JPH068952B2 - Color image forming method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a color image forming method of a silver halide color photographic light-sensitive material, and more specifically, to a halogenation having improved color density and gradation (γ). The present invention relates to a color image forming method for silver color photographic light-sensitive materials. More specifically, a silver halide color photographic light-sensitive material is treated with an aromatic primary in the presence of a 1H-pyrazolo [1,5-b] -1,2,4-triazole magenta coupler having a substituted or unsubstituted aryl group at the 2-position. The present invention relates to a color image forming method in which development processing is performed with a developing solution containing an amine.

(Prior Art) Conventionally, most of the 5-pyrazolones have been widely put into practical use as magenta color image forming couplers and studied. However, the dye formed by the coupling of the 5-pyrazolone type coupler and the oxidation product of the aromatic primary amine developing agent has a secondary absorption having a yellow component near 430 nm, which causes the color to be turbid. Things were known.

Pyrazolobenzimidazole nucleus described in British Patent No. 1,047,612 as a magenta color image-forming nucleus that reduces this yellow component, British Patent No. 3,770,447.
Indazolone bone nucleus described in U.S. Pat.
No. 25,067, pyrazolo [5,1-c]-
1,2,4-triazole bone nuclei have been proposed.

However, the magenta couplers described in these patents, when dispersed in a hydrophilic protective colloid such as gelatin, when mixed with a silver halide emulsion,
It was still unsatisfactory because it gave only unsatisfactory color images, its solubility in high boiling organic solvents was low, it was synthetically difficult, and the light fastness of the dye was extremely low.

In order to solve these drawbacks, JP-A-59-171,
956 and 1 H-pyrazolo [1,5-b] -1,2,4 as shown in US Pat. No. 4,540,654.
The triazole skeleton magenta coupler has been developed and solved the above problems. That is, it does not have the inversion absorption of the yellow component as seen in the 5-pyrazone type coupler,
It has sufficient solubility in high boiling point organic solvents, easy to synthesize,
Further, the 1H-pyrazolo [1,5-b] -1,2,4-triazole bone nucleus magenta coupler has the characteristics such as high light fastness of a color image.

(Problems to be Solved by the Invention) By the way, the coupler reacts with the oxidized product of the developing agent in the photographic film within a certain period of time, and the coupler has a sufficient reaction rate to give a good color image, in other words, , Sufficient color density, and gradation (γ) must be exhibited. These change depending on the type of the high boiling point organic solvent, but the degree thereof is small, and it is desired that the coupler has a high coupling reaction rate as an inherent property. In the case of the conventional 1H-pyrazolo [1,5-b] -1,2,4-triazole magenta coupler, the coupling reaction rate has a coupling leaving group such as a halogen atom, an alkylthio or arylthio group, which is easy to synthesize. In the case of the coupler, it was somewhat unsatisfactory.

Therefore, a first object of the present invention is to provide a method for forming a color image having sufficiently high color density and gradation (γ).

A second object of the present invention is to provide a silver halide color photographic light-sensitive material containing a coupler which gives a sufficiently high color density and gradation.

A third object of the present invention is to provide a magenta coupler which gives a sufficiently high color density and gradation.

(Means for Solving the Problems) The above object is to develop a silver halide light-sensitive material with a developing solution containing an aromatic primary amine in the presence of at least one coupler represented by the following general formula (I). And a color surface image forming method.

General formula (I) In the formula, R ₁ represents a substituted or unsubstituted alkyl group or aryloxy group, and R ₂ represents a substituted aryl group. X represents a halogen atom. However, R ₂ is 4-t
-Butylphenyl group, 2,4-di-t-amylphenyl group, 4-tetradecanamidephenyl group, hexadecyloxyphenyl group, 4 '-[α- (4 "-1-butylphenoxy) tetradecanamidephenyl group, Or And R ₁ is not the following general formula (II).

(Wherein, _{R A} represents an alkylene group, _{R B} represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.) In formula _{(II) -R A -SO 2 -R} B R 1 is preferably alkyl It is a base. The aryl group for R ₂ includes a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenylyl group, and the like.
These have one or more substituents. Of these, a substituted phenyl group, a substituted naphthyl group, and a substituted biphenyl group are preferable, and a substituted phenyl group is more preferable. R ₁ and R ₂ may be a divalent group to form a bis form.

More specifically, R ₁ is an alkyl group (a linear or branched alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group,
Alkynyl group, cycloalkyl group, cycloalkenyl group, which are oxygen atom, nitrogen atom, sulfur atom, substituent group linked by carbonyl group, hydroxy group, amino group, nitro group, carboxy group, cyano group, or halogen atom May be substituted with, for example, thimel group, propyl group, t-butyl group, trifluoromethyl group, tridecyl group, 2-methanesulfonylethyl group, 3- (3-pentadecylphenoxy) propyl group, 3- {4- {2-
[4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl group, 2-ethoxytridecyl group, trifluoromethyl group, cyclopentyl group, 3- (2,4-di-t-amylphenoxy) propyl Group, etc.) and an aryloxy group (eg, phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.).

The substituent which R ₂ has is the group shown for R ₁ above, an aryl group (for example, a phenyl group, a 4-t-butylphenyl group, a 2,4-di-t-amylphenyl group, 4
-Tetradecanamidophenyl group, etc.), heterocyclic group (e.g., 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, acyl group, (e.g., totyl group, 3- Phenylpropanoyl group, benzoyl group, 4-dodecyloxybenzoyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group) , Octadecylcarbonyl group, etc.), carbamoyl group (eg, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N-
(2-dodecyloxyethyl) carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N- {3- (2,
4-tert-amylphenoxy) propyl} carbamoyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecylethoxy group, 2-methanesulfonyltoxy group, etc.), heterocyclic oxy Group (for example, 1-phenyl, tetrazole-5-oxy group, 2-tetrahydropyranyloxy group, etc.), acyloxy group (for example, acetoxy group, etc.), carbamoyloxy group (for example, acetylaminooxy group, benzoylaminooxy group) Groups, etc.), silyloxy groups (eg,
Trimethylsilyloxy group, dibutylmethylsilyloxy group, etc.), aryloxycarbonylamino group (eg, phenoxycarbonylamino group, etc.), acylamino group (eg, acetamide group, benzamide group, tetradecanamide group, α- (2,4 -Di-t-amylphenoxy) butyramide group, γ- (3-t-butyl-4-
Hydroxyphenoxy) butyramide group, α- {4-
(4-hydroxyphenylsulfonyl) phenoxy} decanamide group, etc., anilino group (for example, phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecaneamidoanilino group, 2-chloro-5-dodecyloxycarbonylani). Rino group, N-acetylanilino group,
2-chloro-5- {α- (3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino group, etc.),
Ureido group (for example, phenylureido group, methylureido group, N, N-dibutylureido group, etc.), sulfamoylamino group (for example, N, N-dipropylsphamoylamino group, N-methyl-N-decyl group) Sulfamoylamino group, etc.), alkoxycarbonylamino group (eg, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), sulfonamide group (eg, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide) Group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5-t-butylbenzenesulfonamide group, etc.), aryloxycarbonylamino group (for example, phenoxycarbonylamino group, naphthoxycarbonylamino group, p-meth Phenoxycarbonyl Bruno amino group, etc.), an imido group (e.g., N- succinimido group,
N-phthalimide group, 3-octadecenylsulfinimide group, etc.), nitro group, alkylthio group (for example, methylthio group, octylthio group, tetradecylthio group, 2-
Phenoxyethylthio group, 3-phenoxypropylthio group, 3- (4-t-butylphenoxy) propylthio group, etc.), arylthio group (for example, phenylthio group,
2-Putoxy-5-t-octylphenylthio group, 3-
Pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, heterocyclic thio group (for example, 2-benzothiazolylthio group,
2,4-di-phenoxy-1,3,5-triazole-
6-thio group, 2-pyridylthio group, etc.), sulfamoyl group (eg, N-ethylsulfamoyl group, N, N-
Dipropylsulfamoyl group, N- (2-dodecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N, N-diethylsulfamoyl group, etc., sulfonyl group (for example, methanesulfonyl) Group, octansulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (eg, dodecanesulfinyl group, 3-pentadecylphenylsulfinyl group), and halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.) .

X represents a halogen atom (eg, chlorine atom, bromine atom, iodine atom, etc.).

More specifically, the divalent group in which R ₁ and R ₂ are a divalent group to form a bis form is described in more detail. An alkyl group or an aryloxy group of R ₁ is a substituted or unsubstituted alkylene group (for example, a methylene group). , Ethylene group, 1,10-decylene group,
-CH ₂ CH ₂ -O-CH ₂ CH _2- , etc.), a substituted or unsubstituted phenylene group (for example, 1,4-phenylene group, 1,3-phenylene group, -NHCO-R ₃ -CONH- group (R ₃ represents a substituted or unsubstituted alkylene group or phenylene group, for example, -NHCOCH ₂ CH
₂ CONH-, (R ₃ represents a substituted or unsubstituted alkylene group, for example, —S—CH ₂ CH ₂ —S—, Of the above divalent linking group, and R ₂ represents the above aryl group bound by the above divalent linking group.

The divalent linking group contained in the ethylene-like monomer represented by the general formula (I), which is contained in the alkyl group or aryloxy group of R ₁ , is an alkylene group (a substituted or unsubstituted alkylene group , For example, a methylene group, an ethylene group,
1,10-decylene group, —CH ₂ CH ₂ OCH ₂ CH ₂ —, etc., phenylene group (substituted or unsubstituted phenylene group, for example, 1,4-phenylene group, 1,3-phenylene group, -NHCO-, -CONH-, -O-, -OCO- and aralkylene groups (for example, Etc.) and groups that are established by combining those selected from R
₂ represents a divalent group bonded to the linking group represented by R ₁ via an aryl group.

The following are preferred linking groups.

-NHCO-, -CH ₂ CH ₂ , -CONH-CH ₂ CH ₂ NHCO-, -CH ₂ CH ₂ O-CH ₂ CH ₂ -NHCO-, The vinyl group may have a substituent other than those represented by the general formula (I), and a preferable substituent is a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group). Represents

Monomers including those represented by general formulas (I) and (II) may form copolymers with non-color forming ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developers. .

Acrylic acid, α is used as the non-color-forming ethylene-like monomer that does not couple with the oxidation product of the aromatic primary amine developing agent.
-Chloroacrylic acid, α-alkylacrylic acid (such as methacrylic acid) and esters or amides derived from these acrylic acids (such as acrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide, Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate,
Ethyl methacrylate, n-butyl methacrylate and β-hydroxymethacrylate), methylenedibisacrylamide, vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg Styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether), maleic acid, maleic anhydride, maleic acid ester , N-vinyl-2-pyrrolidone, N-vinyl pyridine, and 2- and 4-vinyl pyridine. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can be used together. For example, n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the art of polymer color couplers, the non-chromogenic, ethylenically unsaturated monomers for copolymerization with the solid water-insoluble monomer coupler are the physical and / or chemical properties of the copolymer formed, such as Solubility, compatibility with photographic colloid composition binders such as gelatin, its flexibility,
It can be chosen such that the thermal stability etc. is positively affected. The polymer coupler used in the present invention may be water-soluble or water-insoluble, and among them, the primer coupler latex is particularly preferable.

Next, specific examples of typical couplers in the invention will be shown, but the couplers are not limited thereto.

Next, a general method for synthesizing the coupler of the present invention will be shown. Basically, it is synthesized by the method shown in JP-A-60-197688, but the synthesis of amido oxime (III) is better than that of orthoesters. (R ₁ , R ₂ and X represent the same groups as described above, R ₃ represents an alkyl group or an aryl group, and Y represents an acid radical.) It is easier to use imidad (II).

R ₃ and Y will be described in detail. When R ₃ is an alkyl group, it is a primary or secondary alkyl group having 1 to 10 carbon atoms, and when it is an aryl group, it is a phenyl group, a tolyl group, or p.
Represents a methoxyphenyl group, a β-naphthyl group and the like.
Y represents a halide ion, a sulfate ion, a nitrate ion, or the like.

The method for synthesizing the polymer coupler will be described for solution polymerization and emulsion polymerization. First, for solution polymerization, it can be synthesized by the method described in US Pat. No. 3,451,820 and JP-A-58-28745. And a non-color-forming ethylenic monomer (for example, acrylic acid such as acrylic acid, α-chloroacrylic acid, methacrylic acid, or an ester derived from acrylic acid or An amide (eg, acrylamide, n-butylacrylamide, n-butylmethacrylate, methylmethacrylate, ethylmethacrylate, etc.) in a suitable ratio is dissolved in a soluble organic solvent (eg, dioxane, methylcellosolve, etc.) or Mix and start polymerization at an appropriate temperature (about 30 to 100 °). Radiation, high energy radiation, etc., or as a chemical action, initiated by the generation of free radicals by an initiator such as persulfate, hydrogen peroxide, benzoyl peroxide, azobis alkylonitrile). After completion of the polymerization reaction, the polymer can be isolated by extrusion into an organic solvent, concentration, or pouring into water. Regarding the emulsion polymerization method, US Pat.
It can be synthesized by the method described in No. 0,952.

A general method for introducing a halogen atom into a coupling-off group will be described.

The 4-equivalent mother nucleus coupler can be synthesized by halogenating the 7-position with a suitable halogenating agent such as sulfuryl chloride, chlorine gas, bromine, N-chlorosuccinimide, N-bromosuccinimide and the like.

<Synthesis Example 1> (Synthesis of Exemplified Coupler (8)) (Synthesis Scheme) 153 g (1.03 mol) of m-nitrobenzonitrile,
To 36.2 g (1.13 mol) of methanol, ether 6 was added.
00 m and chloroform 250 m are added, and the mixture is stirred at room temperature. The m-nitrobentonitrile is in a dispersed state. 75 g (20.5 mol) of hydrogen chloride gas was passed through this. The temperature at this time is maintained at 25 to 28 ° C. After introducing hydrogen chloride gas,
Stir for about 8 hours. The crystal form changes. Then, after leaving it at room temperature for about one night, the crystals are attached and washed with ether. The obtained crystals are dried in a desiccator under reduced pressure to obtain 183 g (82.0%) of imide ester hydrochloride (A).

28.0 g (0.3 mol) of aminomethylpyrazole are dissolved in 300 m of acetonitrile. To this solution is added 65 g (0.3 mol) of the imidate obtained above. After reacting for about 12 hours at room temperature, the precipitated amidine crystals are collected.

Hydroxylamine hydrochloride 23.0 g (0.33 mol)
Is dissolved in 200 m of methanol by heating. 3 after completely dissolved
After cooling to 0 ° C., SM-2866.5 m (0.33 mol) is added to neutralize. After removing the precipitated salt,
The amidine obtained by the above method is added to the liquid with stirring. After performing the reaction at room temperature for about 4 hours, pour the reaction solution into the water of 2,
The precipitated amidoxime (B) is taken, washed with water and dried.

Yield 55.3 g (75.8%) mp.200-203 ° C. 50 g (0.19) of the amidoxime (B) obtained by the above method.
(Mol) is stirred and dispersed in 250 m of acetonitrile.
38.3 g of p-toluenesulfonyl chloride
(0.20 mol) is added and stirred for about 30 minutes at room temperature. During this time, the crystals gradually dissolve. Then pyridine 1
5.8 g (0.2 mol) is slowly added dropwise. After completion of the dropping, the reaction is carried out at room temperature for about 2.5 hours, and then the reaction solution is poured into 1.5 of water with stirring, and the tosyl body which precipitates is taken out and washed with water.

Pyridine (15.8 g, 0.2 mol) was added to the obtained tosyl derivative.
And 800 m of methanol are added and the mixture is heated with stirring. The reaction is performed for about 2.5 hours. Crystals of a ring-closed body are deposited on the way. After completion of the reaction, the reaction solution was ice-cooled to sufficiently precipitate crystals, and the crystals were taken, washed with methanol and dried to obtain 27.3 g (59.1%) of (C). mp 250
℃ or more 40g reduced iron, 2g ammonium chloride and 20m water
, 200 ml of isopropyl alcohol and 3 m of acetic acid are added, and the mixture is heated and stirred. After heating and stirring for about 30 minutes, 19.5 g (0.08 mol) of the nitro compound (C) obtained by the above method
Is added in several portions. After the addition is completed, the reaction is completed by heating and stirring for about 3 hours. After the reaction is complete, add 3
After cooling to 0 ° C, 9.6 g of NaOH (0.24 mol), 20 of water
m solution is added and stirred for about 20 minutes to dissolve the precipitated amine compound. After the amine body is dissolved, it is passed under reduced pressure using Celite to remove inorganic substances (Fe etc).
Pour over into water 1.5 and acetic acid 20m (0.35mol)
When the mixture is made acidic, crystals of the amine compound (D) are precipitated. The precipitated crystals are collected, washed with water and dried.

Yield of (D) 14.5 g (8.5%) mp. 250 ° C or higher 2.13 g (0.01 mol) of amine compound (D) with 10 m of DMA _c
And stir at room temperature. To this, 7.0 g (0.01 mol) of TOS-C was added and stirred for about 20 minutes. Then, 0.8 g (0.01 mol) of pyridine is added dropwise. The reaction is completed at room temperature for about 2 hours. After completion of the reaction, 100 m of ethyl acetate is removed, and then the solution is concentrated to dryness. To the residue are added 150 m of n-Hexsne and 50 m of ethyl acetate to crystallize crystals. The precipitated crystals are collected and then recrystallized from n-hexane / ethyl acetate (5/1) to give 4-equivalent coupler (E) as pure crystals.

Yield 4.5 g (51.3%) 25 g of ethyl acetate was added to 4.5 g (0.0051 mol) of the obtained 4-equivalent coupler (E), and the mixture was stirred at room temperature. N- in this
0.7 g (0.0052 mol) of chlorosuccinimide (NCS) is added in several portions. After stirring for about 1 hour after the addition is complete,
Wash the ethyl acetate layer with water. After drying the ethyl acetate solution with Glauber's salt,
Concentrate the ethyl acetate to dryness. The residue is recrystallized twice with n-hexane / ethyl acetate (5/1).

Yield 3.1 g (66.7%) mp 208 to 210 ° C. <Synthesis Example 2> The melting points of the main couplers synthesized in the same manner as in the method shown in Synthesis Example 1 are shown below.

The present invention will be described below with reference to examples, but the present invention is not limited thereto.

(Example 1) (Color paper) On a paper support laminated on both sides with polyethylene, a multi-layer color photographic paper having the layer constitution shown in (Table 1) was prepared. The coating liquid was prepared as follows.

Preparation of coating solution for the first layer: 10 g of yellow coupler (a), 2.1 g of color image stabilizer (b), 10 m of ethyl acetate and solvent (c)
4.0 m was added and dissolved, and this solution was emulsified and dispersed in 90 m of a 10% aqueous gelatin solution containing 10 m of 1% sodium dodecylbenzenesulfonate. On the other hand, a blue-sensitive emulsion prepared by adding the following blue-sensitive dye to silver chlorobromide emulsion (containing 50 mol% of silver bromide and 70 g / kg of Ag) at 2.25 × 10 ⁻⁴ mol per mol of silver chlorobromide. Made 95g. The emulsified dispersion and the emulsion were mixed and dissolved, and the concentration was adjusted with gelatin so that the composition shown in Table I was obtained to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer by adjusting the concentration with gelatin so as to have the composition shown in I. 1-oxy-3,5-as a gelatin hardening agent for each layer
Dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizer for each emulsion.

Blue sensitive emulsion layer; Green-sensitive emulsion layer; Red-sensitive emulsion layer; The following dyes were used as the anti-irradiation dye in each emulsion layer.

Green-sensitive emulsion layer; Red-sensitive emulsion layer; Structural formulas of compounds such as couplers used in this example are as follows.

(a) Yellow coupler (b) Color image stabilizer (c) solvent (d) Color mixing inhibitor (e) solvent 1: 1 mixture (molar ratio) (f) UV absorber 1: 5: 3 mixture (molar ratio) (g) Cyan coupler (h) Color image stabilizer 1: 3: 3 mixture of (i) solvent 1: 2 mixture of A multilayer silver halide color photographic light-sensitive material can be prepared by simultaneously coating the coating solutions for the first to seventh layers after adjusting the balance of surface tension and viscosity.

When the coating solution for the third layer was prepared, the couplers represented by the general formula (I) of the present invention and the comparative couplers were used to prepare Samples A to E having different constitutions only in the third layer as shown in Table II. .

These silver halide color light-sensitive materials were subjected to wedge exposure according to a conventional method and processed according to the processing steps and processing solution formulations shown below.

Sensitometric evaluation was performed on the obtained sample. The results are shown in Table III.

〔Processing method〕

Process Temperature Time Color development 33 ° C. 1 minute 30 seconds 2 minutes 30 seconds 3 minutes 30 seconds Bleaching fixing 33 ° C. 1 minute 30 seconds Washing 33 ° C. 3 minutes [Treatment liquid composition] (color developing solution) Water 800 m Tetrapolyphosphate sodium 2 0.0 g Benzyl alcohol 14.0 m Diethylene glycol 10.0 m Sodium sulfite 2.0 g Potassium bromide 0.5 g Sodium carbonate 30.0 g N-ethyl-N- (β-methansulfonamidoethyl) -3-methyl-4-amino Aniline sulfonate 5.0g Hydroxylamine sulphate 4.0g Add water 1000m pH (25 ° C) 10.20 (Bleach fixer) Water 400m Ammonium thiosulfate (70%) 150m Sodium sulfite 18g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetic acid / 2Na 5g Add water Te 1000ml pH (25 ℃) 7.00 As is apparent from Table III, Samples B, C and D using the coupler of the present invention have improved sensitivity and gradation (γ) and show high color density.

(Example 2) Samples A to E produced in (Example 1) were subjected to wedge exposure according to a conventional method and processed according to the processing steps and processing solution formulations shown below.

Sensitometric evaluation was performed on the obtained sample. The results are shown in Table IV.

〔Processing method〕

Process Temperature Time Color development 35 ° C 30 seconds, 45 seconds, 1 minute 3
0 second Bleaching development 35 ° C 1 minute 30 seconds Rinse 28-35 ° C 1 minute 30 seconds [Treatment liquid composition] (Color developer) Water 800cc Diethylenetriaminepentaacetic acid 1.0g Sodium sulfite 0.2g N, N-diethylhydroxylamine 4 .2 g potassium bromide 0.6 g sodium chloride 1.5 g triethanolamine 8.0 g potassium carbonate 30 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.5 g 4, 4'-Diaminostilbene fluorescent whitening agent (Whitex4, Sumitomo Chemical Co., Ltd.) 2.0 g Water at 1000 cc KOH pH 10.25 (bleach-fix solution formulation) Ammonium thiosulfate (54 wt%) 150 ml Na ₂ SO ₃ 15 g NH ₄ [Fe (III) (EDTA)] 55 g EDTA · 2Na 4g glacial acetic acid 8.61g water to make a total volume to 1000m (pH 5.4) (rinse liquid treatment _{) EDTA · 2Na · 2H 2 O} 0.4g Water to make a total volume to 1000 m (pH 7.0) As is clear from Table IV, Samples B, C and D using the coupler of the present invention have improved sensitivity and gradation (γ), and show high color density.

(Example 3) (Reversal color paper) Sample G was prepared by applying the following first to twelfth layers to a paper support laminated on both sides with polyethylene in multiple layers. Titanium white is contained as a white pigment, and a trace amount of ultramarine is contained as a bluish dye on the coating side of the first layer of polyethylene.

(Composition of Photosensitive Layer) The components and the coating amounts shown in g / m ² are shown below. For silver halide, the coating amount in terms of silver is shown.

First layer (gelatin layer) Gelatin ...... 1.30 Second layer (antihalation layer) Black colloidal silver ...... 0.10 Gelatin ...... 0.70 Third layer (low sensitivity red sensitive layer) Red sensitizing dye ( Silver iodobromide spectrally sensitized in * 1 and * 2) (silver iodide 5.0 mol%, average grain size 0.4μ)
...... 0.15 Gelatin ...... 1.00 Cyan coupler (* 3) ...... 0.14 Cyan coupler (* 4) ...... 0.07 Anti-fading agent (* 5, * 6 and * 7) ...... 0. 10 Coupler solvent (* 8 and * 9) ... 0.06 4th layer (high sensitivity red sensitive layer) Silver iodobromide (silver iodide) spectrally sensitized with a red sensitizing dye (* 1 and * 2) 6.0 mol%, average particle size 0.7μ) ... 0.15 Gelatin ... 1.00 Cyan coupler (* 3) ... 0.20 Cyan coupler (* 4) ... 0.10 Anti-fading agent (* 5, * 6 and * 7) ... 0.15 Coupler solvent (* 8 and * 9) ... 0.10 Fifth layer (intermediate layer) Magenta colloidal silver ... 0.02 Gelatin ... 1.00 Color mixing inhibitor ( * 10) ...... 0.08 Color mixture inhibitor solvent (* 11 and * 12) ...... 0.16 Polymer latex (* 13) ...... 0.10 6th layer (low sensitivity) Green Sensitive Layer) Silver iodobromide spectrally sensitized with a green sensitizing dye (* 14) (silver iodide 2.5 mol%, grain size 0.4μ) …… 0.10 gelatin …… 0.80 magenta coupler (* 15) …… 0.10 Anti-fading agent (* 16) …… 0.10 Anti-staining agent (* 17) …… 0.01 Anti-staining agent (* 18) …… 0.001 Coupler solvent (* 11 and *) 19) ...... 0.15 7th layer (high-sensitivity green-sensitive layer) Silver iodobromide spectrally sensitized with a green sensitizing dye (* 14) (3.5 mol% silver iodide, grain size 0.9μ). 0.10 Gelatin: 0.80 Magenta coupler (* 15): 0.10 Anti-fading agent (* 16): 0.10 Anti-staining agent (* 17): 0.01 Anti-staining agent (* 18) ) ...... 0.001 8th layer (yellow filter layer) Yellow colloidal silver ...... 0.20 Gelatin ...... 1.00 Color mixing inhibitor ( 10) …… 0.06 Color mixture inhibitor solvent (* 11 and * 12) …… 0.15 Polymer latex (* 13) …… 0.10 9th layer (low sensitivity blue sensitive layer) Blue sensitizing dye (* 20) Spectral-sensitized silver iodobromide (silver iodide 2.5 mol%, grain size 0.5μ) …… 0.15 Gelatin …… 0.50 Yellow coupler (* 21) …… 0.20 Stain inhibitor (* 18) ...... 0.001 Coupler solvent (* 9) ...... 0.05 10th layer (high sensitivity blue sensitive layer) Blue sensitizing dye (* 20 silver iodobromide spectrally sensitized (iodination) Silver 2.5 mol%, particle size 1.2μ) 0.25 Gelatin 1.00 Yellow coupler (* 21) 0.40 Stain inhibitor (* 18) 0.002 Coupler solvent (* 9) ...... 0.10 11th layer (ultraviolet absorbing layer) Gelatin ...... 1.50 Ultraviolet absorber (* 22, * 6 and * 7) ...... 1. 0 Color mixing inhibitor (* 23) …… 0.06 Color mixing inhibitor solvent (* 9) …… 0.15 Irradiation prevention dye (* 24) …… 0.02 Irradiation prevention dye (* 25) …… 0 .02 12th layer (protective layer) Fine grain silver chlorobromide (97 mol% silver chloride, average size 0.2μ) ...... 0.07 Gelatin ...... 1.50 Gelatin hardening agent (* 26) ...... 0.17 * 1 5,5'-Dichloro-3,3'-di (3-sulfobutyl) -9-ethylthiacarbonylcyanine Na salt * 2 Triethylammonium-3- [2- {2- [3
-(3-Sulfopropyl) naphtho (1,2-d) thiazoline-2-indenemethyl] -1-butenyl} -3-naphtho (1,2-d) thiazolino] propanesulfone * 3 2- [α- (2,4-di-t-amylphenoxy)
Hexanamide] -4,6-dichloro-5-ethylphenol * 4 2- [2-chlorobenzoylamide] -4-chloro-5- [α- (2-chloro-4-t-amylphenoxy) octanamide] -Phenol * 5 2- (2-hydroxy-3-sec-5-t-butylphenyl) benzotriazole * 6 2- (2-hydroxy-5-t-butylphenyl) benzotriazole * 7 2- (2-hydroxy -3,5-Di-t-butylphenyl) -6-chlorobenztriazole * 8 Dioctyl phthalate * 9 Trinonyl phosphate * 10 2,5-Di-t-octyl hydroquinone * 11 Tricresyl phosphate * 12 Dibutyl phthalate * 13 Polyethyl acrylate * 14 5,5'-Diphenyl-9-ethyl-3,3'-disulfopropyloxacarbocyanine Na salt * 15 Comparison coupler * 16 3,3,3 ', 3'-Tetramethyl-5,6,5', 6'-
Tetrapropoxy-1,1'-bisspiroindane * 17 3- (2-ethylhexyloxycarbonyloxy) -1- (3-hexadecyloxyphenyl) -2-
Pyrazoline * 18 2-Methyl-5-t-octylhydroquinone * 19 Trioctyl phosphate * 20 Triethylammonium-3- [2- (3-benzylrhodanine-5-ylidene) -3-benzoxazolinyl] propanesulfonate * 21 α-pivaloyl-α-[(2,4-dioxo-1-
Benzyl-5-ethoxyhydantoin-3-yl) -2
-Chloro-5- (α-2,4-di-t-amylphenoxy) butanamide] acetanilide * 22 5-chloro-2- (2-hydroxy-3-t-butyl-5-t-octyl) phenylbenztriazole * 23 2,5-di-sec-octylhydroquinone * 24 *twenty five * 26 1,4-bis (ganylsulfonylacetamide) ethane Next, except that the comparative magenta coupler (* 15) of this sample G was replaced with the exemplified couplers (5), (8) and (11) in equimolar amounts. Samples H, I, and J were similarly prepared. These samples G
To J were subjected to wedge exposure according to a conventional method and processed according to the processing steps and processing solution formulations shown below.

Sensitometric evaluation was performed on the obtained sample. The results are shown in Table V.

Processing step First development (black and white development) 38 ° C 75 seconds Water washing 38 ° C 90 seconds Reverse exposure 100lux or more 60 seconds or more Color development 38 ° C 135 seconds Water washing 38 ° C 45 seconds Bleach fixing 38 ° C 120 seconds Water washing 38 ° C 135 seconds Drying treatment liquid Composition (first developer) Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 0.6 g Diethylenetriamine pentaacetic acid pentasodium salt 4.0 g Potassium sulfite 30.0 g Potassium thiocyanate 1.2 g Potassium carbonate 35. 0 g Hydroquinone monosulfonate / potassium salt 25.0 g Diethylene glycol 15.0 m 1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0 g Potassium bromide 0.5 g Potassium iodide 5.0 m Water was added 1 (PH 9.70) (Color developer) Benzyl alcohol 15.0 ml Ciethylene glycol 12.0 ml 3,6-Dithia-1,8-octanediol 0.2 g Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 0.5 g Diethylenetriaminepentaacetic acid pentasodium salt 2 0.0 g sodium sulfite 2.0 g potassium carbonate 25.0 g hydroxylamine sulfate 3.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g potassium bromide 0 0.5 g potassium iodide 1.0 m Water was added 1 (pH 10.40) (bleach-fixing solution) 2-mercapto-1,3,4-triazole 1.0 g Ethylenediaminetetraacetic acid / disodium dihydrate 5.0 g Ethylenediaminetetraacetic acid / Fe (III) / ammonium monohydrate 80.0g Sodium sulfite 15.0g Sodium thiosulfate Mu (700g / liquid) 160.0m
Glacial acid 5.0m Add water 1 (pH6.50) As is apparent from Table V, Samples H, I and J using the coupler of the present invention have improved gradation (γ) and show high color density.

(Example 4) (Color positive film) Next, the first to twelfth layers were applied in the following order on a triacetate film base to prepare a sample K.

1st layer; antihalation layer UV absorber 5-chloro-2- (2-hydroxy-3,5
-Di-t-butylaenyl) -2H-benzotriazole 15g, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole 30g, 2- (2-
With 35 g of hydrooxy-3-sec-butyl-5-t-butylphenyl) -2H-benzotriazole and 100 g of dodecyl 5- (N, N-diethylamino) -2-benzenesulfonyl-2,4-pentadienoate. Tricresyl phosphate 200m, ethyl acetate 200m
, Sodium tridecylbenzenesulfonate 20 g,
An emulsion (hereinafter referred to as emulsion (a)) obtained by stirring a 10% aqueous gelatin solution at high speed is mixed with 10% gelatin, black colloidal silver, water, and a coating aid to give a dry film thickness of 2
It was applied so as to obtain μ.

Second layer: gelatin intermediate layer 2,5-di-t-octylhydroquinone is dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate to prepare 1
2 kg of an emulsion (hereinafter referred to as emulsion (b)) obtained by high-speed stirring with 1 kg of 0% gelatin aqueous solution was mixed with 1.5 kg of 10% gelatin, and the mixture was applied so as to have a dry film thickness of 1 μm.

Third layer; low-sensitivity red-sensitive emulsion layer 10 g of 2- (heptafluorobutyramide) -5- {2 '-(2 ", 4" -di-t-aminophenoxy) butylamide} -phenol which is a cyan coupler, 500 g of an emulsion (hereinafter referred to as emulsion (c)) obtained by dissolving in 100 cc of tricresyl phosphate and 100 cc of ethyl acetate and stirring at high speed with 1 kg of 10% gelatin aqueous solution was added to 1 kg of a red-sensitive silver iodobromide emulsion. (Containing 70 g of silver and 60 g of gelatin, iodine content is 4 mol%), and dried film thickness 1 μ
Was applied. (Amount of silver 0.5 g / m ² 4th layer; high-sensitivity red-sensitive emulsion layer) Emulsion (c) was mixed with 1 kg of red-sensitive silver iodobromide emulsion (70 g of silver,
It was mixed with 60 g of gelatin and had an iodine content of 2.5 mol%) and coated so that the dry film thickness was 2.5 μm. (Amount of silver: 0.8 g / m ² ) Fifth layer: Intermediate layer 1 kg of the emulsion layer (b) was mixed with 1 kg of 10% gelatin and coated so that the dry film thickness was 1 μm.

6th layer; low-green emulsion layer Comparative magenta coupler instead of cyan coupler 300 g of an emulsion (hereinafter, referred to as emulsion (d)) obtained in the same manner as the emulsion of the third layer except that 1 g of green-sensitive silver iodobromide emulsion (1 kg (70 g of silver, 60 g of gelatin) was used). , Iodine content was 3 mol%), and applied so that the dry film thickness was 2.0 μ. (Silver amount: 0.7 g / m ² ) Seventh layer: High-sensitivity green-sensitive emulsion layer Emulsion (d) (1000 g) was replaced with green-sensitive silver iodobromide emulsion (1 kg)
(Contains 70g silver and 60g zeratan, iodine content is 2.5
(Mol%) and coated so that the dry film thickness was 2.0 μm. (Silver amount: 0.7 g / m ² ) Eighth layer; gelatin intermediate layer 1 kg of the emulsion (b) was mixed with 1 kg of 10% gelatin, and the mixture was applied so as to have a dry film thickness of 0.5 μ.

Ninth layer: yellow filter layer An emulsion containing yellow colloidal silver was applied so as to have a dry film thickness of 1 μm.

10th layer: Low blue-sensitive emulsion layer α- which is a yellow coupler instead of a cyan coupler
(Pivaloyl) -α- (1-benzyl-5-ethoxy-
1000 g of an emulsion (hereinafter, referred to as emulsion (e)) obtained in the same manner as the emulsion of the third layer except that 3-hydantoinyl) -2-chloro-5-dodecyloxycarbonylacetanilide was used was blue-sensitive. 1 kg of silver iodobromide emulsion (70 g of silver
g, and 60 g of gelatin, the iodine content was 2.5 mol%), and the mixture was applied so that the dry film thickness was 1.5 μm. (Silver amount: 0.6 g / m ² ) Eleventh layer: High-sensitivity blue-sensitive emulsion layer 1000 g of emulsion (e) was added to 1 kg of blue-sensitive silver iodobromide emulsion.
(It contains 70 g of silver and 60 g of gelatin, and the iodine content is 2.
5 mol%) and coated so that the dry film thickness would be 3 μm. (Amount of silver: 1.1 g / m ² ) Twelfth layer; second protective layer Emulsion (a) was mixed with 10% gelatin, water, and a coating aid, and coated so that the dry film thickness was 2 μm.

13th layer; 1st protective layer Fine grain emulsion whose surface is fogged (grain size 0.06μ, 1
A 10% gelatin aqueous solution containing (mol% silver iodobromide emulsion) was coated so that the silver coating amount was 0.1 g / m ² and the dry film thickness was 0.8 μ.

A gelatin hardening agent 1,4-bis (vinylsulfonylacetamide) ethane and a surfactant were added to each layer.

Next, Samples L, M and N were prepared in the same manner except that the comparative magenta coupler of Sample K was replaced with the exemplified couplers (5), (8) and (9) in equimolar amounts.

These samples K to N were exposed through a neutral gray sensitometric wedge and then subjected to the following reversal processing.

Treatment process Temperature Time First development 6 minutes 38 ° C Water wash 2 minutes 〃 Inversion 2 minutes 〃 Color development 6 minutes 〃 Adjustment 2 minutes 〃 Bleach 6 minutes 〃 Fixing 4 minutes 〃 Water washing 4 minutes 〃 Stable 1 minute Room temperature Drying composition Uses the following:

First developer water 700 m Nitrilo-N, N, N-trimethylene phosphonic acid pentatonalium salt 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4methyl-4-hi Droxymethyl-3 pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2m Add water 1000m Reversal liquid water 700m Nitrilo-N, N, N-trimethylene hesphonic acid-5 Sodium salt 3 g Stannous chloride (dihydrate) 1 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 m Water was added 1000 m Color developer water 700 m Nitrilo-N, N, N-trimethylene phosphonic acid-5 Sodium salt 3g Sodium sulfite 7g Sodium triphosphate ( Dihydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 m Sodium hydroxide 3 g Citrazinic acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4 -Aminoaniline / sulfate 11g 3,6-dithiaoctane-1,8-diol 1g Water was added to 1000m Adjusted water 700m Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4m Glacial acetic acid 3m Water 1000m Bleach solution Water 800g Ethylenediaminetetraacetate sodium (dihydrate) 2g Ethylenediaminetetraacetic acid iron (III) ammonium (dihydrate) 120g Potassium bromide 100g Water is added 1000m Fixer water 800m Sodium thiosulfate 80. 0g sodium sulfite 5.0g sodium bisulfite Lithium 5.0 g Water added 1000 m Stabilized water 800 m Formalin (37% by weight) 5.0 m Fuji Drywell (Fuji Film Co., Ltd. surfactant) 5.0 m Water added 1000 m Sensitivity of sample obtained The results of the tomometry evaluation are shown in Table VI.

As is clear from Table VI, the samples L, M and N using the coupler of the present invention have improved gradation (γ) and exhibit high color density.

(Example 5) (Color negative film) A multi-layer color light-sensitive material sample composed of each layer having the composition shown below was prepared on a triacetyl cellulose film support to prepare a sample.

First layer: Antihalation layer Gelatin layer containing black colloidal silver Second layer: Intermediate layer Gelatin layer containing emulsified dispersion of 2,5-di-t-octylhydroquinone Third layer: First red-sensitive emulsion layer Odor Silver halide emulsion (silver iodide: 5 mol%): Silver coating amount: 1.6 g / m ² Sensitizing dye I: 4.5 × 10 ⁻⁴ mol per 1 mol of silver Sensitizing dye II: Silver 1.5 mol per 1 mol 1.5 × 10 ⁻⁴ mol Coupler EX-1 ... 0.04 mol relative to 1 mol silver Coupler EX-3 ... 0.003 mol relative to 1 mol silver Coupler EX-9 ... ... 0.0006 mol per 1 mol of silver Fourth layer: second red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 10 mol%) ... Silver coating amount 1.4 g / m ² Sensitizing dye I 1 × ^{10 -4} mol coupler relative to 3 × ^{10 -4} mol sensitizing dye II ...... 1 mol of silver relative ...... silver mole EX- ...... 0.002 mol to 1 mol of silver Coupler EX-2 ...... 0.02 mol to 1 mol of silver Coupler EX-3 ...... 0.0016 mol to 1 mol of silver Fifth layer; intermediate layer Same as the second layer Sixth layer; first green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 4 mol%) ... Silver coating amount 1.2 g / m ² Sensitizing dye III ... 1 mol of silver On the other hand, 5 × 10 ⁻⁴ mol Sensitizing dye IV: 2 × 10 ⁻⁴ mol for 1 mol of silver Comparative magenta coupler: 0.05 mol for 1 mol of silver 7th layer: second green feeling Emulsion layer Silver iodobromide emulsion (silver iodide: 8 mol%) ... Silver coating amount 1.3 g / m ² Sensitizing dye III ... 3 × 10 ⁻⁴ mol with respect to 1 mol of silver Sensitizing dye IV ... ... 0.017 8th layer against 1.2 × ^{10 -4} mol comparative Magellan data coupler ...... silver mole per silver mole, yellow filter layer peptidase A gelatin layer containing colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone in a tin aqueous solution Ninth layer; First blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 6 mol%) ...... Silver coating amount 0.7 g / m ² Coupler EX-4 ...... 0.25 mol per 1 mol silver Coupler EX-5 ...... 0.015 mol per 1 mol silver 10th layer; second blue Emulsion-sensitive layer Silver iodobromide (silver iodide: 6 mol%) ... Silver coating amount 0.6 g / m ² Coupler EX-4 ... 0.06 mol per 1 mol of silver 11th layer; 1st protection Layer Silver iodobromide (1 mol% silver iodide, average grain size 0.07μ)
Silver coating amount 0.5 g / m ² Gelatin layer containing emulsified dispersion of UV absorber UV-1 Twelfth layer; Second protective layer A gelatin layer containing polymethylmethacrylate particles (diameter about 1.5 μm) was coated.

In addition to the above composition, a gelatin hardening agent H-1 and a surfactant were added to each layer.

(Structural Formula of Compound Used in Example 5) Coupler EX-1 EX-2 EX-3 EX-4 EX-5 EX-6 Magenta coupler for comparison H-1 UV-1 x: y = 7: 3 (weight ratio) Sensitizing dye I Sensitizing dye II Sensitizing dye III Next, samples P, Q and R were prepared in the same manner except that the comparative magenta coupler of this sample was replaced with the exemplified couplers (5), (8) and (10) in equimolar amounts. These samples to R were wedge-exposed according to a conventional method and processed according to the processing steps and processing solution formulations shown below.

The development process used here was carried out at 38 ° C. as described below.

1. Color development: 3 minutes 15 seconds 2. Bleach: 6 minutes and 30 seconds 3. Washing with water …… 3 minutes 15 seconds 4. Fixation: 6 minutes and 30 seconds 5. Washing with water ... 3 minutes 15 seconds 6. Stability: 3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2,4 g 4- (N-ethyl-N-β-hydroxyethylamino) -2 -Methylaniline Sulfate 4.5g Add water 1 Bleach Ammonium bromide 160.0g Ammonia water (28%) 25.0CC Ethylenediaminetetraacetic acid sodium iron salt 130.0g Glacial acetic acid 14.0cc Add water 1 Fixing Liquid sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 CC Sodium bisulfite 4.6 g Water was added 1 Stabilized liquid Formalin 8.0 cc Water was added 1 Thus obtained Each sample was evaluated for sensitometry. The results are shown in Table VII.

*) Relative sensitivity with the sample being 100, which is the reciprocal of the exposure amount giving the density of fog + 0.2 **) Density at the exposure amount (log E) showing magenta density and D = 2.0 in the sample Clear from Table VII Thus, it can be seen that the samples P, Q, and R using the coupler of the present invention have improved sensitivity and gradation (γ) and exhibit high color density.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-60-97353 (JP, A) JP-A-60-190779 (JP, A) JP-A 61-53664 (JP, A) JP-A 62- 166340 (JP, A) JP 62-209460 (JP, A) JP 62-246054 (JP, A)

Claims (1)

[Claims] 1. A color image forming method, which comprises developing a silver halide light-sensitive material with a developer containing an aromatic primary amine in the presence of at least one coupler represented by formula (I). General formula (I) In the formula, R ₁ represents a substituted or unsubstituted alkyl group or aryloxy group, and R ₂ represents a substituted aryl group. X represents a halogen atom. However, R ₂ is 4-t
-Butylphenyl group, 2,4-di-t-amylphenyl group, 4-tetradecanamidephenyl group, hexadecyloxyphenyl group, 4 '-[α- (4 "-1-butylphenoxy) tetradecanamidephenyl group, Or And R ₁ is not the following general formula (II). Formula _{(II) -R A -SO 2 -R} B ( wherein, _{R A} represents an alkylene group, _{R B} represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.)