by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or by using them in combination with styryl dye, etc., as necessary. It is possible to perform strong color sensitization. These color sensitization techniques have been known for a long time, and their selection can be arbitrarily determined depending on the wavelength range to be sensitized, the sensitivity, etc. of the color photosensitive material to be obtained, and the purpose and use. be. The above silver halide emulsion contains 1-phenyl-5-
Mercaptotetrazole, 3-methylbenzothiazole, 4-hydroxy-6-methyl-1,3,
Heterocyclic compounds such as 3a,7-tetraazaindene,
Various compounds such as mercapto compounds and metal salts can be added. Further, the hardening treatment of the emulsion is carried out according to a conventional method. A surfactant may be added alone or in combination to the above silver halide emulsion. These surfactants include coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, antistatic agents, adhesive resistance agents, and various active agents for improving photographic properties or controlling physical properties. agent can be used. The color photosensitive material of the present invention contains ultraviolet absorbers such as benzotriazoles,
It may also contain triazines, benzophenone compounds, or acrylonitrile compounds. In particular, Tinuvin PS (manufactured by Ciba Geigy, Tinuvin is a trade name), Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 328, etc. are preferably used alone or in combination. The color photosensitive material of the present invention is produced by coating it on a support that has good flatness and exhibits little dimensional change during the production process or processing. These supports can generally be subbed using various subbing materials to enhance adhesion with the silver halide emulsion layer. In addition to the above-mentioned undercoating process, the support surface is subjected to treatments such as corona discharge, glow discharge, other electronic impact flame treatments, ultraviolet irradiation, oxidation treatment, saponification treatment, and surface roughening to bond the support and emulsion layer. can do. After exposure of the color photosensitive material of the present invention, a dye image can be obtained by a commonly used color development method.
The basic steps in the negative to positive method include color development, bleaching, and fixing steps. The basic steps in the reversal method include development with a first developer, followed by exposure to white light or treatment with a bath containing a fogging agent, color development, bleaching, and fixing steps. Each of these basic steps may be performed independently, but two or more steps may be performed in one using a processing solution that has these functions.
Sometimes this is done in one process. For example, a one-bath color processing method containing a color developing agent, a ferric salt bleaching component, and a thiosulfate fixing component, or a one-bath bleach-fixing method containing an ethylenediaminetetraacetate iron() complex salt bleaching component and a thiosulfate fixing component. etc. There are no particular restrictions on the processing method, and any processing method can be applied. In addition, these treatments may be carried out at high temperatures of 30°C or higher in order to be carried out quickly, and may be carried out at room temperature or below 20°C in special cases. It is generally advantageous to carry out the reaction at a temperature in the range of 20°C to 70°C. The color photosensitive material of the present invention has excellent coloring efficiency and can be made into a thin film, making it suitable for high-temperature and rapid processing. Note that the set temperature for each step in the series of processing may be the same or different. The color developing agent used in processing the color photosensitive material of the present invention is an alkaline aqueous solution containing the developing agent and having a pH of 8 or more, preferably 9 to 12. The aromatic primary amine developing agent used as the developing agent is a compound having a primary amino group on an aromatic ring and capable of developing exposed silver halide, or a precursor for forming such a compound. means body. The above-mentioned developing agent is typically p-phenylenediamine type, and the following are preferred examples. 4-amino-N,N-diethylaniline, 3-
Methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-
Methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethyl-4-amino-N,N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-
N,N-diethylaniline, 4-amino-N,N
-dimethylaniline, N-ethyl-N-β-[β
-(β-methoxyethoxy)ethoxy]ethyl-
3-methyl-4-aminoaniline, N-ethyl-
N-β-(β-methoxyethoxy)ethyl-3-
Methyl-4-aminoaniline and salts thereof such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. Moreover, various additives can be added to these color developing solutions as necessary. After the color light-sensitive material of the present invention is subjected to imagewise exposure and color development processing, bleaching processing can be carried out by a conventional method. This treatment may be done simultaneously with fixing or separately. This processing solution can also be used as a bleach-fixing bath by adding a fixing agent if necessary. Various compounds can be used as bleaching agents, and various additives including bleaching accelerators can also be added. The present invention is realized in various forms of color photosensitive materials. One method is to process a photographic light-sensitive material having a silver halide emulsion layer containing a diffusion-resistant coupler on a support with an alkaline developer containing an aromatic primary amine color developing agent to make it water-insoluble or diffusion-resistant. This is to leave the coloring dye in the emulsion layer. In another form, a photographic light-sensitive material having a silver halide emulsion layer combined with a diffusion-resistant coupler on a support is processed with an alkaline developer containing an aromatic primary amine color developing agent to form an aqueous medium. A soluble and diffusible dye is produced and transferred to an image-receiving layer consisting of another hydrophilic colloid. That is, it is a diffusion transfer color method. The color photosensitive material of the present invention includes all kinds of color photosensitive materials such as color negative film, color positive film, color reversal film, and color paper. The color photosensitive material of the present invention has a West German patent (OLS).
It can be applied to color light-sensitive materials with a small amount of silver halide, such as those described in No. 2357964. For example, a color photosensitive material with a small amount of silver halide, when obtaining the same density, is a fraction to a hundredth of a normal color photosensitive material, for example, about 65 to 375 particles per single layer.
Composed of mg/m ³ silver halide. Such a color photosensitive material with a reduced amount of silver halide that can be used in the present invention is produced by bleaching developed silver produced by color development described in, for example, U.S. Pat. Nos. 2,623,822 and 2,814,565. After that, a good result is obtained by applying a development method that increases the amount of dye produced by performing color development again, such as a method using peroxide, or a development method that utilizes color intensification using, for example, a cobalt complex salt. be able to. EXAMPLES Next, the present invention will be specifically explained using Examples, but the embodiments of the present invention are not limited thereby. Example 1 A coating composition having the following composition was coated on a transparent triacetate film base to form a sample according to Table 1 below.
(1) to (5) were created. (Coating liquid composition) Green-sensitive silver iodobromide emulsion (silver iodide 6 mol%, silver bromide
94 mol%, coated silver amount 20 mg/dm ² ) Magellanta coupler coated amount 5 x 10 ^-5 mol/dm ² Coupler dispersion method: coupler with the same amount of tricresyl phosphate and 3 times the amount of ethyl acetate as the coupler. Dissolved, alkanol B
(Sodium alkylnaphthalene sulfonate)
The mixture was mixed with a 5% aqueous gelatin solution containing the following ingredients, and emulsified and dispersed using a colloid mill. Hardener: 1,2-bis(vinylsulfone)ethane

[Color developer composition]

4-amino-3-methyl-N-ethyl-N-
(β, hydroxyethyl)aniline sulfate
4.75g Anhydrous sodium sulfite 4.25g Hydroxyamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g Potassium hydroxide 1.0g Add water to make 1, and use potassium hydroxide to adjust the pH.
Adjust to 10.0. [Bleach solution composition] Ethylenediaminetetraacetic acid iron animonium salt
100.0g Ethyleneduaminetetraacetic acid diammonium salt
10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make 1, and adjust the pH using ammonia water.
Adjust to 6.0. [Fixer composition] Ammonium thiosulfate (50% aqueous solution) 162ml Anhydrous sodium sulfite 12.4g Add water and adjust to PH6.5 using acetic acid. [Stabilizing liquid composition] Formalin (37% aqueous solution) 5.0ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. The resulting color images were measured, and the color development sensitivity and fog are shown in the table below.

[Table] As is clear from Table 2 above, when Comparative Phenidone-D was used, no anti-fogging effect was observed in high temperature storage and high temperature and high humidity storage with respect to the comparative coupler and the coupler of the present invention. Moreover, when the phenidone derivative according to the present invention is used in combination with the comparative coupler, no antifogging effect is observed under the above-mentioned high temperature and high humidity conditions, but when used in combination with the coupler according to the present invention, an excellent antifogging effect is observed. I understand that it has a preventive effect. Next, coated samples (4) and (4-
1), (4-2), (5), (5-1) and (5-2)
After storing unexposed at 25℃ and 60% RH for 4 months, the coupler was exposed and developed in the same manner as above, and the results were as follows: It is shown in Table 3 below. The fog values in the table indicate actual values after storage over time.
Dmax is the Dmax value obtained without storage over time.
It is expressed as a percentage value.

[Color developer composition]

N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate
4.0g Hydroxyamine 2.0g Potassium carbonate 25.0g Sodium chloride 0.1g Natrium 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 solution composition] Ethylenediaminetetraacetic acid iron sodium salt
60.0g Ammonium thiosulfate 100.0g Sodium bisulfite 10.0g Sodium metabisulfite 3.0g Add water to make 1, and use ammoure water to adjust the pH.
Adjust to 6.6. [Stabilizing liquid composition] Succinic acid 10.0 g Formalin (37% aqueous solution) 15.0 ml Add 800 ml of water, add sodium acetate to adjust the pH to 3.9, and then add water to bring the pH to 1. The photographic properties of the magenta image obtained above are shown in Table 4 below.

【table】

[Table] According to Table 4 above, only when the coupler according to the present invention is used in combination with the phenidone derivative according to the present invention, excellent antifogging effects and color development can be obtained under high temperature storage conditions and high temperature and high humidity storage conditions. I found out. Next, the desilvering properties of samples (5-2) to (8-2) obtained by developing the unprocessed sample as the comparative sample were examined. The values in the table below are the values obtained by measuring the amount of silver in the maximum density area using fluorescent X-rays.

[Table] According to Table 5 above, it was found that comparative coupler C caused desilvering defects, but couplers according to the present invention and comparative coupler A did not cause desilvering defects. Example 3 Coupler according to the invention instead of comparative coupler A
Sample (10) was prepared in the same manner as in Example 1 except that (1) was used.
It was created. On the other hand, the phenidone derivatives (8), (13) and (18) of the present invention were used in combination with the coupler (1) of the present invention and coated in the same manner as described above to obtain samples (11) to (13). These samples were stored at high temperature and high humidity in the same manner as in Example 1, and then exposed and developed. As a result, it was found that when the phenidone derivative according to the present invention was used in combination, there was no increase in fog and an excellent antifogging effect was exhibited. Ta.

Claims (1)

[Scope of Claims] 1. In a silver halide emulsion layer containing at least one 2-equivalent magenta coupler represented by the following general formula () and/or in a hydrophilic colloid layer adjacent to the emulsion layer, the following general compound is present. A silver halide color photographic material containing a non-diffusible 1-phenyl-3-pyrazolidone derivative represented by the formula (). General formula () CP-OR (in the formula, CP is a magenta color image-forming coupler residue, OR is a group that can be separated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent, and here R represents a substituted or unsubstituted aryl group or aralkyl group.) General formula () (In the formula, R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, an alkenyl group, a hydroxy group, an alkoxy group, an alkylthio group, an amino group, an allylamino group, or a sulfonamide group. , R ₂ to _{R 5} each represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and at least one of the above substituents represented by R ₂ to _{R 5} represents a substituent having 8 or more carbon atoms.)