JPH068955B2 - Silver halide photographic light-sensitive material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material containing a novel magezane dye-forming coupler, and more specifically, it has high color-developing sensitivity and high maximum density, and has excellent storage stability. The present invention relates to a silver halide photographic light-sensitive material containing an excellent novel magenta dye-forming coupler.

Background Art and Problems Thereof As is well known, color-reducing color photographs show that an aromatic primary amine color developing agent is an oxidation product of a color developing agent produced by reducing exposed silver halide grains. Color images are formed by oxidative coupling of couplers that form yellow, cyan, and magenta dyes in silver halide emulsions. In these cases, as a yellow coupler for forming a yellow dye, a compound having an open-chain active methylene group is generally used, and as a magenta coupler for forming a magenta dye, a pyrazolone type, a pyrazolinobenzimidazole type, Indazolone compounds are used, and as cyan couplers for forming cyan dyes, compounds having phenol and naphthol hydroxyl groups are used.

Each coupler is a substantially water-insoluble high boiling organic solvent,
Alternatively, if necessary, an auxiliary solvent may be used in combination and dissolved, and then added to the silver halide emulsion, or dissolved in an alkaline aqueous solution and added to the silver halide emulsion. The former is an oil droplet dispersion method and the latter is an alkali dispersion method, but it is generally said that the former is superior to the latter in light resistance, heat resistance, moisture resistance, color sharpness and the like.

The basic properties required for each coupler are not only to form a dye but also to have a large solubility in a high-boiling organic solvent or an alkaline aqueous solution, and dispersibility and stability in a silver halide photographic emulsion. Is good,
The dye formed thereby has firmness against light, heat, humidity, etc., and has good spectral absorption characteristics,
It is desired to have various characteristics such as good transparency, high color density, and clear images.

However, as far as the present inventors know, no magenta coupler known hitherto has been found to satisfy all the above-mentioned required properties.

Various pyrazolone derivatives are known as magenta couplers, but these couplers have low coloring efficiency, and in the so-called four equivalent coupler in which the coupling active site is unsubstituted, the proportion of the coupler used for dye formation is about half. However, there is a defect that the rest is not useful for pigment formation and the coloring efficiency is low.

A so-called two-equivalent magenta coupler in which a substituent (leaving group) capable of split-off at the time of color development is introduced into the active position of a pyrazolone derivative is known as a method for improving the color development efficiency. As these two-equivalent magenta couplers, for example, a coupler having an acyloxy group as a leaving group in U.S. Pat.No. 3,311,476, a coupler having an aryloxy group in U.S. Pat.No. 3,419,391, a coupler having a thiocyano group is U.S. Pat.No. 3,214,437. No. and the same
No. 3,253,924, couplers having a 2-triazolyl group are described in U.S. Pat. No. 3,617,291, and couplers having an acylthio group or a thioacylthio group are described in U.S. Pat. No. 4,032,346. However, when these two-equivalent magenta couplers are used, it causes remarkable color fog, has a low coupling activity, and the coupler is chemically unstable and changes into a substance that cannot be colored over time. However, there are some inconveniences such as the fact that there are many difficulties in synthesis.

Also, from before, U.S. Pat.Nos. 3,227,554 and 3,701,783
As disclosed in the publication, compounds in which the 4-position which is the active position of a pyrazolone derivative is substituted with an arylthio group or a heterocyclic thio group are also known. However, many of these known thio-substituted pyrazolone compounds are so-called development inhibitor releasing couplers (DIR couplers),
The mercaptan formed as a result of the coupling reaction had a function of interacting with silver halide and delaying development.

For the purpose of preventing the strong photographic action of mercaptan, a thio-substituted pyrazolone coupler having a mercaptan compound having a diffusion resistant group as a leaving group is described in JP-B-53-34044, but these couplers have a coupling activity. This is not sufficient and there is a problem in the storage stability of the magenta dye that is formed, and there is a difficulty in application to general color photographic light-sensitive materials.

Further, JP-A-55-62454 describes a magenta coupler in which the 4-position of a pyrazolone derivative is substituted with R'-S- (R 'represents a straight chain or branched chain alkyl or aralkyl). In these couplers, the metalcaptan compound which is released after coupling has a drawback that the coupling activity of the coupler is still low even though it does not substantially have a development-inhibiting action, and image storability, especially light resistance is poor. Was.

Further, JP-A-57-35858 discloses 3-anilino-5-
Although pyrazolone mazetan couplers have been described, these couplers also suffered from poor coupling activity.

II Object of the Invention The present invention has been made in view of the above circumstances, and a first object thereof is to have a sufficient reaction activity, a high yield without generating unnecessary fog and stain. It is to provide a novel two-equivalent magenta coupler which forms a dye.

A second object of the present invention is to provide a silver halide photographic light-sensitive material in which a novel two-equivalent magenta coupler is used to reduce the amount of silver halide and the amount of coupler used in a photographic emulsion layer containing the same. It is in.

A third object of the present invention is to provide a silver halide photographic light-sensitive material having a fast dye image which is excellent in light resistance, heat resistance and humidity resistance by using a novel two-equivalent magenta coupler.

A fourth object of the present invention is to provide a silver halide photographic light-sensitive material in which the active site-substituting component of the coupler is eliminated during color development and reacts with silver halide to cause no adverse effect.

A sixth object of the present invention is to provide a silver halide photographic light-sensitive material excellent in storage stability that does not develop abnormal color due to development processing even if left in a place where formalin exists before development.

III Specific Structure of the Invention As a result of various studies, the present inventors have found that on the support,
The inventors have found that the above objects can be achieved by using a silver halide photographic light-sensitive material having at least one photographic constituent layer containing a magenta coupler represented by the following general formula, and have completed the present invention.

General formula In the formula, Ar represents an aryl group, R ₁ represents an acylamino group or a ureido group, R ₂ and R ₃ each represent an alkyl group or an aryl group, and R ₄ represents a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group. Represents an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an alkyloxycarbonyl group, an alkylthio group, an acyl group, a nitro group, an amino group or a carboxy group, and m represents an integer of 0 to 4.

Examples of the aryl group represented by Ar in the general formula include a phenyl group and a naphthyl group. Preferred is a phenyl group. The aryl group may have a substituent, and examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydroxyl group, a nitro group, a cyano group, a hydroxycarbonyl group, a trifluoromethyl group, Linear or branched alkyl group (eg, methyl group, ethyl group, isopropyl group, dodecyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group (eg, phenyloxy group, etc.), carbamoyl group , An alkylcarbamoyl group (eg, methylcarbamoyl group), a dialkylcarbamoyl group (eg, dimethylcarbamoyl group), an arylcarbamoyl group (eg, phenylcarbamoyl group), an alkylsulfonamide group (eg, methanesulfonamide group) , Arylsulfonamide group ( For example, phenylsulfonamide group etc.), alkylsulfonyl group (eg methylsulfonyl group etc.), arylsulfonyl group (eg phenylsulfonyl group etc.), sulfamoyl group, alkylsulfamoyl group (eg methylsulfamoyl group etc.) ), Dialkylsulfamoyl group (eg, dimethylsulfamoyl group), arylsulfamoyl group (eg, phenylsulfamoyl group), alkylcarbonylamino group (eg, acetylamino group), arylcarbonylamino Groups (eg,
Benzoylamino group etc.), alkylthio group (eg methylthio group etc.), arylthio group (eg phenylthio group etc.), alkyloxycarbonyl group (eg methyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group) Groups, etc.) and the like. These substituents can have two or more,
In this case, these substituents may be the same or different. Preferably, the aryl group represented by Ar has two or more substituents.

As the substituent that the aryl group represented by Ar has, a halogen atom, an alkyl group, a trifluoromethyl group and a dialkylsulfamoyl group are preferable, and a halogen atom is particularly preferable. In the case where an aryl group, for example, a phenyl group has a substituent, when the number of the substituent is one, it has the substituent at the 2-position or 4-position with respect to the nitrogen atom of the pyrazolone ring to which the phenyl group is bonded. Is preferred. When the aryl group represented by Ar, for example, a phenyl group, has two substituents, the positional relationship between these two substituents may be para, ortho, or meta with respect to each other. The substituent is preferably bonded to the 2-position with respect to the nitrogen atom of the pyrazolone ring.

R _{1 in the} general formula is an acylamino group (for example, an alkylcarbonamide group, a phenylcarbonamide group, an alkoxycarbonamide group, an aryloxycarbonamide group, etc.), or a ureido group (for example, an alkylureido group, a phenylureido group, etc.). ) Is represented. It can have these substituents. As the substituent, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), a linear or branched alkyl group (eg, methyl group, t-butyl group, octyl group, tetradecyl group, etc.),
Alkoxy group (eg, methoxy group, ethoxy group, 2-
Ethylhexyloxy group, tetradecyloxy group, etc.),
Acylamino group (eg, acetamide group, benzamide group, butanamide group, octanamide group, tetradecanamide group, α- (2,4-di-t-amylphenoxy) acetamide group, α- (2,4-di-t- Amylphenoxy) butyramide group, α- (3-pentadecylphenoxy) hexanamide group, α- (4-hydroxy-)
3-t-butylphenoxy) tetradecanamide group, 2
-Oxo-pyrrolidin-1-yl group, 2-oxo-5-
Tetradecylpyrrolidin-1-yl group, N-methyl-tetradecanamide group, etc.), sulfonamide group (eg,
Methanesulfonamide group, benzenesulfonamide group,
Ethylsulfonamide group, p-toluenesulfonamide group, octanesulfonamide group, p-dodecylbenzenesulfonamide group, N-methyl-tetradecanesulfonamide group, etc., sulfamoyl group (for example, sulfamoyl group, N-methylsulfamoyl group) Group, N-ethylsulfamoyl group, N, N-dimethylsulfamoyl group,
N, N-dihexylsulfamoyl group, N-hexadecylsulfamoyl group, N- [3- (dodecyloxy)-
Propyl] sulfamoyl group, N- [4- (2,4-di-t-amylphenoxy) butyl] sulfamoyl group,
N-methyl-N-tetradecylsulfamoyl group, etc.),
A carbamoyl group (for example, an N-methylcarbamoyl group,
N-butylcarbamoyl group, N-octadecylcarbamoyl group, N- [4- (2,4-di-t-amylphenoxy) butyl] carbamoyl group, N-methyl-N-tetradecylcarbamoyl group, etc.), diacylamino group [N-succinimide group, N-phthalimide group, 2,5-dioxo-1-oxazolidinyl group, 3-dodecyl-2,5-
Dioxo-1-hydantoinyl group, 3- (N-acetyl-N-dodecylamino) succinimide group, etc.], alkoxycarbonyl group (eg, methoxycarbonyl group, tetradecyloxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxysulfonyl group (For example, methoxysulfonyl group, butoxysulfonyl group, octyloxysulfonyl group, tetradecyloxysulfonyl group, etc.), aryloxysulfonyl group (for example, phenoxysulfonyl group, p-methylphenoxysulfonyl group,
2,4-di-t-amylphenoxysulfonyl group etc.),
Alkylsulfonyl group (for example, methanesulfonyl group,
Ethanesulfonyl group, octanesulfonyl group, 2-ethylhexylsulfonyl group, hexadecanesulfonyl group, etc.), arylsulfonyl group (eg, benzenylsulfonyl group, 4-nonylbenzenylsulfonyl group, etc.), alkylthio group [eg, methylthio group, ethylthio group Group, hexylthio group, benzylthio group, tetradecylthio group, 2
-(2,4-di-t-amylphenoxy) ethylthio group, etc.], arylthio group (for example, phenylthio group, p-
Tolylthio group etc.), alkyloxycarbonylamino group (eg methoxycarbonylamino group, ethyloxycarbonylamino group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group etc.), alkylureido group (eg N-methylureido group) , N,
N-dimethylureido group, N-methyl-N-dodecylureido group, N-hexadecylureido group, N, N-dioctadecylureido group, etc., acyl group (for example, acetyl group, benzoyl group, octadecanoyl group, P-dodecanamide benzoyl group, etc.), nitro group, carboxy group,
Examples thereof include a sulfo group, a hydroxy group and a trichloromethyl group.

The alkyl group represented by R ₂ and R ₃ in the above general formula is a linear or branched alkyl group, and preferably,
A linear or branched alkyl group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, amyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc.) is there. These alkyl groups can have a substituent, and as the substituent, a hydroxyl group, a hydroxycarbonyl group, a cyano group, an aryl group (for example, a phenyl group, a tolyl group, etc.),
Alkyloxycarbonyl group (eg, ethoxycarbonyl group, hexadecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, tolyloxycarbonyl group, naphthyloxycarbonyl group, etc.), alkylsulfonamide group (eg, methanesulfone group) Amide group), acylamino group (eg acetamide group, benzamide group etc.), alkoxy group (eg methoxy group, benzyloxy group etc.), aryloxy group (eg phenoxy group etc.), sulfonyl group (eg methanesulfonyl group) Groups, etc.) and the like.

Examples of the aryl group represented by R ₂ and R ₃ in the above general formula include a phenyl group and a naphthyl group, and a phenyl group is preferable. The aryl group may have a substituent, and examples of the substituent include, for example,
Halogen atom (for example, chlorine atom, bromine atom, etc.), hydroxyl group, nitro group, cyano group, hydroxycarbonyl group, alkyl group (straight or branched alkyl group, for example, methyl group, ethyl group, propyl group , Butyl group, amyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, octyloxy group, decyloxy group). Group, dodecyloxy group, etc.), alkylcarbonylamino group (eg, undecylcarbonylamino group, dodecylcarbonylamino group, etc.), arylcarbonylamino group (eg, naphthoylamino group, toluoylamino group, benzoylamino group, etc.) , An alkylsulfonamide group (for example, dode Lesulfonamide group, etc.), arylsulfonamide group (eg, benzensulfonamide group), alkylaminosulfonamide group (eg, dimethylaminosulfonamide group), arylaminosulfonamide group (eg, anilinosulfonamide) Group), an alkylcarbamoyl group (eg, hexadecylcarbamoyl group), an arylcarbamoyl group (eg, phenylcarbamoyl group), a sulfonyl group (eg, methylsulfonyl group, n-dodecylsulfonyl group, etc.), an alkyloxycarbonyl group (For example, dodecyloxycarbonyl group and the like), aryloxycarbonyl group (for example, phenoxycarbonyl group and the like), alkylsulfamoyl group (for example, N-methylsulfamoyl group,
N, N-dimethylsulfamoyl group, etc.), arylsulfamoyl group (eg, phenylsulfamoyl group, etc.)
Etc. Among the alkyl groups or aryl groups represented by R ₂ and R ₃ , preferred are alkyl groups, particularly alkyl groups having 1 to 8 carbon atoms.

R _{4 in the} above general formula is a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), a linear or branched alkyl group (preferably an alkyl group having 1 to 22 carbon atoms, for example, a methyl group. , Ethyl group, t-butyl group,
Tetradecyl group etc.), alkoxy group (eg methoxy group, ethoxy group, tetradecyloxy group etc.), hydroxyl group, acylamino group (eg acetamide group, benzamide group, tetradecanamide group etc.), sulfonamide group (eg methane Sulfonamide group, benzensulfonamide group, etc.), carbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (eg, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.) Famoyl group), alkanesulfonyl group (eg, methanesulfonyl group, hexadecanesulfonyl group, etc.), alkyloxycarbonyl group (eg, methoxycarbonyl group, tetradecyloxycarbonyl group, etc.),
Alkylthio group (eg, methylthio group, tetradecylthio group, etc.), acyl group (eg, acetyl group, benzoyl group, octadecanoyl group, etc.), nitro group, amino group (eg, N, N-dipropylamino group) Represents a carboxy group. These groups may have a substituent,
Examples of the substituent include the same substituents as described for the alkyl group of R ₂ and R ₃ .

Further, m in the general formula is an integer of 0 to 4, but preferably an integer of 1 to 2. When m is 1, the substituent represented by R ₄ is -N in the above general formula. , Which can be in any position of the phenyl group, but is preferably in the para position. When m is 2, the above R ₄
May be the same or different and are preferably the same, and in this case, the substituent represented by R ₄ is --N of the phenyl group. Can be in any position with respect to, and is preferably the 2nd and 4th positions.

Specific examples of typical compounds of the magenta coupler of the present invention represented by the above general formula are shown below, but the present invention is not limited thereto.

Exemplified compound (1) (2) (4) (5) (6) (7) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (22) (23) (24) (25) (26) (27) (28) (29) (30) (31) (32) (33) (34) (36) (37) The coupler of the present invention represented by the above general formula can be synthesized by a conventionally known method. In particular, there are the following synthetic methods for introducing a thio group as a leaving group into the 4-position of pyrazolone. That is, in accordance with the method for synthesizing a DIR magenta coupler having an arylthio group or a heterocyclic thio group as a leaving group described in U.S. Pat.Nos. 3,227,554 and 3,701,783, a 4-equivalent pyrazolone having a sulphenyl chloride and an active methylene group. A method of reacting a coupler, as described in JP-A-49-62464, a method in which the 4-position of a pyrazolone coupler is dibrominated and then reacted with about 3 times mol of mercaptan, Research Disclosure 13
806 (1975), bromine is added dropwise in the presence of a 4-equivalent pyrazolone coupler and a mercaptan.

Typical synthetic examples of the magenta coupler of the present invention are shown below, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Exemplified Coupler (2) 1- (2,4,6-trichlorophenyl) -3- [3- (4
-Dodecyloxybenzenesulfonamide) benzamide] -5-pyrazolone 36.1 g and 2- (N, N-di-n-butylamino) -5-n-butylphenyl mercaptan 1
4.7 g was dissolved in 200 m of dimethylformamide, and 2.5 m of bromine was added dropwise thereto. After the dropping, the mixture was reacted at room temperature for 2 hours. The reaction solution was poured into ice water 1 to precipitate a solid. This solid was filtered, washed with water and dried. This was recrystallized from 150 m of toluene to obtain 39.5 g of the desired product.
Yield 78%, melting point 158-159 ° C, FD mass spectrum M / e
= 1011 (M ⁺ ).

Synthesis Example 2 Synthesis of Exemplified Coupler (25) 1- (2,3-Dichlorophenyl) -3- (2-methylpropanamide) 5-pyrazolone 31.4 g and 2- (N, N-di-n-hexylamino)- 5-chlorophenylcaptan
32.8 g was dissolved in 200 m of dimethylformamide, and 4.9 m of bromine was added dropwise thereto. After the dropping, the mixture was reacted at room temperature for 2 hours. The reaction solution was poured into ice water 1 to precipitate a solid. This solid was filtered, washed with water and dried. This was recrystallized from an ethanol-water mixed solvent to obtain 40.3 g of the desired product. Yield 63%, melting point 103-105 ° C, FD mass spectrum
It was M / e = 638 (M ⁺ ).

As described above, the coupler of the present invention can be easily manufactured by applying a conventionally known method.

In order to produce a silver halide photographic light-sensitive material, the couplers of the present invention may be used alone or in combination of two or more. The coupler of the present invention can be used in either an internal type or an external type, and particularly when used in a photographic constituent layer, good results can be obtained. In the present invention,
"Photographic layer" means a silver halide emulsion layer and an intermediate layer,
A non-photosensitive hydrophilic colloid layer such as an undercoat layer or a protective layer.
The coupler of the present invention is preferably contained in a silver halide emulsion layer among these photographic constituent layers.

When the coupler of the present invention is incorporated into the silver halide emulsion layer of the internal photographic light-sensitive material, a solution or dispersion of these couplers is used as a mixture with the silver halide emulsion. The timing of addition is arbitrary, but it is usually preferable to add it to the emulsion after the second ripening.

When at least one of the couplers of the present invention is contained in the silver halide emulsion layer, the content is usually 1
The amount is 0.007 to 0.7 mol, preferably 0.01 to 0.1 mol per mol. Further, the coupler of the present invention can be incorporated in a non-photosensitive layer adjacent to the silver halide emulsion layer, in which case 0.001 to 10 mmol, preferably 1 to 10 mmol per 1 m ^{2 of} gelatin, preferably
It is contained in the range of 0.1 to 0.01 mmol.

As a method for adding the coupler of the present invention to the photographic constituent layer, a conventionally known method can be adopted. That is, the couplers of the present invention can be used as dibutyl phthalate, dioctyl phthalate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, N, N-diethylcaprylamide, N, N-diethyllaurylamide, N, N-dibutyllaurylamide, etc. Water-immiscible organic solvent, ethyl acetate, butyl acetate or other low-boiling organic solvent or methanol, ethanol, acetone, dioxane, tetrahydrofuran or other aqueous organic solvent, or high-boiling water immiscible It is preferably added to a photographic emulsion by dissolving it in an organic solvent and / or a low boiling and / or water-soluble organic solvent.

It is advantageous to use surfactants to help finely disperse the solutions or dispersions of the couplers of this invention in the hydrophilic colloids used in photographic emulsions. The coupler is dissolved in a suitable organic solvent, mixed with an aqueous gelatin solution containing a surfactant, and then emulsion-dispersed with a high-speed rotary mixer or a colloid mill, and then directly added into the silver halide emulsion, or the above-mentioned emulsion is used. After the dispersion is set, it is finely chopped, the low boiling point organic solvent is removed by a means such as washing with water, and then this is added to the silver halide emulsion. Further, the magenta coupler of the present invention can be added by the Fisher dispersion method.

As the surfactant that can be used in the present invention,
Anionic systems such as, for example, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, sulfosuccinates, and sulfoalkyl polyoxyethylene alkyl phenyl ethers. Surfactants, nonionic surfactants such as steroidal saponins, alkylene oxide derivatives and glycidol derivatives, amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids and alkyl betaines, and quaternary ammonium salts Cationic surfactants such as Specific examples of these surfactants are "Surfactant Handbook" (industrial books, 1
966) and "Emulsifiers / Emulsifiers, Research / Technical Data" (Kagakugenron, 1978).

The silver halide photographic light-sensitive material using the magenta coupler according to the present invention, if necessary, other conventionally known magenta couplers, specifically, pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, Indazolone couplers may be used in combination. As such a magenta coupler, U.S. Pat.No. 2,600,788,
2,983,608, 3,062,653, 3,127,269, 3,3
11,476, 3,419,391, 3,519,429, 3,558,31
No. 9, No. 3,582,322, No. 3,615,506, No. 3,834,908,
3,891,445, West German patent 1,810,464, West German patent application (OLS) 2,408,665, 2,417,945, 2,418,959
No. 2,424,467, JP-B-40-6031, JP-A-51-20826
No. 52-58922, 49-129538, 49-74027, 5
0-159336, 52-42121, 49-74028, 50-60233
No. 51-26541, No. 53-55122, and Japanese Patent Application No. 55-110943.

Among such magenta couplers, as the colored magenta coupler, an arylazo-substituted or heteroarylazo-substituted compound is used at the active site of the colorless magenta coupler, and, for example, U.S. Patent No. 2,983,608.
No. 2,455,170, 2,725,292, 3,005,712,
No. 3,519,429, No. 2,688,539, British Patent No. 800,262
No. 1,044,778, Belgian Patent No. 676,691 and the like.

The silver halide photographic light-sensitive material applicable to the present invention may contain other dye-forming couplers such as yellow couplers and cyan couplers together with the magenta couplers of the present invention to form a multicolor image. Examples of the yellow coupler which can be used together with the magenta coupler of the present invention include benzoylacetanilide type and pivaloylacetanilide type yellow couplers, and further, the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction. Equivalent yellow couplers can be mentioned.

Specific examples of yellow couplers that can be used in the present invention are described in US Pat.
5,057, 3,265,506, 3,408,194, 3,551,155
No., No. 3,582,322, No. 3,725,072, No. 3,891,445,
West German Patent 1,547,868, West German Published Application 2,219,917, 2,
261,361, 2,414,006, British Patent 1,425,020, Japanese Patent Publication No. 51-10783, JP-A-47-26133, 48-73147,
51-102636, 50-6341, 50-123342, 50-1304
42, 51-21827, 50-87650, 52-82424, 52-82424
It is described in Nos. 52-115219 and 58-95346.

Examples of cyan couplers include phenol or naphthol derivatives, and examples of colored cyan couplers include compounds in which an arylazo-substituted phenoxy group is substituted at the coupling position of a colorless cyan coupler through an alkoxy group. You can

Such cyan couplers include, for example, US Pat.
No. 2,423,730, No. 2,474,293, No. 2,801,171, No. 2,895,826, No. 3,476,563, No. 3,737,326,
No. 3,758,308, No. 3,893,044, JP-A-47-3
7425, JP-A-50-10135, JP-A-50-25228, JP-A-SHO
50-112038, JP-A-50-117422 and JP-A-50-13044
It includes those described in Publication No. 1 and the like. As a colored cyan coupler as a masking coupler, for example, U.S. Pat.Nos. 2,521,908 and 3,034,892
No. 1,255,111, JP-A No. 48-22028, and the like.

Further, U.S. Pat.No. 3,476,563, JP-A-50-10135, 50-
Colored cyan couplers of the type in which the dye flows out into the processing bath upon reaction with the oxidation product of a color developing agent as described in 123341 can also be used.

The above-mentioned yellow and cyan couplers other than the magenta coupler of the present invention are generally used in an amount of 0.000 per mol of silver halide in the emulsion layer.
7 mol to 0.7 mol, preferably 0.01 mol to 0.1 mol is used.

Further, for the purpose of improving the sharpness, graininess, etc. of the color image, so-called repeating couplers, development inhibitor releasing type couplers (so-called DIR couplers), or development where no dye is formed by reaction with an oxidized product of a developing agent. It is also possible to use inhibitor-releasing substances. These may be used alone or in combination of two or more.

The magenta coupler of the present invention can also be used in the dye image forming method described in JP-B-49-26585, US Pat. No. 3,486,890, Research Disclosure 12044, and 12840. That is, the magenta coupler of the present invention and an aromatic primary amine developing agent are both contained in a light-sensitive material, and after the actual exposure, color development is carried out by treatment with an alkali bath, a black and white developer, or heat treatment. However, it is possible to obtain a dye image with uniform gradation.

The silver halide photographic light-sensitive material applied to the present invention basically comprises a support and a light-sensitive emulsion layer, but depending on the type of silver halide photographic light-sensitive material, an undercoat layer, an intermediate layer,
In general, auxiliary layers such as a filter layer, an antihalation layer, an anti-curl layer, a pack layer and a protective layer are appropriately combined and laminated. Further, the photosensitive layer itself is layered with a layer containing a relatively high sensitivity silver halide spectrally sensitized in the same wavelength range or a different wavelength range and a layer containing a relatively low sensitivity silver halide. It may be configured.

The emulsion layer containing the coupler of the present invention, other emulsion layers or other auxiliary layers may contain a reducing agent or an antioxidant such as sulfite (sodium sulfite, potassium sulfite, etc.), bisulfite (sodium bisulfite, potassium bisulfite). Etc.), hydroxylamines (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-aminophenol, gallic acid, catechol, pyrogallol, resorcin, 2,3-dihydroxynaphthalene, etc.) are used. It is preferable to fully exert the effect of.

Further, for the purpose of increasing the stability of the formed dye image,
Alkyl-substituted hydroquinones and their alkoxy derivatives, bishydroquinones, polymer hydroquinones and the like can be incorporated alone or in combination in an emulsion layer containing the coupler of the present invention or in an adjacent layer. Furthermore, p-alkoxyphenols, 6-chromanol, 6,
6'-Dihydroxy-2,2'-spirochroman and their alkoxy or acyloxy derivatives are likewise used.

The silver halide photographic light-sensitive material according to the present invention comprises a benzotriazole compound, a triazine compound, a benzophenone compound or an acrylonitrile compound as an ultraviolet absorber in its constituent layers (eg, protective layer, intermediate layer, emulsion layer, back layer, etc.). It may contain a compound.

To form the light-sensitive material, the silver halide is dispersed in a suitable protective colloid to form the photographic constituent layer of the light-sensitive silver halide emulsion layer, which is the light-sensitive material of the light-sensitive silver halide emulsion layer. In addition, it may have a non-photosensitive layer, for example, a photographic constituent layer such as an intermediate layer, a protective layer, a filter layer and the like. As the protective colloid forming these photographic constituent layers, alkali-processed gelatin is generally used, and other acid-processed gelatin, derivative gelatin, colloidal albumin, cellulose derivative or polyvinyl alcohol, synthetic resin such as polyvinylpyrrolidone, etc. are used. These may be used alone or in combination of two or more.

The silver halide photographic light-sensitive material according to the present invention is produced by applying it on a support which has good flatness and whose dimensional change is small during the production process or processing. In this case, as the support, a hard material such as a plastic film, a plastic laminated paper, a baryta paper, a synthetic paper, a glass plate, a metal, or a pottery can be used.

These supports can be subjected to surface treatments such as various hydrophilic treatments for the purpose of improving the adhesiveness with the photographic emulsion layer. For example, saponification treatment, corona discharge treatment, undercoating treatment and setting treatment. Processing such as processing is performed.

The silver halide emulsion used in the silver halide photographic light-sensitive material according to the present invention usually comprises a water-soluble silver salt (eg silver nitrate) solution and a water-soluble halogen salt (eg potassium bromide) solution,
It is prepared by mixing in the presence of an aqueous polymer solution such as gelatin. The silver halide may be any of the halogenated silver halides such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodobromide which are used in ordinary silver halide photographic light-sensitive materials. Silver can be used.

These silver halide emulsions can be prepared by known methods (e.g., single or double jet method, control double jet method, etc.). Further, two or more kinds of silver halide photographic emulsions formed separately may be mixed.
Further, even if the crystal structure of the silver halide grains is uniform to the inside, it also has a layered structure in which the inside and the outside are different, a so-called conversion emulsion, Lippmann emulsion, covered grain emulsion or previously optical or It may be chemically fogged. The latent image may be mainly formed on the surface or the internal latent image type may be formed inside the particles. These photographic emulsions can be prepared by various methods such as generally accepted ammonia method, neutral method and acidic method. Further, the type of silver halide, the content and mixing ratio of silver halide, the average grain size, the size distribution, etc. are appropriately selected according to the type and application of the photographic light-sensitive material.

The above silver halide emulsion can be sensitized with a chemical sensitizer. Chemical sensitizers are precious metal sensitizers (potassium aurithiocyanate, ammonium chloroparadate,
Potassium chloroplatinate etc.), sulfur sensitizers (allylthiocarbamide, thiourea, cystine etc.), selenium sensitizers (active and inactive selenium compounds etc.) and reduction sensitizers (stannous salts, polyamines etc.) It is roughly divided into four types. The silver halide emulsion can be chemically sensitized with these sensitizers alone or in combination.

Further, the photographic emulsion according to the present invention, if necessary, cyanine,
Spectral sensitization and supersensitization can be performed by using cyanine dyes such as merocyanine and carbocyanine alone or in combination, or by using them in combination with a styryl dye.

These color sensitization techniques have been known for a long time, and the selection of the combination of the dyes should be arbitrarily determined according to the wavelength range to be sensitized, the sensitivity, the purpose of the silver halide photographic light-sensitive material and the application. Is possible.

The above silver halide emulsion contains 1-phenyl-5-mercaptotetrazole, 3-methylbenzothiazole, for the purpose of preventing the occurrence of fog during the production process, storage or processing of the silver halide photographic light-sensitive material. Various compounds such as a heterocyclic compound such as 4-hydroxy-6-methyl-1,3,3a, 7-tetradeindene, a mercapto compound, and metal salts can be added.

Hardening treatment of the emulsion is carried out according to a conventional method. The hardener used is a conventional photographic hardener, for example, aldehyde compounds such as formaldehyde, glyoxal and glutaraldehyde and their derivative compounds such as acetal or sodium bisulfite adduct, and further methanesulfonic acid ester compounds. , Mucochromic acid, mucohalogen acid compounds, epoxy compounds, aziridine compounds,
Active halogen compounds, maleic acid imide compounds, active vinyl compounds, carboximide compounds, isoxazole compounds, N-methylol compounds, isocyanate compounds, or inorganic hardeners such as chromium alum and zirconium sulfate. I can give you.

A surfactant may be added to the above silver halide emulsion alone or as a mixture. They are coating aids, emulsion dispersions,
It is applied for sensitization, improvement of photographic characteristics, antistatic, and adhesion prevention. These surfactants include natural surfactants such as saponin, alkylene oxide-based, glycerin-based,
Nonionic surfactants such as glycidol-based, higher alkylamines, quaternary ammonium salts, pyridine, other heterocycles, cation surfactants such as phosphonium or sulfonium, carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid It is divided into anionic surfactants containing an acidic group such as an ester group and a phosphoric acid ester group, and amphoteric surfactants such as amino acids, aminosulfonic acids, sulfuric acid or phosphoric acid esters of aminoalcohols.

The formation of the color photographic image of the present invention is realized in various forms of light-sensitive materials. One is to treat a 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 prepare a water-insoluble or diffusion-resistant material. It is a method of leaving a sex dye in the emulsion layer. In another form, a light-sensitive material having a silver halide emulsion layer in combination with a diffusion-resistant coupler on a support is treated with an alkaline developer containing an aromatic primary amine color developing agent to form an aqueous medium. It is made soluble to form a diffusible dye, and transferred to an image receiving layer composed of another hydrophilic colloid. That is, it is a diffusion transfer color system.

The silver halide photographic light-sensitive material of the present invention includes all kinds of silver halide photographic light-sensitive materials such as a color negative film, a color positive film, a color reversal film and a color paper.

As one embodiment of the silver halide photographic light-sensitive material according to the present invention, a green-sensitive silver halide emulsion layer containing the mazetan coupler of the present invention, a blue-sensitive silver halide emulsion layer containing a yellow coupler, and a cyan coupler are contained. There is a multilayer multicolor silver halide photographic light-sensitive material having a red-sensitive silver halide emulsion layer on a support. Known blue-sensitive silver halide emulsions, green-sensitive silver halide emulsions and red-sensitive silver halide emulsions can be appropriately used in such light-sensitive materials.

The silver halide photographic light-sensitive material according to the present invention can obtain a color image after exposure by a commonly used color development method. The basic steps of the negative-positive method include color development, bleaching and fixing steps. The basic steps in the reversal method include the steps of color development, bleaching and fixing by developing with a first developing solution and then exposing to white or treating with a bath containing a fog agent.

Each of these basic steps may be carried out independently, or two or more steps may be carried out once with a processing solution having these functions. 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 containing an ethylenediaminetetraacetic acid iron (III) complex salt bleaching component and a thiosulfate fixing component. There are ways.

Further, each step can be processed in two or more times as required, or a combination of color development, first fixing and bleach-fixing can be performed. In addition to the above, various steps such as a pre-hardening bath, a neutralizing bath, an image stabilizing bath, and a water washing are combined with the developing process. Processing temperature is 18 ℃
It may be less than 18 ° C, but is often 18 ° C or higher. The range of 20 ° C to 60 ° C is particularly often used. About 30 ° C to 60 ° C is suitable for rapid processing. The set temperatures of the series of processing steps do not have to be the same.

The color developer contains a developing agent and has a pH of 8 or more, preferably 9
~ 12 alkaline aqueous solution. The developing agent means a compound having a primary amino group on the aromatic ring and capable of developing exposed silver halide, or a precursor forming such a compound. P-phenylenediamine type is preferable, and for example, 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-methyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-methoxyethylaniline, 3-β
-Methanesulfonamidoethyl-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-diethylaniline, 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, sulfite, hydrochloride and p-toluenesulfonate.

If necessary, various additives are added to the color developing solution. Typical examples are alkaline agents (eg, alkali metal or ammonium hydroxides, carbonates, phosphates, etc.), pH adjusting or buffering agents (eg, weak acids or weak bases such as acetic acid, boric acid, etc.).
These salts, etc., development accelerators (eg pyridinium compounds, cationic compounds, potassium nitrate and sodium nitrate, polyethylene glycol condensates and their derivatives, nonionic compounds such as polythioethers, sulfite esters) Polymer compounds, other pyridines, ethanolamines, organic amines, benzyl alcohol, hydrazines, etc., antifoggants (eg alkali bromide, alkali iodide and nitrobenzimidazoles, mercaptobenzimidazoles, 5-
Methylbenzotriazole, 1-phenyl-5-mercaptotetrazole, compounds for rapid processing liquids, thiosulfonyl compounds, phenazine N oxides, benzothiazolium nitrobenzoate derivatives, etc.), stain or sludge inhibitor, acceleration of heavy metal effect Agents, preservatives (eg sulfite,
Acid sulfite, hydroxylamine hydrochloride, form sulfite, alkanolamine sulfite adduct, etc.) and the like.

The silver halide photographic light-sensitive material containing the coupler of the present invention is
For example, color development processing can be performed without impairing the practicality even in the presence of a competitive coupler such as citrazinic acid.

The silver halide photographic light-sensitive material according to the present invention can be bleached by a conventional method after color development processing. This process may be simultaneous with fixing or may be separate. This processing solution can be used as a bleach-fixing bath by adding a fixing agent as required.

Various compounds are used as the bleaching agent, and among them, red blood salts; dichromate; iron (III), cobalt (II
I), copper (II) and other polyvalent metal compounds, especially complex salts of these polyvalent metal cations and organic acids, for example aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diaminopropanoltetraacetic acid, citric acid ,
Metal complex salts such as tartaric acid and malic acid and peracids such as alkyl peracids, persulfates, permanganates and hydrogen peroxides, hypochlorites such as chlorine, bromine and coconut powder, etc., alone or in a suitable form. Combinations are common. Further, various additives such as a bleaching accelerator can be added to this processing liquid.

After the color development processing, ordinary photographic processing, for example, a stop solution containing an organic acid, a stop fixing solution containing a fixing component such as organic acid and hypo or ammonium thiosulfate, a fixing solution containing a fixing component such as hypo or ammonium thiosulfate, A bleaching solution containing a ferric salt of aminopolycarboxylic acid and an alkali halide as main components, a bleach-fixing solution containing a ferric salt of aminopolycarboxylic acid and a fixing component such as hypo or ammonium thiosulfate, and other stabilizing solutions. Each treatment selected from treatments such as the above and treatments such as washing and drying may be appropriately combined.

The coupler according to the present invention is also used for a low silver amount light-sensitive material in which the amount of silver halide in the emulsion is a fraction to one-hundredth of that of a normal silver halide light-sensitive material. be able to.

In the case of a color light-sensitive material in which the amount of silver halide is reduced as described above, a development processing method in which developed silver produced by color development is subjected to halogenation bleaching, and then color development is performed again to increase the amount of dye formed, peroxide, cobalt complex salt Alternatively, a sufficient dye image can be obtained by applying a development processing method utilizing color intensification using sodium chlorite.

The silver halide photographic light-sensitive material of the present invention may contain the above-mentioned color developing agent as the color developing agent itself or as a precursor thereof in the hydrophilic colloid layer. Color developing agent precursor is a compound capable of forming a color developing agent under alkaline conditions, 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 sugar amine reactant precursors and urethane type precursors. The precursors for these aromatic primary amine color developing agents are described, for example, in US Pat. No. 3,342,599.
No. 2,507,114, 2,695,234, 3,719,49
No. 2, British Patent No. 803,783, JP-A-53-135628
No. 54-79035, Research Disclosure 15159, No. 12146, and No. 13924.

It is necessary to add these aromatic primary amine color developing agents or their precursors in such an amount that sufficient color can be obtained during development processing. This amount largely depends on the type of the light-sensitive material, but it is generally photosensitive silver halide 1
It is used in a range of from 0.1 to 5 mol, preferably 0.5 to 3 mol, per mol. 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 or the like, and it can be added in a high solvent such as dibutyl phthalate, dioctyl phthalate or tricresyl phosphate. It can also be added as an emulsified dispersion using a boiling organic solvent. Research Disclosure
It can also be added by impregnating a latex polymer as described in 14850.

IV Specific Examples of the Invention Next, the present invention will be specifically described with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 2 × 10 ⁻² mol of the exemplified coupler (15) was heated and melted in a mixed solution of 15 m of dibutyl phthalate and 30 m of ethyl acetate, and this solution containing 5 g of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) was added in an amount of 5%. It was mixed with 300 m of an aqueous gelatin solution and emulsified and dispersed in a colloid mill. A dispersion of this coupler is used as a green-sensitive silver odorant (silver iodide 6
Mol%, silver bromide 94 mol%) 0.2 mol and gelatin 40 g
Was mixed with 1 Kg of a photographic emulsion containing 20 mg of a 2% solution of 1,2-bis (vinylsulfonyl) ethane as a hardener, coated on a cellulose triacetate film base and dried. A gelatin protective layer was coated on this layer to prepare a sample (1) of a silver halide photographic light-sensitive material. Sample at this time
The coating amount of silver of (1) was 2 g / m ² , and in the same manner as described above, the exemplified couplers (19), (25), and (36) were used in place of the exemplified coupler (15). Samples (2), (3) and (6)
It was created.

Further, as comparative samples, instead of the exemplified coupler (1), comparative couplers (A) and (B) described later were used, and comparative samples (4) and (5) were prepared in exactly the same manner as above.

Each of these samples (1), (2), (3), (4), (5) and (6) was wedge-exposed by a conventional method, and then developed with the next processing step and the processing solution composition shown below. Treated with liquid.

[Processing step (38 ° C)] Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds [Color developer composition] 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to adjust to 1 and the pH is adjusted to 10.0 with potassium hydroxide.

[Bleaching liquid composition]

Ethylenediaminetetraacetic acid ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 m Add water to make 1 and adjust the pH to 6.0 using ammonia water.

[Fixer composition]

 Ammonium thiosulfate (5% aqueous solution) 162.0 g Anhydrous sodium sulfite 12.4 g Water is added to make 1 and the pH is adjusted to 6.5 with acetic acid.

[Stabilizing liquid composition]

 Formalin (37% aqueous solution) 5.0m Conidax (Konishi Rokusha Kogyo KK) 7.5m Add water to make 1.

The magenta dye image obtained as described above was measured with a densitometer (PD-
7R Konishi Rokusha Kogyo Co., Ltd.) was used to measure green light, and color development sensitivity (displayed as a relative value when the sensitivity of Sample (4) was 100), fog and maximum density were calculated. Is shown in Table 1 below.

From the results shown in Table 1 above, the samples (1), (2), (3), and (6) using the coupler of the present invention were compared with the samples (4) and (5) using the comparative coupler. It has a high color development sensitivity and maximum density, and shows improved color development performance with no increase in fog.

Comparative coupler (A) (compound described in US Pat. No. 3,227,554) Comparative coupler (B) (compound described in JP-A-55-62454) Example 2 The samples (1) to (6) obtained in Example 1 were tested for light resistance, heat resistance and humidity resistance. The light resistance was determined by attaching an ultraviolet absorption filter to each of the obtained images and measuring the residual concentration after 100 hours of exposure with a xenon fade meter and the concentration before exposure to 1
Represented as 00. The humidity resistance is 50 ° C and the relative humidity is 8
The residual concentration after storage for 2 hours under the condition of 0% was expressed as 100 before the test. Furthermore, the heat resistance is 2 at 77 ° C.
The residual concentration after storage for a week was expressed as 100 before the test. The results are shown in Table 2.

From the results shown in Table 2, it can be seen that the couplers of the present invention are excellent in light resistance, moisture resistance and heat resistance as compared with the comparative couplers, and are excellent couplers that hardly cause a decrease in image density during storage. .

Example 3 After coating the samples (1) to (6) prepared in Example 1, under a non-exposed dark room, in a sealed container containing a 1% formaldehyde aqueous solution, without touching the solution, Left for days. These samples and untreated samples for comparison were exposed and developed in the same manner as in Example 1 to measure the sensitivity and the maximum density, and the% formalin resistance (treated sample / untreated sample × 1)
00) was calculated. The results obtained are shown in Table 3.

From the results shown in the above table, samples (1) ~ (3) and (6) using the coupler according to the present invention, the sample using the comparative coupler
Compared with (4) and (5), it can be seen that the coupler has a property of being excellent in raw sample storability, which is less likely to be adversely affected by formalin, such as a decrease in sensitivity and a decrease in maximum concentration.

Continuation of the front page (56) References JP-A-60-162256 (JP, A) JP-A-55-62454 (JP, A) US Patent 3227554 (US, A)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one photographic constituent layer containing a magenta coupler represented by the following general formula on a support. General formula [In the formula, Ar represents an aryl group, R ₁ represents an acylamino group or an ureido group, R ₂ and R ₃ represent an alkyl group or an aryl group, respectively, and R ₄ represents a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group. Group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, alkyloxycarbonyl group, alkylthio group, acyl group, nitro group, amino group or carboxy group, and m represents an integer of 0 to 4 . ]