JPS6322573B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material that exhibits high sensitivity and high color density and provides magenta dye images with improved storage stability. Prior art and its problems Usually, in silver halide color photographic light-sensitive materials, exposed silver halide grains are reduced with an aromatic primary amine color developing agent, and an oxidized product of the color developing agent is generated at this time. A dye image can be obtained by coupling the dyes with couplers that form yellow, magenta, and cyan dyes. The coupler that has been practically used to form the magenta dye is the pyrazolone type magenta coupler, but this coupler has low maximum color density and sensitivity, has unfavorable side absorption, and has poor storage stability. In particular, it had the disadvantage of poor formalin resistance, resulting in significant changes in color tone and a marked decline in color development. Many proposals have been made in the past to improve these drawbacks. For example, the
No. 30895 includes 1H that does not have unfavorable side absorptions.
-Pyrazolone[3.2-C]-S-triazole type magenta couplers have been disclosed, but the maximum color density and sensitivity and formalin resistance are hardly improved. Further, Japanese Patent Publication No. 16058/1983 discloses a screw type pyrazolone type magenta coupler. Although this coupler shows some improvement in sensitivity and formalin resistance, the maximum color density is insufficient. Further, JP-A-58-42045 discloses a ballast group containing a hydroxyphenylenesulfonyl group at the end as a ballast group for couplers for the purpose of improving the maximum color density, but this is still insufficient. OBJECTS OF THE INVENTION The first object of the present invention is to provide a photographic magenta coupler that has high maximum color density and high sensitivity, as well as excellent formalin resistance. A second object of the invention is to provide a photographic magenta coupler that does not exhibit undesirable side absorptions. A third object of the present invention is to provide a photographic magenta coupler with excellent dispersion stability. A fourth object of the present invention is to provide a silver halide color photographic light-sensitive material that provides excellent dye images using a photographic magenta coupler having these excellent properties. Structure of the Invention The object of the present invention is to provide a silver halide color photographic material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has the following general formula []. This is achieved by a silver halide color photographic material containing at least one of the magenta couplers shown below. General formula [] [In the formula, R ₁ represents a hydrogen atom or an alkyl group, R ₂ represents a monovalent group, R ₃ represents an alkyl group, an aryl group, or a heterocyclic group, and R ₄
represents a hydrogen atom, an alkyl group, or an aryl group, Z represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of a color developing agent, l represents an integer from 0 to 5, and m represents an integer from 0 to 5. 4
represents an integer. ] Detailed Description of the Invention In the above general formula, R ₁ represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and includes, for example, a methyl group, an ethyl group, an ethoxyethyl group, and a t-butyl group. These alkyl groups may have a substituent. R ₂ is a halogen atom (chloro group, etc.), an alkoxy group (methoxy group, t-butoxy group, etc.), an alkyl group (methyl group, ethyl group, methoxyethyl group, benzyl group, etc.), nitro group, cyano group, etc. Represents a valence group. R ₃ represents an alkyl group, an aryl group or a heterocyclic group, preferably an alkyl group or an aryl group. The alkyl group preferably has 1 to 25 carbon atoms, and represents a straight-chain or branched alkyl group such as a methyl group, isopropyl group, t-butyl group, or dodecyl group. Preferred substituents include a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group,
Examples include an alkylthio group, an arylthio group, a carbonyl group, a sulfamoyl group, an acylamino group, a sulfonyl group, a sulfinyl group, a hydroxy group, and a heterocyclic group. This aryl group and the above R ₃
The aryl group represented by is preferably a phenyl group, and this phenyl group may have a substituent, such as a halogen atom, an alkyl group, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group. , carboxy group, sulfamoyl group, carbamoyl group, acylamino group, dialkylamino group, sulfonyl group, sulfinyl group,
Hydroxy group, etc. R ₄ represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom or an alkyl group. This alkyl group preferably has 1 to 38 carbon atoms, more preferably 1 to 38 carbon atoms.
to 4 alkyl groups, for example, methyl group,
Examples include ethyl group, ethoxyethyl group, and t-butyl group. These alkyl groups may have a substituent. The aryl group represented by R ₄ is preferably a phenyl group, and this phenyl group may have a substituent, for example, p-methoxyphenyl group, m-chlorophenyl group, p-(t)- Butylphenyl group, etc. Groups that can be separated by the coupling reaction of the oxidized color developing agent represented by Z include halogen atoms (e.g., chlorine atom, bromine atom, etc.), aryloxy groups, e.g., phenoxy group, p-methoxyphenoxy group. , p-butanesulfonamidophenoxy group, p-tert, butylcarboamidophenoxy group, etc.), heterocyclic thio group (e.g., 1-
(ethyltetrazole-5-thioyl group), etc., preferably a halogen atom, particularly preferably a chlorine atom. l represents an integer from 0 to 5, particularly preferably an integer from 1 to 3. m represents an integer from 0 to 4, particularly preferably 0, and in this case, in the general formula []

The group is preferably a ballast group sufficient to provide diffusion resistance to the photographic magenta coupler of the general formula. In addition,

[Formula] The group is

It can be bonded to any position of the phenyl group relative to the bonding position of [Formula], but it is preferably bonded to the para position. Typical specific examples of magenta couplers in the present invention will be described below, but the present invention is not limited thereto.

【table】

【table】

【table】

【table】

【table】

[Table] The magenta coupler of the present invention can be easily synthesized by conventionally known methods. A specific synthesis example is shown below. Synthesis Example 1 Synthesis of exemplified coupler (M-1) 6-Methyl-3-[3-(p-
Dissolve 30 g of aminophenyl)-propyl]-IH-pyrazole[3,2-C]-S-triazole,
After adding 42.4 g of p-dodecyloxybenzenesulfonyl chloride little by little at room temperature and stirring for 2 hours, the reaction solution was poured into ice water and extracted with ethyl acetate. After washing twice with saturated brine, the ethyl acetate solution is dried over sodium sulfate, and then ethyl acetate is distilled off under reduced pressure to obtain a solid. This was chromatographed on silica gel using ethyl acetate/hexane (1:1) as a developing solvent, and then recrystallized from acetonitrile to obtain white crystals. Yield: 53.8g. 53.8 g of the obtained crystals were dissolved in 500 ml of methylene chloride, and 12.4 g of N-chlorosuccinimide was added little by little while stirring at room temperature. After stirring for 1 hour,
The reaction solution was washed twice with saturated brine, and the methylene chloride solution was dried over sodium sulfate. The methylene chloride is then distilled off to obtain a solid. The desired exemplary coupler (M-1) was obtained by recrystallization from acetonitrile. Yield 32.1g, mp97~
100℃. The structure was confirmed by NMR and FD-Mass, and the measurement data was obtained using an exemplary coupler (M-Mass).
1) structure was supported. Photographic emulsions made using couplers of this invention may also contain dye-forming couplers other than those of this invention. Further, it is desirable that the coupler has a hydrophobic group called a ballast group in its molecule and is resistant to diffusion, or one that allows the generated dye to not flow out of the photographic emulsion and to be able to move only slightly. Furthermore, it may contain couplers (eg, DIR couplers, eg, blocked couplers, eg, colored couplers) that exhibit various effects upon development. As the yellow dye-forming coupler, a known open-chain ketomethylene coupler can be used. Among these, pivaloylacetanilide couplers or benzoylacetanilide couplers are useful. Specific examples of yellow dye-forming couplers that can be used can be found in U.S. patents.
No. 2875057, UK Patent No. 1077874, US Patent
No. 3408194, Japanese Patent Application Publication No. 1973-123342, Japanese Patent Application Publication No. 1973
-87650, JP 54-133329, JP 46-19031, JP 48-66835, JP 48-94432, JP 50-28834,
JP-A-54-99433, JP-A-55-70841, JP-A-56-74249, JP-A-45-19956, JP-A-51-102636, JP-A-56-
This is described in Publication No. 87041, etc. As the cyan dye-forming coupler, phenol compounds, naphthol compounds, etc. can be used. Specific examples include U.S. Patent No. 2369929;
No. 2474293, No. 2772162, No. 2895826, British Patent No. 1038331, Japanese Patent Publication No. 1974-36894, Japanese Patent Application Publication No. 1977-
Publication No. 21139, U.S. Patent No. 3737316, Japanese Unexamined Patent Publication No. 1973-
Publication No. 74844, U.S. Patent No. 3880661, U.S. Patent No. 4124396,
No. 4333999, JP-A-55-21094, No. 50-
No. 112038, No. 50-117422, No. 52-18315, No. 54-115230, No. 55-163537, No. 57-136650, No. 57-155538,
No. 57-204545, No. 55-32071, No. 55
-108662 publication, 56-1938 publication, 56-
Publication No. 27147, Publication No. 56-80045, Publication No. 56-104333
Publication No. As the magenta dye-forming coupler, the couplers of the present invention may be used alone or in combination of two or more, and furthermore, conventionally known pyrazolone compounds,
Indazolone compounds, cyanoacetyl compounds, birazolinobenzimidazole compounds, pyrazolotriazole compounds, etc. may be used in combination as appropriate. However, at least one is a coupler of the invention. To use the magenta couplers of the present invention, the methods used for conventional magenta dye-forming couplers are similarly applicable. Typically, a magenta coupler is blended into a silver halide emulsion, and this emulsion is coated on a base to form a silver halide color photographic light-sensitive material. This photographic material may be monochromatic or multicolored. In multicolor photographic materials, the magenta coupler of the present invention is usually contained in a green-sensitive emulsion, but it may also be contained in a non-sensitized emulsion or an emulsion sensitive to the three primary color regions of the spectrum other than green. Each structural unit forming a dye image in the present invention consists of a single emulsion layer or multiple emulsion layers that are sensitive to a certain region of the spectrum. The layers necessary for color photographic materials, including the layers of the image-forming units described above, can be arranged in various orders as known in the art. Typically, a cyan dye image-forming unit consists of at least one red-sensitive silver halide emulsion containing at least one cyan dye-forming coupler, at least one green-sensitive silver halide emulsion containing at least one magenta dye-forming coupler. a magenta dye image-forming unit consisting of an emulsion layer, provided that at least one of the magenta dye-forming couplers is a magenta coupler of the present invention, at least one blue-sensitive silver halide emulsion containing at least one yellow dye-forming coupler; A yellow dye image-forming structural unit consisting of layers is supported on a support. Color photographic materials can have additional layers, such as filter layers, interlayers, protective layers, undercoat layers, etc. In order to incorporate the magenta coupler according to the present invention into a silver halide photosensitive material, a conventionally known method may be followed. For example, after dissolving the magenta coupler of the present invention in a mixture of a known high boiling point solvent and a low boiling point solvent such as butyl acetate or butyl propionate,
It may be mixed with an aqueous gelatin solution containing a surfactant, then emulsified using a high-speed rotary mixer, a colloid mill, or an ultrasonic disperser, and then added to the silver halide emulsion. Known high boiling point solvents include phthalate esters (e.g. dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (tricresyl phosphate, trioctyl phosphate), N
-Substituted acid amides (N,N-diethyl laurylamide, etc.) and the like are included. The silver halide color photographic light-sensitive material according to the present invention contains a phenolic compound (hereinafter referred to as the phenolic compound of the present invention) that is non-color-forming and has diffusion resistance.
It is preferable to use them together. In that case, it is preferable to contain it in the same layer as the silver halide emulsion layer containing the magenta coupler according to the present invention. The phenolic compound of the present invention may be non-color-forming and preferably diffusion-resistant; for example, conventionally known phenolic high-boiling organic solvents used for coupler dispersion can be used. In the present invention, the phenolic compound of the present invention includes a phenolic compound that has a melting point of 50°C or less and is solid at room temperature (25°C), or a phenolic compound that is liquid at room temperature and has a boiling point higher than 200°C at normal pressure (1 atm). is included. Furthermore, the phenolic compound of the present invention preferably has a group for imparting diffusion resistance. The phenolic compound of the present invention is preferably a phenolic compound represented by the following general formula []. General formula [] [In the formula, R ₅ and R ₆ are each a halogen atom,
It represents an alkyl group, a cycloalkyl group, or an alkoxy group, K represents an integer from 0 to 4, and when K is 2 or more, two or more R ₆ may be the same group or different groups, and R ₅ and R ₆ may be bonded to each other to form a 5- or 6-membered ring. ] In the general formula [], the halogen atoms represented by R ₅ and R ₆ are preferably chlorine atoms. The alkyl group represented by R ₅ and R ₆ preferably has 1 to 20 carbon atoms, such as methyl group, ethyl group, phenethyl group, 2-(p-hydroxyphenyl)propan-2-yl group, 1- (p
-hydroxyphenyl)butan-1-yl group,
iso-propyl group, butyl group, tert-butyl group,
Represents a substituted or unsubstituted linear or branched alkyl group such as amyl group, sec-amyl group, tert-amyl group, hexyl group, octyl group, tert-octyl group, decyl group, dodecyl group, 8-hexadecenyl group, etc. , R ₅ and R ₆ are, for example, cyclohexyl groups, and
The alkoxy group represented by R ₅ and R ₆ preferably has 1 to 20 carbon atoms, such as methoxy group, ethoxy group, iso-propoxy group, tert-
Examples include butoxy group, phenethyloxy group, ethoxyethyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group and the like. In the general formula [], K represents an integer from 0 to 4, preferably from 0 to 3, and particularly preferably from 0 or 1. In the above general formula [], the alkyl group, cycloalkyl group, or alkoxy group represented by R ₅ and R ₆ is preferably a group that can make the phenol compound of the present invention diffusion resistant, each singly or jointly. The sum of the numbers is preferably from 6 to 30, particularly preferably from 8 to 25. In the general formula [], when R ₅ and R ₆ combine with each other to form a ring, preferably hydroxyindan (e.g. 2,2-dimethyl-4
-tert-octyl-6-indanol), hydroxychroman (e.g. 2,2-dimethyl-4-
tert-butyl-7-octyl-6-chromanol), dihydroxyspirochroman (e.g. spiro[7-tert-butyl-6-hydroxy-4,4
-dimethyl-2,2'-chroman]), hydroxycoumaran (e.g. 2-butyl-6-octyl-5-
coumaranol), hydroxybenzdioxane (e.g. 2,3-dimethyl-6-tert-octyl-7-hydroxybenzoxane), hydroxybenzdioxolane (e.g. 2,2-dimethyl-
Examples include rings such as 4-dodecyl-5-hydroxybenzoxolane). Particularly preferred is a hydroxychroman ring. Typical specific examples of the phenolic compound of the present invention are described below, but the present invention is not limited thereto. The phenolic compound of the present invention can be easily synthesized by conventionally known methods. For example, it can be synthesized by the method described in US Pat. No. 2,835,579. In addition, there are many compounds that are generally commercially available, such as the specific examples listed above.
Examples include (3), (5), (6), and (21). In order to incorporate the magenta coupler of the present invention and the phenolic compound of the present invention into a silver halide light-sensitive material, conventionally known methods may be followed. For example, after dissolving the magenta coupler and phenolic compound of the present invention alone or in combination in a mixture of a known high boiling point solvent and a low boiling point solvent such as butyl acetate or butyl propionate, a gelatin aqueous solution containing a surfactant is prepared. The silver halide emulsion used in the present invention can be prepared by mixing with silver halide, followed by emulsification with a high-speed rotary mixer, colloid mill, or ultrasonic dispersion, and then adding it to silver halide. Known high-boiling point solvents include phthalate esters (e.g. dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (tricresyl phosphate, trioctyl phosphate, etc.), N
-Substituted acid amides (N,N-diethyl laurylamide, etc.) are representative. In addition, some of the phenolic compounds of the present invention can themselves be used as high-boiling point solvents, such as specific examples of compounds (2), (3), (6), (10), (21
)
etc. fall under this category. In this case, there is no need to use other high boiling point solvents such as phthalate esters. Although the phenolic compound of the present invention and the magenta coupler of the present invention may be dispersed separately and each added to the same silver halide emulsion, it is preferable to dissolve and add both at the same time. When the magenta coupler of the present invention is added to a silver halide emulsion, it is usually about 0.01 to 2 mol, preferably 0.03 to 2 mol per mol of silver halide.
It is added in a range of 0.5 mol. In addition, the effect of the present invention will be greater as the amount of the phenol compound of the present invention is added to the magenta coupler of the present invention, but specifically, 0.1 to 10
g, preferably in the range of 0.25 to 3 g. The silver halide used in the silver halide emulsion used in the present invention may include ordinary silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Includes anything used. The silver halide emulsion constituting the silver halide emulsion layer according to the present invention can be produced by a conventional manufacturing method,
Various manufacturing methods, such as those described in Japanese Patent Publication No. 46-7772, can be used to form an emulsion of silver salt grains consisting of at least a portion of a silver salt having a solubility greater than that of silver bromide, and then to process the grains. For all manufacturing methods, such as the manufacturing method of so-called conversion emulsions such as converting at least a part of silver bromide or silver iodobromide, or the manufacturing method of Lippmann emulsions consisting of fine-grained silver halide having an average grain size of 0.1 μm or less. It can be created by Furthermore, the silver halide emulsion of the present invention may contain sulfur sensitizers such as arylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers.
Noble metal sensitizers such as stannous salts, polyamines, etc., such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2
- Sensitizers such as aurosulfobenzthiazole methyl chloride, or water-soluble salts such as ruthenium, rhodium, and iridium, specifically ammonium chloroparadate, potassium chlorobratinate, and sodium chloroparadite, alone or as appropriate Can be used in combination to chemically sensitize. Furthermore, the silver halide emulsion used in the present invention is
Various known photographic additives can be included. For example, “Research Disclosure”
A photographic additive as described in No. 17643, December 1978. The silver halide used in the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the wavelength range necessary for green-sensitive emulsions. Various spectral sensitizing dyes are used, and these may be used alone or in combination of two or more. Spectral sensitizing dyes usefully used in the present invention include, for example, U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in the specifications of No. 2270378, No. 2442710, No. 2454520, and No. 2776280. The support according to the present invention may be appropriately selected from conventionally known supports such as plastic film, plastic laminate paper, baryta paper, synthetic paper, etc. depending on the intended use of the photographic material. These supports are generally subjected to a subbing process to enhance adhesion with the photographic emulsion layer. Specific Applications of the Invention The silver halide color photographic material of the present invention thus constructed can be subjected to various photographic processing methods for color development treatment 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.
Specific examples of this color developing agent include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, and dimethyl-p-phenylenediamine hydrochloride. Nylenediamine 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-β-hydroxyethylamino)aniline, 2
-amino-5-(N-ethyl-β-methoxyethyl)aminotoluene and the like. These color developing agents 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,
Alternatively, it may contain a development regulator such as hydrazine acid. The silver halide color photographic material of the present invention includes:
The above color developing agent is contained in the hydrophilic colloid layer,
It may be contained as the color developing agent itself or as its precursor. The color developing agent precursor is a compound that can generate 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 sulfur amine reactant precursors and urethane type precursors. Precursors for these aromatic primary amine color developing agents are described, for example, in U.S. Pat. No. 3,342,599 and U.S. Pat.
No. 2695234, No. 3719492, British Patent No.
Specification No. 803783, Japanese Unexamined Patent Publication No. 135628, No. 53-135, No. 54-
It is described in each publication No. 79035, Research Disclosure No. 15159, No. 12146, and 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. The amount varies depending on the type of photosensitive material, but 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, water, methanol, ethanol,
It can be added dissolved in a suitable solvent such as acetone, or it can be added as an emulsified dispersion using a high boiling point organic solvent such as dibutyl phthalate, dioctyl phthalate, or tricresyl phosphate. They can also be added by impregnation into latex polymers as described in Rosier No. 14850. The silver halide color photographic light-sensitive material of the present invention is usually subjected to bleaching and fixing, bleach-fixing, and water washing after color development. Many compounds are used as bleaching agents, among them polyvalent metal compounds such as iron, cobalt, and tin, especially complex salts of these polyvalent metal cations and organic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N - aminopolycarboxylic acids such as hydroxyethylenediaminediacetic acid, malonic acid,
Metal complex salts such as tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, ferricyanates, dichromates, etc. are used alone or in appropriate combinations. Specific Examples of the Invention The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 A magenta coupler of the invention and a comparative coupler as shown in Table 1 were each added to 1 mole of silver.
Tricresyl phosphate in an amount of 1 time the weight of the coupler and ethyl acetate in an amount 3 times the weight of the coupler were added to 0.1 mole portions and heated to 60°C to completely dissolve. This solution was added to a solution containing 120 ml of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by Dupont).
% gelatin aqueous solution and emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion. Thereafter, this dispersion was added to 4 kg of green-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide), and a 2% solution of 1,2-bisvinylsulfonyl)ethane (water: methanol = 1) was added as a hardening agent. :1) Add 120 ml and coat it on the undercoated transparent polyester base and dry it to make the sample (1-
1) to (1-16) were created. (Coated silver amount 20mg/
100cm ² ) The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following phenomenon treatment. The results are shown in Table 1. [Processing process] (38℃) Processing time Color development 3 minutes 15 seconds Bleaching 1 minute 30 seconds Washing with water 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds Used in the processing process The composition of the treatment solution was as follows. [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) 2.1g Hydroxide Potassium 1.0g Add water to make 1 and use potassium hydroxide
Adjust to PH10.0. [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make 1, and adjust the pH using aqueous ammonia.
Adjust to 6.0. [Fixer composition] Ammonium thiosulfate (50% aqueous solution) 162ml Anhydrous sodium sulfite 12.4g Add water to make 1, 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.) 7.5ml Add water to make 1.

【table】

[Table] From the results shown in Table 1 above, samples (4), (5), and (6) using the coupler of the present invention are superior to samples (1), (2), and (3) using the comparative coupler. It was found that it has a higher color development sensitivity and a maximum density than that, and also shows improved performance in terms of formalin resistance. Example 2 Magenta couplers of the invention and comparative couplers were prepared and processed as in Example 1. The results are shown in Table 2.

【table】

[Table] From the results shown in Table 2, samples (10), (11), and (12) using the coupler of the present invention are superior to samples (7), (8), and (9) using the comparative coupler. It was found that it had a higher color development sensitivity and the highest sensitivity, and also showed improved performance in terms of formalin resistance. As shown in Examples 1 and 2, the magenta coupler of the present invention is a material that exhibits high sensitivity and high color density, and also exhibits stable color development even when stored, especially in the presence of formalin. Therefore, by a conventionally known method, an open-chain active methylene yellow coupler was added to a blue-sensitive silver halide emulsion, the magenta coupler of the present invention was added to a green-sensitive silver halide emulsion, and a phenol or naphthol-based cyan coupler was added to the blue-sensitive silver halide emulsion. By adding each of these to a red-sensitive silver halide emulsion and further using various additives as appropriate and coating them on a transparent support, we succeeded in obtaining a completely new silver halide color photographic light-sensitive material with stable color balance. Example 3 A magenta coupler of the present invention as shown in Table 3 and a comparative coupler below were each added to 1 mole of silver.
Take 0.1 mol each, add tricresyl phosphate in the same weight as the coupler, an appropriate amount of the phenol compound of the present invention, and ethyl acetate in an amount three times the weight of the coupler, and heat to 60°C to completely dissolve. .
This solution was mixed with a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by Dupont) at 120%
ml of 5% aqueous gelatin solution, and emulsified and dispersed using an ultrasonic dispersion liquid to obtain an emulsion.
Thereafter, this dispersion was added to 4 kg of green-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide) and used as a hardening agent.
2% of 1,2-bis(vinylsulfonyl)ethane
Add 120ml of solution (water:methanol=1:1),
Samples 13 to 27 were prepared by coating and drying on a subbed transparent polyester base. (Coated silver amount 20mg/
100cm ² ) The samples thus obtained were subjected to wedge exposure according to a conventional method and then developed.Table 3 shows the results. The processing steps, color developing solution composition, bleaching solution composition, fixing solution composition, and stabilizing solution composition were the same as in Example 1.

[Table] Comparative couplers 4, 5 and 6 are the same as those described in Example 2. As is clear from Table 3, although Comparative Coupler 4 has improved maximum color density and formalin resistance, it is still not sufficient in terms of sensitivity, and even the addition of phenolic compounds has little effect. Comparative coupler 5 shows improvement in formalin resistance, but sensitivity and maximum color density are still insufficient. Comparative coupler 6 has improved sensitivity and maximum color density, but has poor formalin resistance and needs improvement. In comparison, it can be seen that the sample combining the magenta coupler of the present invention and a phenolic compound has excellent characteristics in all cases. Example 4 0.1 mol of each of the magenta couplers of the present invention shown in Table 4 was taken per 1 mol of silver, and the same weight of 2,4-di-tert-aminophenol as the coupler was added (Specific Example (6)). Then, ethyl acetate in an amount three times the weight of the coupler was added and heated to 60°C to completely dissolve the coupler. This solution was mixed with a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by Dupont).
Mix with 1200ml of 5% gelatin aqueous solution containing 120ml,
The mixture was emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion. Thereafter, this dispersion was added to 4 kg of green-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide), and a 2% solution of 1,2-bis(vinylsulfonyl)ethane (water:methanol= 120 ml of 1:1) was added, coated and dried on a subbed transparent polyester base, and the coated silver amount was adjusted to 10 mg/100 cm ² . For comparison, Samples 13, 15, and 17 used in Example 3 were used, respectively. The sample thus obtained was subjected to wedge exposure according to a conventional method, and then developed in the same manner as in Example 3. The results are shown in Table 4.

[Table] Shows Milphenol.
As shown in Table 4, the system using the coupler of the present invention and the phenolic compound of the present invention has sensitivity and maximum color density equivalent to or higher than that of the comparative coupler, despite having half the amount of silver. It shows. This suggests that the combination of the coupler of the present invention and the phenolic compound of the present invention has a high utilization efficiency for silver halide, and it is possible to reduce the amount of silver, thin the film based on it, and apply it to other layers. It is understood that this material can fully satisfy the objectives of the present invention, such as improved sharpness. As shown in Examples 3 and 4, the combined use of the magenta coupler of the present invention and the phenolic compound of the present invention provides high sensitivity and
The open-chain active methylene yellow coupler was blue-sensitive halogenated using a conventionally known method because it shows high color density and stable color development even when stored, especially in the presence of formalin. The magenta coupler and phenolic compound of the present invention are added to a green-sensitive silver halide emulsion, and the phenol or naphthol-based cyan coupler is added to a red-sensitive silver halide emulsion to a silver emulsion, and various additives are used as appropriate to transfer them onto a transparent support. Through coating, we succeeded in obtaining a completely new silver halide color photographic material with stable color balance.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers contains a magenta compound represented by the following general formula []. A silver halide color photographic material containing at least one coupler. General formula [] [In the formula, R ₁ represents a hydrogen atom or an alkyl group, R ₂ represents a monovalent group, R ₃ represents an alkyl group,
represents an aryl group or a heterocyclic group, R ₄ represents a hydrogen atom, an alkyl group, or an aryl group, Z represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of a color developing agent, l is 0 represents an integer from 0 to 5, m is from 0 to 4
represents an integer. ]