JPH063785A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility and graininess by forming a nonphotosensitive hydrophilic colloid layer and incorporating a specified magenta dye-forming coupler into a green-sensitive emulsion layer. CONSTITUTION:This silver halide color photographic sensitive material has at least one blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer on a supporting body. The green-sensitive emulsion layer has at least two silver halide emlulsion layers and nonphotosensitive hydrophilic colloid layers between any two layers of the emulsion layers. At least one green-sensitive emulsion layer contains a magenta dye-forming coupler expressed by the formula. In formula, R1 is a hydrogen atom or substituent, Z is nonmetal atoms necessary to form an five-member azole ring containing 2-4 nitrogen atoms. The azole ring may have a substituent (including condensed ring) and X is a hydrogen atom or group which is released by the coupling reaction with the oxidizer of an developing agent.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a silver halide color photographic light-sensitive material having excellent color reproducibility and improved graininess.
In particular, it relates to a silver halide color reversal photographic light-sensitive material.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material for photographing is required to have high sensitivity regardless of whether it is negative or reversal and to have excellent image quality such as graininess and color reproducibility.

The formation of a dye image in a silver halide color photographic light-sensitive material is usually carried out when an aromatic primary amine type color developing agent reduces the silver halide grains in the exposed silver halide color photographic light-sensitive material. This oxidant is subjected to a coupling reaction with a coupler previously contained in the silver halide color photographic material.

In a silver halide color photographic light-sensitive material, a combination of each light-sensitive silver halide emulsion with a yellow coupler, a cyan coupler and a magenta coupler is usually used for color reproduction by the subtractive color method.

Among these, as a magenta coupler, the improvement of the hue of magenta color by using a pyrazoloazole type magenta coupler in place of the 5-pyrazolone type coupler which has been used until now has been attracting attention.

The dye produced by the reaction between these couplers and the color developing agent has a small amount of sub-absorption harmful to color reproduction, so that the color reproduction region can be expanded. For these couplers, see, for example, US Pat. No. 3,725,06.
No. 7, JP-A-60-172982 and others.

However, when these couplers are used,
Since the coupling reactivity with the oxidized color developing agent is extremely high, the color reversal light-sensitive material has a drawback that sensitivity and graininess are deteriorated.

Color photographic light-sensitive materials usually have a red color-sensitive layer,
Having different color sensitivity of the green color sensitive layer and the blue color sensitive layer,
Further, each color-sensitive layer is composed of two or more silver halide emulsion layers having different sensitivities. The ratio of silver to coupler in the emulsion layers having different sensitivities is different, but the oxidized developing agent generated in the emulsion layer having a high ratio of silver to coupler diffuses into a layer having a lower ratio of coupler to silver to form a color. , The graininess of an emulsion layer having a high ratio of silver to coupler is deteriorated.

Deterioration of graininess due to diffusion of oxidized developing agent from an emulsion layer having a high silver to coupler ratio to a low emulsion layer occurs regardless of whether it is a negative or a reversal photographic light-sensitive material. In the case of a color reversal photographic material in which the ratio of silver to coupler is higher than that of the high-sensitivity layer, the oxidation product of the developing agent from the low-sensitivity silver halide emulsion layer to the high-sensitivity silver halide emulsion layer is Diffusion causes deterioration of graininess.

On the other hand, for example, JP-A-60-13
No. 0736 discloses a method of providing a non-photosensitive intermediate layer between the same color-sensitive layers in order to prevent deterioration of graininess due to diffusion of an oxidation product of a developing agent in a color reversal photographic light-sensitive material. .

The deterioration of graininess due to the mechanism described above is
This has been a serious problem when using pyrazolazole type couplers.

Further, European Patent 0486929A1 disclosed by Eastman Kodak Company discloses that the presence of a higher alcohol at the same time as a magenta color forming coupler significantly improves the color forming property of the coupler.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material having good color reproduction and good graininess.

[0014]

In a silver halide color photographic light-sensitive material having at least one blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer on a support, the green-sensitive emulsion layer is sensitive. Of at least two different silver halide emulsion layers, a non-photosensitive hydrophilic colloid layer provided between any two layers of the green-sensitive emulsion layer, and at least one of the green-sensitive emulsion layers. The following general formula [M]
A silver halide color photographic light-sensitive material containing at least one magenta dye-forming coupler represented by: General formula [M]

[0015]

[Chemical 3] Here, R ₁ represents a hydrogen atom or a substituent. Z represents a group of non-metal atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.

Furthermore, a silver halide color photographic light-sensitive material characterized in that at least one layer of the same color-sensitive layer contains at least one compound represented by the following general formula [N].

[0017]

[Chemical 4] Hereinafter, the coupler will be described in detail. The skeleton of the coupler skeleton represented by the formula [M] is preferably 1 H -imidazo [1,2- b ] pyrazole, 1 H -pyrazolo [1,5
- b] [1,2,4] triazole, 1 H - pyrazolo [5,1- c] [1,2,4] triazole, 1 H - pyrazolo [1,5-d] tetrazole and 1 H - pyrazolo [ 1,5- a ] benzimidazole and has the formulas [MI], [M-II], [M-III], and [M-IV], respectively.
And [MV].

[0018]

[Chemical 5] Substituents R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , n in these formulas
And X will be described in detail.

R ₁₁ is a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkoxy group, aryloxy group, acylamino group, Alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo A group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group, an acyl group, or an azolyl group, and R ₁₁
May form a bis form with a divalent group.

More specifically, R ₁₁ is each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl). Group, alkynyl group,
A cycloalkyl group or a cycloalkenyl group, more specifically,
For example, methyl, ethyl, propyl, isopropyl, t-
Butyl, tridecyl, 2-methanesulfonylethyl, 3
-(3-Pentadecylphenoxy) propyl, 3- {4
-{2- [4- (4-hydroxyphenylsulfonyl)
Phenoxy] dodecanamide} phenyl} propyl, 2
-Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (eg phenyl, 4-t-butylphenyl, 2,4-di- t-amylphenyl, 2,
4,6-Trimethylphenyl, 3-tridecanamide-
2,4,6-trimethylphenyl, 4-tetradecanamidophenyl), a heterocyclic group (eg, 2-furyl, 2
-Thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2 -Methanesulfonylethoxy), aryloxy groups (eg phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3
-Methoxycarbamoyl), an acylamino group (for example,
Acetamide, benzamide, tetradecanamide, 2
-(2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino A group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino),
Anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino,
2-chloro-5-dodecyloxycarbonylanilino,
N-acetylanilino, 2-chloro-5- {2- (3-
t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoyl) Amino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-)
t-butylphenoxy) propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,
2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl)) Carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3
-(2,4-di-t-amylfesoxy) propyl} carbamoyl), a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl,
N- (2-dodecyloxyethyl) sulfamoyl, N
-Ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl) , Dodecyloxycarbonyl, octadecyloxycarbonyl), a heterocyclic oxy group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pi). Valoylaminophenylazo,
2-hydroxy-4-propanoylphenylazo), acyloxy group (eg acetoxy), carbamoyloxy group (eg N-methylcarbamoyloxy, N-
Phenylcarbamoyloxy), silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (eg,
Phenoxycarbonylamino), imide group (eg, N
-Succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2-
Benzothiazolylthio, 2,4-di-phenoxy-1,
3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl) , Phenylphosphonyl), aryloxycarbonyl groups (eg, phenoxycarbonyl), acyl groups (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl groups (eg, imidazolyl, pyrazolyl, 3- Chloro-pyrazol-1-yl, triazolyl). Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferred R ₁₁ is alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, ureido group, urethane group,
An acylamino group can be mentioned.

R ₁₂ is a group having the same meaning as the substituent exemplified for R ₁₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group or an acyl group. Or a cyano group.

R ₁₃ is a group having the same meaning as the substituent exemplified for R ₁₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group or an alkoxy group. It is a carbonyl group, a carbamoyl group or an acyl group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group or an arylthio group.

R ₁₄ is a group having the same meaning as the substituent exemplified for R ₁₁ , and preferably a hydrogen atom, an alkyl group,
Aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, acylamino group, alkoxycarbonylamino group, sulfonamide group, sulfamoylamino group, or cyano It is a base.

N represents an integer of 1 to 4, preferably 1 to 3.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine color developing agent. The splitting-off group is specifically described as a halogen atom, an alkoxy group, an aryloxy group or an acyloxy group. Group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, 5-membered or 6-membered group A nitrogen heterocyclic group, an imide group, an arylazo group, etc., and these groups may be further substituted with a group acceptable as the substituent for R ₁₁ .

More specifically, halogen atom (eg, fluorine atom, chlorine atom, bromine atom), alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryl An oxy group (for example, 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarbonylphenoxy, 4-methoxycarbonylphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyl) Oxy), an alkyl or aryl sulfonyloxy group (eg, methanesulfonyloxy, toluenesulfonyloxy), an acylamino group (eg, dichloroacetylamino, heptafluorobutyrylamino), an alkyl or aryl sulfonamide group (eg, methanesulfonamino) , Trifluoromethanesulfonamino, p-toluenesulfonamino), alkoxycarbonyloxy groups (eg, ethoxycarbonyloxy, benzyl) Xycarbonyloxy), aryloxycarbonyloxy groups (eg phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio groups (eg dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio) , 2-benzyloxycarbonylaminophenylthio, tetrazolylthio), a carbamoylamino group (eg (N-methylcarbamoylamino, N-
Phenylcarbamoylamino), 5- or 6-membered nitrogen-containing heterocyclic group (for example, 1-imidazolyl, 1-pyrazolyl, 1,2,4-triazol-1-yl, tetrazolyl, 3,5-dimethyl-1-pyrazolyl , 4-cyano-1-pyrazolyl, 4-methoxycarbonyl-1-pyrazolyl, 4-acetylamino-1-pyrazolyl, 1,
2-dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, phenylazo, 4-methoxyphenylazo), and the like. In addition to these, X is an aldehyde or ketone as a leaving group bonded via a carbon atom.
It may also take the form of a bis-type coupler obtained by condensing an equivalent coupler. Further, X may contain a photographically useful group such as a development inhibitor or a development accelerator. Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, a 5-membered or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom, particularly preferably a halogen atom or a substituent. It is an aryloxy group, a substituted arylthio group, or a substituted 1-pyrazolyl group.

Examples of the magenta coupler compound represented by the formula [M] are shown below, but the invention is not limited thereto.

[0029]

[Chemical 6]

[0030]

[Chemical 7]

[0031]

[Chemical 8]

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

[0035]

[Chemical 12]

[0036]

[Chemical 13]

[0037]

[Chemical 14]

[0038]

[Chemical 15]

[0039]

[Chemical 16]

[0040]

[Chemical 17]

[0041]

[Chemical 18]

[0042]

[Chemical 19]

[0043]

[Chemical 20]

[0044]

[Chemical 21]

[0045]

[Chemical formula 22]

[0046]

[Chemical formula 23]

[0047]

[Chemical formula 24]

[0048]

[Chemical 25]

[0049]

[Chemical formula 26]

[0050]

[Chemical 27]

[0051]

[Chemical 28]

[0052]

[Chemical 29]

[0053]

[Chemical 30]

[0054]

[Chemical 31]

[0055]

[Chemical 32]

[0056]

[Chemical 33]

[0057]

[Chemical 34] References which describe a method for synthesizing the coupler represented by the formula [M] are listed below.

The compound of formula [M-I] is described in US Pat.
The compounds of the formula [M-II], such as U.S. Pat. Nos. 00,630, U.S. Pat. Nos. 4,540,654, 4,705,863, JP-A-61-65245, 62-209457, and 62- 249155 and the like, compounds of the formula [M-III] are disclosed in JP-B-47-27411, U.S. Pat. No. 3,725,0.
No. 67, etc., compounds of the formula [M-IV] are disclosed in JP-A-60-33.
It can be synthesized by the method described in No. 552 or the like.

Next, the compound represented by the general formula [N] will be described.

[0060]

[Chemical 35] In the formula, at least one of R ₁ , R ₂ , and R ₃ represents a substituted or unsubstituted alkyl or alkenyl group, and R
The sum of carbon numbers of ₁ , R ₂ , and R ₃ is 10 or more. The substituents which the above alkyl, alkenyl and aralkyl groups may have are a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxy group, a sulfo group and an amino group. , Alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group , An alkoxycarbonyl group, a heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group,
Aryloxycarbonyl group, an acyl group, or a substituent such as an azolyl group, preferably a halogen atom,
It is an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group, a sulfonyl group, an alkoxycarbonyl group, an acyloxy group, or an acyl group.

Specific examples of the alcohol represented by the general formula [N] are shown below, but the alcohol is not limited to these.

[0062]

[Chemical 36]

[0063]

[Chemical 37]

[0064]

[Chemical 38] The silver halide color photographic light-sensitive material of the present invention usually has a plurality of silver halide emulsion layers having different color sensitivities such as a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. The above-mentioned color-sensitive layer is usually arranged in the order of a red-color sensitive layer, a green color-sensitive layer and a blue color-sensitive layer from the support side. However, the above arrangement may be different depending on the purpose. Further, a non-photosensitive layer may be provided between each color-sensitive layer.

At least one color-sensitive layer of the present invention is composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The color sensitivities are substantially the same when the spectral sensitivity ranges under the normal conditions of the two silver halide emulsion layers are substantially the same, and the wavelength widths of the spectral sensitivity ranges are substantially the same and within 20 nm. If one of the spectral sensitivity regions is included in the other spectral sensitivity region or has at least a considerable overlap, and at least one of the short wavelength side and the long wavelength side does not deviate by 20 nm or more, or both. It refers to the case where the shift of the peak wavelength is within 20 nm. The difference in sensitivity between these silver halide emulsion layers having substantially the same color sensitivity is 0.2 or more in log E display.

A plurality of silver halide emulsion layers constituting each light-sensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. Two-layer structure, or Japanese Patent Publication No. Sho 49-
The three-layer structure described in No. 15495 is preferably used.

It is preferable that the emulsion layers having the same color sensitivity with different sensitivities are usually arranged so that the sensitivities are gradually lowered toward the support. However, JP-A-57-11
No. 2751, No. 62-200350, No. 62-206.
As described in Nos. 541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

In the present invention, a non-photosensitive layer containing at least one layer of gelatin and / or a synthetic high molecular weight compound adjacent to each emulsion layer between any two layers having different sensitivities belonging to the green color-sensitive layer. A hydrophilic hydrophilic colloid layer is provided. This non-photosensitive hydrophilic colloid layer may contain a DIR compound or a color mixing inhibitor in addition to the above-mentioned gelatin and high molecular weight compound. Further, a coupler having the same color forming property as the silver halosaponified emulsion layer adjacent to the non-photosensitive hydrophilic colloid layer may be contained.

The thickness of the non-photosensitive hydrophilic colloid layer is preferably 0.2 μm or more and 3.0 μm or less, and 0.3 μm.
It is more preferably 2.0 μm or less.

When the green color-sensitive layer is composed of three or more layers, this non-photosensitive hydrophilic colloid layer is provided at any position between the low-sensitivity layer, the medium-sensitivity layer and the high-sensitivity layer. Can also obtain the effects shown in the present invention.

In the two emulsion layers sandwiching the non-photosensitive hydrophilic colloid layer of the present invention, the molar ratio of silver to the coupler in the slower emulsion layer is higher than that in the higher sensitive emulsion layer. Is also high. Here, the mole ratio of the coupler is the total number of moles of all the couplers contained in each emulsion layer, and the number of moles of silver is the silver amount of the photosensitive emulsion contained in each emulsion layer. The molar ratio of silver to the coupler in the low-sensitivity emulsion layer is preferably 1.5 times or more, and more preferably 2 times or more the molar ratio of silver to the coupler in the high-sensitivity emulsion layer. Further, the molar ratio of silver to the coupler in the low-sensitivity emulsion layer is 5 to 10
0 is preferable, and the molar ratio of silver to the coupler in the high sensitivity emulsion layer is preferably 2 to 30.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448,
BL, GL, described in the specification of 63-89850.
It is preferable to arrange a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as RL, adjacent to or in proximity to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.
The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 μm or less, large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18
716 (November 1979), p.648, ibid. Thirty
7105 (November 1989), pages 863-865, and "Graphide's Physics and Chemistry" by Graphide, published by Paul Montel (P. Glafkides, Chemieet).
Phisique Photographique, P
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff).
in, Photographic Emulsion
Chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
otographic Emulsion, Focal
Press, 1964) and the like.

US Pat. Nos. 3,574,628, and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, Photographhp.
ic Science and Engineering
g), 14: 248-257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157, and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image in both the surface and the inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and the same No. No. 307105, and the relevant parts are summarized in the table below.

The light-sensitive material of the present invention includes the light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
The thickness is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse grains (at least 95% of the weight or number of silver halide grains are within ± 40% of the average grain size) (Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average value of equivalent circle diameters of projected areas) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The compound represented by the general formula [N] of the present invention is preferably added by an oil-in-water dispersion method. The addition amount thereof is preferably 5% by weight to 300% by weight, more preferably 10% by weight to 200% by weight, and most preferably 50% by weight to 150% by weight, based on the addition amount of the magenta color forming coupler in the layer to be added.

The amount of silver coated on the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three research disclosures, and the relevant portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, to page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Fogging prevention page 24 to 25 page 649 right column 868 to 870 page agents and stabilizers 6. Light absorber, pages 25 to 26, page 649, right column, page 873, filter dye, page 650, left column, ultraviolet absorber 7. Stain page 25 right column page 650 left column page 872 Inhibitor to right column 8. Dye image stabilizer page 25 page 650 page left column page 872 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Binder page 26 page 651 left column 873 to page 874 11. Plasticizers, lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Antistatic agent Page 27 Page 650 Right column 876-877 Page 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being added to the light-sensitive material.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,454, 4,788,132, JP-A-62-
18539 and the mercapto compounds described in JP-A-1-283551 are preferably contained.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Application Laid-Open No. 1-1060.
It is preferable to include a compound described in No. 52, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

International Publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-2593
It is preferable to include the dye described in No. 58.

Various color couplers can be used in the light-sensitive material of the present invention, specific examples of which are described in Research Disclosure No. 17643, VII-C-
G, and the same No. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620,
No. 4,326,024, No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760.
U.S. Pat. Nos. 3,973,968 and 4,314,
023, 4,511,649, European Patent No. 24
Those described in No. 9,473A, etc. are preferable.

As the magenta coupler, 5-pyrazolone type compounds and pyrazoloazole type compounds can be used in combination with the compound of the present invention. US Pat. No. 4,310,61
9, No. 4,351,897, European Patent No. 73,6
36, U.S. Pat. Nos. 3,061,432 and 3,7.
No. 25,067, Research Disclosure No.
24220 (June 1984), JP-A-60-3355.
No. 2, Research Disclosure No. 24230
(June 1984), JP-A-60-43659, 6
1-72238, 60-35730, 55-1
No. 18034, No. 60-185951, U.S. Patent Nos. 4,500,630, 4,540,654, 4,556,630, and International Publication WO88 / 0479.
Those described in No. 5 and the like are particularly preferable.

Examples of cyan couplers include phenol type and naphthol type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable. Further, JP-A 64-553 and 64-5.
No. 54, No. 64-555 and No. 64-556, and pyrazoloazole couplers described in US Pat.
The imidazole couplers described in No. 8,672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A.
No. etc.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. Of 307105
Item VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in 6,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD1 above.
7643, Item VII-F and No. 307105, VII
Patents described in section F, JP-A-57-151944
No. 57-154234, No. 60-184248.
No. 63-37346, No. 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,01.
Those described in No. 2 are preferable.

RD. No. 11449, 24241,
The bleaching accelerator releasing coupler described in JP-A No. 61-201247 is effective for shortening the time of the processing step having a bleaching ability, and particularly for a light-sensitive material using the above-mentioned tabular silver halide grains. When added, its effect is great. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-15763.
Those described in No. 8 and No. 59-170840 are preferable. Also, JP-A-60-107029 and JP-A-60-25
No. 2340, JP-A Nos. 1-44940 and 1-4568.
Compounds which release a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in No. 7 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. 173,302A and 313,308A , A ligand releasing coupler described in US Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a fluorescent dye described in US Pat. No. 4,774,181. Examples thereof include releasing couplers.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl)).
Phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate) , Tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc., benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-
p-hydroxybenzoate, etc., amides (N, N
-Diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol,
2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl))
Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, Dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C. or higher, preferably 5
An organic solvent having a temperature of 0 ° C. or more and about 160 ° C. or less can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol as a preservative or a fungicide or JP-A-63-63 is used.
No. 257747, No. 62-272248, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethyl described in JP-A No. 1-80941. Phenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole and the like are preferably added.

Suitable supports which can be used in the present invention are, for example, those described in RD. No. 17643, page 28, ibid.
No. 18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gr
een) and others in Photographic Science and Engineering (Photogr. Sci. E.
ng. ), Vol. 19, No. 2, pp. 124-129, can be measured by using a swellometer (swelling meter) of the type, and T _1/2 is treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness reached at that time is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or by changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
Calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred.

Conventional methods can be applied to form a dye image. For example, the negative-positive method (for example, “Journal o
f the Society of Motion P
image and Television Eng
iners ", Volume 61 (1953), 667-70.
(Described on page 1): Developing with a developer containing a black and white developing agent to produce a negative silver image, followed by at least one uniform exposure or other suitable fog treatment followed by color development. For example, a color reversal method for obtaining a positive dye image is carried out; a silver dye bleaching method is used in which a photographic emulsion layer containing the dye is exposed and then developed to form a silver image, and the silver image is bleached using the bleaching catalyst.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-amino-N, N-diethylaniline, 3-
Methyl-4-amino-N, N-diethylaniline, 4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline) can be used.

In addition to this, for example, L. F. A. Mason
By Photographic Processing
Chemistry (Focal Press, 19
66), pages 226-229, US Pat. No. 2,193,
015, 2,592,364 and JP-A-48-6.
You may use what is described in 4933.

The color developer may further contain, for example, a pH buffer, a development inhibitor or an antifoggant. If necessary, for example, a water softener, a preservative,
It may contain an organic solvent, a development accelerator, a dye-forming coupler, a competitive coupler, a fogging agent, an auxiliary developing agent, a tackifier, a polycarboxylic acid type chelating agent, and an antioxidant.

The photographic emulsion layer of the color developer is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. As the bleaching agent, compounds of polyvalent metals such as iron (III), cobalt (IV), chromium (VI) and copper (II), peracids, quinones and nitroso compounds are used.

As the bleaching or bleach-fixing solution, for example, US Pat. Nos. 3,042,520 and 3,241,966 can be used.
In addition to the bleaching accelerators described in JP-B Nos. 458506 and 45-8836, and the thiol compounds described in JP-A-53-65732, various additives can be added.

In the present invention, color reversal processing is most preferable, and the processing solution and processing steps of the color reversal photosensitive material will be described below.

Among the processing steps, the steps from black and white development to color development are as follows.

1) Black-white development-water washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development Steps 1) to 3) are all performed in US patents. Fourth,
In place of the rinse process described in No. 804,616, it is possible to simplify the process and reduce waste liquid.

Next, the steps after color development will be described.

4) Color development-adjustment-bleaching-fixing-washing-
Stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Color development-adjusting-bleaching-washing-fixing-washing-stable 7) Coloring development-washing-bleaching-washing-fixing-washing-stable 8) Color development Development-bleaching-fixing-washing-stable 9) Color development-bleaching-bleaching fixing-washing-stable 10) Coloring development-bleaching-bleaching fixing-fixing-washing-stable 11) Coloring development-bleaching-washing-fixing-washing- Stable 12) Color development-adjustment-bleach-fix-washing-stable 13) Color development-wash-bleach-fix-wash-stable 14) Color development-bleach-fix-wash-stable 15) Color development-fix-bleach-fix-wash- In the treatment steps of Stability 4) to 15), the washing step immediately before the stabilizing step may be omitted, or conversely, the stabilizing step of the final step may not be performed. The color reversal process is formed by connecting any one of the processes 1) to 3) and any one of the processes 4) to 15).

Known developing agents can be used in the black and white developing solution used in the present invention. As a developing agent,
For example, dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-
Pyrazolidone), aminophenols (eg N-methyl-p-aminophenol), 1-phenyl-3-pyrazolins, ascorbic acid and U.S. Pat. No. 4,067,
The heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline ring and indrene ring described in No. 872 may be used alone or in combination.

The black-and-white developer used in the present invention may optionally contain, for example, a preservative (eg, sulfite or bisulfite),
Buffering agents (eg carbonate, boric acid, borate, alkanolamine), alkaline agents (eg hydroxide, carbonate),
Dissolution aids (eg polyethylene glycols and their esters), pH adjusters (eg organic acids such as acetic acid), water softeners (eg aminopolycarboxylic acids,
Organic phosphonic acids, phosphonocarboxylic acids), sensitizers (for example, quaternary ammonium salts), antifoggants (for example, potassium bromide, benzotriazole, 1-phenyl-5-mercaptotetrazole), development accelerators (for example, Organic thioether compound), a surfactant, a defoaming agent, a film-hardening agent, and a viscosity-imparting agent.

The black-and-white developing solution used in the present invention must contain a compound which acts as a silver halide solvent. However, sulfite, which is usually added as a preservative, plays the role. Specific examples of the sulfite and other silver halide solvents that can be used include KSCN and
NaSCN, K ₂ SO ₃ , Na ₂ SO ₃ , K ₂ S
₂ O ₅ , Na ₂ S ₂ O ₅ , K ₂ S ₂ O ₃ , Na ₂ S ₂ O
_{There are three} .

The pH value of the developer thus adjusted is selected to a value sufficient to give a desired density and contrast, but is in the range of about 8.5 to about 11.5.

The reversal bath used after black and white development may contain a known fogging agent. Examples of the fogging agent include stannous ion complex salts such as stannous ion-organic phosphate complex salts (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salts (Japanese Patent Publication No. 56-32616). Stannous ion-aminopolycarboxylic acid complex salt (US Pat. No. 1,029,050).
No.), boron compounds such as borohydride compounds (US Pat. No. 2,984,567), heterocyclic amine borane compounds (GB Pat. No. 1,011,000). The pH of this fogging bath (reversal bath) is wide ranging from acidic to alkaline.
2-12, preferably 2.5-10, particularly preferably 3
The range is from -9. Instead of the reversal bath, a light reversal process by re-exposure may be performed. Further, the reversal step can be omitted by adding the fogging agent to the color developing solution.

The color developing solution of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Aminophenol compounds are also useful as the color developing agent. However, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-.
N-β-hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developing solution contains, for example, a pH buffering agent such as an alkali metal carbonate, borate or phosphate.
It is common to include development inhibitors or antifoggants such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) s can be used. Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride. , Chelating agents such as auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, for example, Ethylenediamine tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo -
Typical examples thereof include N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

PH of these color developing solution and black and white developing solution
Is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material. When the replenishment amount is reduced, it is preferable to prevent the evaporation and air oxidation of the liquid by reducing the contact area of the processing liquid with air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

If necessary, various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The processing temperature of the color developing solution of the present invention is 20 to
It is 50 ° C., preferably 30 to 40 ° C. Processing time is 2
It is 0 seconds to 11 minutes. The smaller the replenishment amount, the better,
Photosensitive material 1 m ² per 1-3 liters, preferably 2.0
~ 2.5 liters.

If necessary, the color developing bath may be divided into two or more baths, and the color developing replenisher may be replenished from the foremost bath or the last bath to shorten the developing time or the replenishing amount. .

The light-sensitive material of the present invention is desilvered after color development. The desilvering process may be carried out immediately after color development without any other processing step. In addition, in order to prevent unknown post-development, air fogging, and to reduce the carry-in of the color developing solution to the desilvering process, and in the photographic light-sensitive material, for example, a sensitizing dye, a photosensitive material portion of a dye, In order to wash out and render harmless the color developing agent impregnated in the photographic light-sensitive material, it may be subjected to a bleaching treatment or a bleach-fixing treatment after the color developing treatment, for example, after the treatment steps of stopping, adjusting and washing.

The adjusting solution includes, for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-propanediaminetetraacetic acid, cyclohexanediaminetetraacetic acid, sulfites (for example, sodium sulfite and ammonium sulfite) and a bleaching ability. The bleaching accelerator described above (for example, thioglycerin, aminoethanethiol, sulfoethanethiol) can be contained in the treatment liquid having For the purpose of preventing scum, sorbitan esters of fatty acids substituted with ethylene oxide described in US Pat. No. 4,839,262, US Pat. No. 4,059,446, Research Disclosure 191, 19104 ( 198
It is preferable to contain the polyoxyethylene compound described in 0).

The photographic material of the present invention, after desilvering,
Washing with water and / or the above-mentioned treatment steps, for example stabilization, are carried out. It is also possible to use a simple treatment method in which the stabilizing treatment is carried out without substantially washing with water after the treatment having the fixing ability.

The washing water used in the washing step may contain known additives, if necessary. For example, inorganic phosphoric acid, aminopolycarboxylic acid, water softeners such as organic phosphoric acid, bactericides that prevent the growth of various bacteria and algae, antifungal agents (eg, isothiazolone, organochlorine fungicides, benzotriazole). A surfactant for preventing drying load and unevenness can be used. In addition, for example, L. E. West, “Water Qua
light Criteria ", Photo.Sci.a
nd. Eng. , Vol. 9, No. 6, P. 343-
The compounds described in 359 (1965) can also be used.

The washing step is preferably a multi-stage countercurrent system, and the number of stages is preferably 2 to 4. You may carry out two or more types of stabilizing solutions in multiple steps. The replenishment amount is 1 to 50 times, preferably 2 to 30 times the amount brought in from the previous bath per unit area.
Times, more preferably 2 to 15 times.

As the water used in the washing step, in addition to tap water, for example, water deionized to a Ca and Mg concentration of 5 mg / liter or less by an ion exchange resin, for example, water sterilized by halogen or an ultraviolet germicidal lamp. Is preferably used.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid in the washing step is caused to flow into a bath having a fixing ability as a pre-bath.

[0143]

【Example】

[Embodiment 1] The present invention will be specifically described below with reference to embodiments, but the present invention is not limited thereto. Preparation of Sample 101 A multilayer color light-sensitive material composed of each layer having the following composition was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm to prepare Sample 101. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use. First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High boiling point organic solvent Oil-1 0.1 g Dye E -1 microcrystalline solid dispersion 0.1 g Second layer: Intermediate layer Gelatin 0.40 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling point organic solvent Oil-3 0.1 g Dye D-4 0.4 mg Third layer: intermediate layer Finely grained silver iodobromide emulsion on the surface and inside (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) silver amount 0.05 g gelatin 0.4 g fourth layer : Low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.1 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C-3 0.05 g Coupler C-9 0.05 g Compound Cpd-C 10 mg High boiling point organic solvent Oil -2 0.1 g Additive P-1 0.1 g Fifth layer: Medium sensitivity red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C -3 0.2 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Additive P-1 0.1 g Seventh layer: intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-I 2.6 mg UV absorber U-1 0.01 g UV absorber U -0.002 g UV absorber U-5 0.01 g Dye 0.02 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling organic solvent Oil-1 0.02 g Eighth layer: Intermediate Silver iodobromide emulsion whose surface and inside are fogged (average grain size 0.06μ , Variation coefficient 16%, AgI content 0.3 mol%) Silver amount 0.02 g Gelatin 1.0 g Additive P-1 0.2 g Color mixing inhibitor Cpd-A 0.1 g Color mixing inhibitor Cpd-L 0.1 g 9th layer: low sensitivity Green-sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0.5 g Coupler C-7 0.35 g Compound Cpd-B 0.03 g Compound Cpd-C 10 mg Compound Cpd-D 0.02 g Compound Cpd-E 0.02g Compound Cpd-F 0.02g Compound Cpd-G 0.02g Compound Cpd-L 0.15g High boiling organic solvent Oil-1 0.23g High boiling organic solvent Oil-2 0.23g 10th layer: Medium sensitivity green sensitive emulsion Layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler C-4 0.4 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.05 g Compound Cpd-G 0.05 Compound Cpd-M 0.2 g High boiling organic solvent Oil-2 0.56 g 11th layer: High sensitivity green sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.5 g Compound Cpd-B 0.08 g Compound Cpd-C 5 mg compound Cpd-D 0.02 g compound Cpd-E 0.02 g compound Cpd-F 0.02 g compound Cpd-G 0.02 g compound Cpd-J 5 mg compound Cpd-K 5 mg compound Cpd-L 0.2 g high boiling organic solvent Oil- 1 0.35g High-boiling point organic solvent Oil-2 0.35g 12th layer: Intermediate layer Gelatin 0.6 g 13th layer: Yellow filter layer Yellow colloidal silver 0.07 g Gelatin 1.1 g Color mixture inhibitor Cpd-A 0.01 g High-boiling point organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of Dye E-2 0.05 g 14th layer: Intermediate layer Gelatin 0.6 g 15th layer: Low sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.2 g Emulsion K Silver amount 0.3 g Emulsion L Silver amount 0.1 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-6 0.1 g Coupler C-10 0.4 g 16th layer: Middle speed blue sensitive emulsion layer Emulsion L Silver amount 0.1 g Emulsion M Silver amount 0.4 g Gelatin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.1 g Coupler C-10 0.1 g 17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.2 g Coupler C-5 0.3 g Coupler C-6 0.6 g Coupler C-10 0.1 g Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.1 g 19th layer: second protective layer Colloidal silver Ag amount 0.1 mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1 mol%) ) Silver content 0.1 g 0.4 g 20th layer: third protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μ) 0.1 g Copolymer of methylmethacrylate and acrylic acid 4: 6 (average particle size 1.5 μ) 0.1 g Silicone Oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g In addition to the above composition, an additive F- was added to all emulsion layers.
1-F-8 were added. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer.

Further, as an antiseptic and antifungal agent, phenol, 1,
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol were added.

[0145]

[Table 1]

[0146]

[Table 2]

[0147]

[Chemical Formula 39]

[0148]

[Chemical 40]

[0149]

[Chemical 41]

[0150]

[Chemical 42]

[0151]

[Chemical 43]

[0152]

[Chemical 44]

[0153]

[Chemical formula 45]

[0154]

[Chemical formula 46]

[0155]

[Chemical 47]

[0156]

[Chemical 48]

[0157]

[Chemical 49]

[0158]

[Chemical 50]

[0159]

[Chemical 51]

[0160]

[Chemical 52] Ninth layer based on sample 101 (low sensitivity green sensitive emulsion layer)
Sample 102 was prepared in exactly the same manner as Sample 101, except that C-7 of Example 2 was changed to 0.46 g of the coupler M-22 of the present invention.

Next, with reference to Sample 102, the ninth layer (low sensitivity green sensitive emulsion layer) and the tenth layer (medium sensitivity green sensitive emulsion layer)
Sample 103 was prepared in exactly the same manner as Sample 102 except that the following non-photosensitive intermediate layer A was introduced between and.

Non-photosensitive intermediate layer A Gelatin 0.65 g / m ² Ninth layer based on Sample 101 (low-sensitivity green-sensitive emulsion layer)
C-7 was added to 0.46 g of the coupler M-22 of the present invention,
A sample 104 was prepared in exactly the same manner as the sample 101 except that the C-4 of the tenth layer (medium-speed green sensitive emulsion layer) was changed to 0.56 g of the coupler M-22 of the present invention.

Next, with reference to the sample 104, the sample except that the non-photosensitive intermediate layer A was introduced between the tenth layer (medium-sensitive green sensitive emulsion layer) and the eleventh layer (high-sensitive green sensitive emulsion layer). 1
Sample 105 was prepared in exactly the same manner as 04.

With reference to Sample 104, the eleventh layer (high-sensitivity green-sensitive emulsion layer) C-4 was used as coupler M-22 of the present invention.
A sample 106 was prepared in exactly the same manner as the sample 104 except that the amount was changed to 0.7 g.

Next, with reference to the sample 106, the ninth layer and the first layer
A sample 107 was prepared in the same manner except that the non-photosensitive emulsion layer A was introduced between the 0 layer and the 0 layer.

Then, a sample 108 was prepared in the same manner except that the non-photosensitive emulsion layer A was introduced between the ninth layer and the tenth layer based on the sample 101.

Next, based on the sample 101, Oil-1 and Oil-2 of the ninth layer were mixed with alcohol A.
46g, Oil-2 of the 10th layer was replaced with 0.56g of alcohol of A-4, and Oil of the 11th layer was further replaced.
Sample 109 was prepared in the same manner except that -1 and Oil-2 were replaced with 0.7 g of alcohol of A-4.

Oil- of the ninth layer based on sample 104
1 and Oil-2 were replaced with 0.46 g of alcohol of A-4, Oil-2 of the 10th layer was replaced with 0.56 g of alcohol of A-4, and Oil-1 and Oil-2 of the 11th layer were replaced with A Sample 110 was prepared in the same manner except that 0.7 g of alcohol of No. -4 was replaced.

Oil- of the ninth layer based on sample 105
1 and Oil-2 were replaced with 0.46 g of alcohol of A-4, Oil-2 of the 10th layer was replaced with 0.56 g of alcohol of A-4, and Oil-1 and Oil-2 of the 11th layer were replaced with A Sample 111 was prepared in the same manner except that the alcohol of No. -4 was replaced with 0.7 g.

Oil- of the ninth layer based on sample 106
1 and Oil-2 were replaced with 0.46 g of alcohol of A-4, Oil-2 of the 10th layer was replaced with 0.56 g of alcohol of A-4, and Oil-1 and Oil-2 of the 11th layer were replaced with A Sample 112 was prepared in the same manner except that the alcohol of No. -4 was replaced with 0.7 g.

Oil- of the ninth layer based on sample 107
1 and Oil-2 were replaced with 0.46 g of alcohol of A-4, Oil-2 of the 10th layer was replaced with 0.56 g of alcohol of A-4, and Oil-1 and Oil-2 of the 11th layer were replaced with A Sample 113 was prepared in the same manner except that the alcohol of No. -4 was replaced with 0.7 g.

Oil- of the ninth layer based on the sample 108
1 and Oil-2 were replaced with 0.46 g of alcohol of A-4, Oil-2 of the 10th layer was replaced with 0.56 g of alcohol of A-4, and Oil-1 and Oil-2 of the 11th layer were replaced with A Sample 114 was prepared in the same manner except that the alcohol of No. -4 was replaced with 0.7 g.

Table 3 shows the types of couplers, the presence or absence of the non-photosensitive intermediate layer, and the types of high-boiling organic solvents in the green-sensitive layers of these samples.

[0174]

[Table 3] The sample 101 prepared in this manner is used as JIS K760.
Exposure was carried out through a continuous wedge with the ISO daylight illuminant described on page 2-5, and the following development processing was carried out to measure the density. Then, the ISO speed was obtained by the method described on pages 3 to 4 of JISK7613.
It was 0.

Samples 101 to 11 thus obtained
After cutting 4 into strips form, it was exposed through an optical wedge to measure RMS graininess. The treatment was performed in the following steps. Aperture diameter is 48 for processing agent only sample
Measure magenta density with micro densitometer under the condition of μm
MS granularity was determined. RMS concentration 0.5 and 1.5
The measured values of the two points are shown. In practice, it is necessary to improve both low and high concentrations. Furthermore, the maximum density of magenta was measured.

Further, Samples 101 to 114 were processed into a 35 mm size Patrone form and actually photographed. The subjects were a Macbeth color checker and a set centered on red. The obtained practical sample was sensory-evaluated by a plurality of evaluators.

The results are summarized in Table 4.

[0178]

[Table 4] From the results in Table 4, it is clear that the combination of the present invention is superior in graininess to other conventionally known combinations. In particular, the graininess at D = 0.5 where the graininess is noticeable is extremely improved. 9th layer, 10th layer and 11th layer
In Samples 107 and 113 in which the magenta dye-forming coupler of the present invention was added to each layer, the graininess at D = 2.0 was also improved. It is also clear that the combinations of the invention are more saturated than those using pyrazolone couplers outside the invention.

Further, from the comparison of the graininess between Samples 111 and 105 of the present invention, Oil-1 and Oil-2 were compared with A-.
It can be seen that by changing to alcohol No. 4, the graininess is further improved and the maximum color density of magenta is increased.

Samples 109 to 114 were Nitrilo-N, N, N-trimethylenephosphonic acid.5 in the color developing solution.
The change in photographic property due to the variation in the amount of sodium salt and sodium sulfite was smaller than that of Samples 101 to 108.

The processing steps after exposure were as follows.

Treatment process time Temperature First development 6 minutes 38 ° C. Water washing 2 minutes 38 ° C. Inversion 2 minutes 38 ° C. Color development 6 minutes 38 ° C. Adjustment 2 minutes 38 ° C. Bleach 6 minutes 38 ° C. Settling 4 minutes 38 ° C. Washing with water 4 minutes 38 ° C Stability 1 minute 25 ° C The composition of each treatment solution was as follows. [First developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 1.5 g Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g Sodium sulfite 30 g Hydroquinone / potassium monosulfonate 20 g Potassium carbonate 15 g Heavy Sodium carbonate 12 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 mg Diethylene glycol 13 g Water added 1000 ml pH 9.60 pH is It was adjusted with hydrochloric acid or potassium hydroxide. [Reversal liquid] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3.0 g Stannous chloride dihydrate 1.0 g p-aminophenol 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml Water was added. 1000 ml pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide. [Color developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5-sodium salt 2.0 g Sodium sulfite 7.0 g Trisodium phosphate-12-hydrate 36 g Potassium bromide 1.0 g Potassium iodide 90 mg Sodium hydroxide 3.0 g citrazinic acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11 g 3,6-dithiaoctane-1,8- Diol 1.0 g Water was added 1000 ml pH 11.80 pH was adjusted with hydrochloric acid or potassium hydroxide. [Preparation liquid] Ethylenediaminetetraacetic acid / disodium salt / dihydrate 8.0 g Sodium sulfite 12 g 1-Thioglycerol 0.4 g Sodium formaldehyde bisulfite adduct 30 g Water added 1000 ml pH 6.20 pH is hydrochloric acid or sodium hydroxide I adjusted it with. [Bleaching solution] Ethylenediaminetetraacetic acid ・ disodium salt ・ dihydrate 2.0 g Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonium ・ dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water 1000 ml pH 5.70 pH Was adjusted with hydrochloric acid or sodium hydroxide. [Fixing solution] Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or aqueous ammonia. [Stabilizer] Benzisothiazolin-3-one 0.02 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Water was added to 1000 ml pH 7.0 [Example 2] Coupler M-22 of the present invention , M-14,
When the same experiment as in Example 1 was conducted by replacing M-26, M-32, and M-55 with each other, the same effect as in Example 1 was obtained. [Example 3] The same effect as in Example 1 was obtained when the same experiment as in Example 1 was carried out by changing the alcohol of A-4 to the alcohol of A-8. [Example 4] Sample 1 in Example of JP-A-2-124566
As a result of conducting the same experiment as in Example 1 with respect to 01, the same effect was obtained.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer on a support, wherein the green-sensitive emulsion layers have at least two different sensitivities. Layer having a silver halide emulsion layer, a non-photosensitive hydrophilic colloid layer provided between any two layers of the green-sensitive emulsion layer, and at least one of the green-sensitive emulsion layers having the following general formula [ A silver halide color photographic light-sensitive material containing at least one magenta dye-forming coupler represented by M]. General formula [M] Here, R ₁ represents a hydrogen atom or a substituent. Z represents a group of non-metal atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein each layer of the green color-sensitive emulsion layer contains at least one magenta dye-forming coupler represented by the formula [M]. 3. The silver halide according to claim 1, wherein at least one layer containing the general formula [M] contains at least one compound represented by the following general formula [N]. Color photographic light-sensitive material. [Chemical 2] In the formula, at least one of R ₁ , R ₂ , and R ₃ represents a substituted or unsubstituted alkyl or alkenyl group, and R
The sum of carbon numbers of ₁ , R ₂ , and R ₃ is 10 or more. The substituents which the above alkyl, alkenyl and aralkyl groups may have are a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxy group, a sulfo group and an amino group. , Alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group , An alkoxycarbonyl group, a heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group,
Aryloxycarbonyl group, an acyl group, or a substituent such as an azolyl group, preferably a halogen atom,
It is an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group, a sulfonyl group, an alkoxycarbonyl group, an acyloxy group, or an acyl group.