JPH0588319A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material high in sensitivity and smooth in gradation from the low exposure region to the high exposure region of the characteristic curve and superior in linearity. CONSTITUTION:The silver halide emulsion layer of the silver halide color photographic sensitive material contains a magenta coupler represented by formula I and a magenta coupler represented by formula II. In formula I and II, Z is a nonmetallic atomic group necessary to form an N-containing hetero ring; X is a group to be released by coupling with the oxidation product of a color developing agent: RA is halogen or alkoxy; RB is acylamino, sulfonamido, imido, carbamoyl, sulfamoyl, alkoxycarbonyl, alkoxycarbonylamino, or alkoxy; and I is an integer of 0-4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having a high sensitivity and a smooth gradation from a low exposure region to a high exposure region.

[0002]

BACKGROUND OF THE INVENTION Silver halide color photographic light-sensitive materials include
Usually, a yellow coupler, a magenta coupler and a cyan coupler are used in combination. Among these, as the magenta coupler, pyrazolone, pyrazolinobenzimidazole, indanone-based coupler and the like have been known, but in recent years, U.S. Pat. Nos. 3,725,065 and 3,810,761. Calligraphy, No. 3,758,309
The pyrazolotriazole-based couplers described in Japanese Patent No. 3,728,067 have been used.

These couplers have many advantages such as little secondary absorption, advantageous color reproducibility, and excellent color developability.

By the way, the general-purpose color negative film is loaded into a camera and used to photograph various subjects under various conditions. The latitude is designed to be wide so that an image can be recorded even if it is slightly deviated from the proper exposure, or more image information can be recorded.

That is, in producing the color negative film, the characteristic curve (horizontal axis GS-log E, E: exposure amount, vertical axis represents image density) from the low exposure area to the high exposure area is smooth. Is required.

However, the color negative film using the above-mentioned pyrazolotriazole-based coupler has excellent color forming property, so that the gamma in the low exposure region is high and the density is close to the maximum density in the medium exposure region, so that high exposure is performed. In the range, gamma decreases, making it difficult to obtain a smooth characteristic curve. In order to overcome this difficulty, it has been attempted to use a compound (hereinafter, referred to as a DIR compound) that releases a development inhibitor at the time of development, but it has a drawback that sensitivity is lowered in a low density portion. Was there.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material having high sensitivity and having a smooth gradation from a low exposure area to a high exposure area.

[0008]

The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer comprises:
A silver halide color photographic light-sensitive material containing at least one magenta coupler represented by the following general formula [MI] and at least one magenta coupler represented by the following general formula [M-II]. Achieved by the material.

[0009]

[Chemical 3] [In the formula, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a substituent which is released by the reaction with the oxidized product of the color developing agent. R represents a hydrogen atom or a substituent. ]

[0010]

[Chemical 4] [In the formula, R _A represents a halogen atom or an alkoxy group, and R _B represents an acylamino group, a sulfonamide group, an imide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an alkoxycarbonylamino group, or an alkoxy group. l represents an integer of 0 to 4. First, the magenta coupler represented by the general formula [MI] according to the present invention (hereinafter, referred to as magenta coupler [MI]) will be described.

The substituent represented by R is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl groups. In addition, halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano,
Alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio Each group, a spiro compound residue, a bridged hydrocarbon compound residue and the like are also included.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

As the sulfonamide group represented by R,
Examples thereof include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R is preferably one having 2 to 32 carbon atoms, and the cycloalkyl group is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The alkenyl group may be linear or branched. Good.

The cycloalkenyl group represented by R is preferably a cycloalkenyl group having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

The sulfonyl group represented by R is an alkylsulfonyl group, an arylsulfonyl group or the like; the sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group or the like; and the phosphonyl group is an alkylphosphonyl group or an alkoxyphosphonyl group. , An aryloxyphosphonyl group, an arylphosphonyl group, etc .; as an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .;
As the carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group and the like; as the sulfamoyl group,
An alkylsulfamoyl group, an arylsulfamoyl group, etc .; an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .; a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; an ureido group , An alkylureido group, an arylureido group, etc .; As a sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc .; As a heterocyclic group, a 5- to 7-membered one is preferable. Is a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group, etc .; As the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferable, for example, 3,4,5,
6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-oxy group, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, 2-pyridylthio group, 2-benzo Thiazolylthio group, 2,4-
Diphenoxy-1,3,5-triazole-6-thio group, etc .; Siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; Imido group, succinimide group, 3-heptadecylsuccinic group Acid imide group, phthalimide group, glutarimide group, etc .; Spiro compound residues include spiro [3.3] heptan-1-yl, etc .; Bridged hydrocarbon compound residues include
Bicyclo [2.2.1] heptan-1-yl, tricyclo [3.3.1.1 ^3,7 ] decan-1-yl, 7,7-
Dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

Examples of the group which can be split off by the reaction with the oxidation product of the color developing agent represented by X include a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyl. Oxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom,
Alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl,

[0021]

[Chemical 5] (R ₁ ′ has the same meaning as R above, Z ′ has the same meaning as Z above, and R ₂ ′ and R ₃ ′ each represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group). Can be mentioned,
Preferred is a halogen atom, especially a chlorine atom.

The nitrogen-containing heterocycle formed by Z or Z'includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring and the like, and the substituent which the ring may have is the above-mentioned R. Are mentioned.

The general formula [M-I] is more specifically represented by, for example, the following general formulas [M-I-1] to [M-I-6].

[0024]

[Chemical 6] In the general formulas [M-I-1] to [M-I-6], R is
_{1 to} R ₈ and X have the same meanings as R and X above. Further, among the general formula [MI], the following general formula [M-
I-7].

[0025]

[Chemical 7]R in the formula₁, X and Z ″ Is R in the general formula [M-I],
It is synonymous with X and Z.

The above general formulas [M-I-1] to [M-I-]
Among the magenta couplers represented by [6], the magenta coupler represented by the general formula [MI-1] is particularly preferable.

The most preferred substituents R and R ₁ on the heterocycle are those represented by the following general formula [MI-8]. Formula [M-I-8] R 9 -CH 2 - wherein, R ₉ is as defined above R. R ₉ is preferably a hydrogen atom or an alkyl group.

Further, by the Z in the general formula [MI],
Formed ring and Z in the general formula [M-I-7] ″ By
Substituents that the ring formed may have, as well as the general formula
R in [M-I-1] to [M-I-5]₂~ R₈age
Of these, those represented by the following general formula [MI-9] are preferable.
Yes. General formula [M-I-9] -R¹ -SO₂-R² Where R¹Is an alkylene group, R²Is an alkyl group, cyclo
It represents an alkyl group or an aryl group.

The alkylene group represented by R ¹ preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms.
And may be linear or branched.

R² The cycloalkyl group represented by
Those having 5 to 6 members are preferable.

Typical examples of the magenta coupler [MI] are shown below.

[0032]

[Chemical 8]

[0033]

[Chemical 9]

[0034]

[Chemical 10]

[0035]

[Chemical 11]

[0036]

[Chemical formula 12]

[0037]

[Chemical 13]

[0038]

[Chemical 14]

[0039]

[Chemical 15]

[0040]

[Chemical 16]

[0041]

[Chemical 17]

[0042]

[Chemical 18]

[0043]

[Chemical 19]

[0044]

[Chemical 20]

[0045]

[Chemical 21] In addition to the typical examples of the magenta coupler [MI] described above, specific examples of the magenta coupler [MI] include pages (18) to (32) of JP-A-62-166339.
Among the compounds listed on the page, Nos. 1-4, 6, 8
~ 17, 19-43, 45-59, 61-104, 10
The compound shown by 6-121,123-162,164-223 can be mentioned.

Further, the coupler is a Journal of the Chemical Society.
Society), Perkin I (1977),
2047-2052, U.S. Pat. No. 3,725,067,
JP-A-59-99437, JP-A-58-42045, JP-A-59-162548, JP-A-59-171956 and JP-A-6.
0-33552, 60-43659, 60-1
72982, 60-190779, and 62-20
It can be synthesized with reference to Nos. 9457 and 63-307453.

Next, the above general formula [M-II] according to the present invention.
The magenta coupler represented by (hereinafter referred to as magenta coupler [M-II]) will be described.

In the general formula [M-II], the halogen atom represented by R _A is, for example, a chlorine atom, a bromine atom,
A fluorine atom may be mentioned, and as the alkoxy group,
Examples thereof include a methoxy group and a dodecyloxy group. R
Preferred as _A is a chlorine atom.

As the acylamino group represented by R _B ,
Examples thereof include a 2,4-di-t-pentylphenoxyacetamide group and a 4- (2,4-di-t-pentylphenoxy) butanamide group. Examples of the sulfonamide group include:
For example, a 4-dodecyloxyphenylsulfonamide group can be mentioned, an imide group can be, for example, an octadecenylsuccinimide group, and a carbamoyl group can be, for example.
Examples include 4- (2,4-di-t-pentylphenoxy) butylaminocarbonyl group, examples of the sulfamoyl group include tetradecanesulfamoyl group, and examples of the alkoxycarbonyl group include tetradecaneoxycarbonyl group. Examples of the alkoxycarbonylamino group include a dodecyloxycarbonylamino group, and examples of the alkoxy group include a methoxy group, an ethoxy group, and an octyloxy group. Preferable for R _B is p for R _A
It is an acylamino group substituted at position. Also, l is preferably 1.

Hereinafter, the above general formula [M-I according to the present invention will be described.
Specific examples of the compound represented by the formula [I] are shown below, but the present invention is not limited thereto.

[0051]

[Chemical formula 22]

[0052]

[Chemical formula 23] These magenta couplers [M-II] are 1-phenyl-
General synthetic methods for synthesizing 5-pyrazolone compounds, for example, US Pat. Nos. 2,369,489 and 2,3
76,380, 2,472,581, 2,600,788, 2,93.
No. 3,391, No. 3,615,506, British Patent No. 956,261, No. 1,13.
It can be synthesized by the method described in Japanese Patent No. 4,329 and Japanese Patent Publication No. 45-20636.

A specific synthesis example of the magenta coupler [M-II] is shown below. Synthesis Example (Synthesis of Exemplified Compound II-5) 1-Pentachlorophenyl-3-in 75 ml of ethyl acetate
11.2-g of (2-chloro-5-aminoanilino) -5-pyrazolone was added, 20 ml of water in which 2.7 g of sodium acetate was dissolved was added, and the mixture was stirred for 1 hour. Next, 9.2 g of 4- (2,4-di-t-pentylphenoxy) butanoyl chloride dissolved in 25 ml of ethyl acetate was added over 10 minutes. After stirring for 3 hours, the aqueous layer was removed, washed with 50 ml of water, and ethyl acetate was removed by distillation under reduced pressure. The obtained residue was recrystallized from toluene to obtain 12.8 g of the desired product. White crystals, melting point 125-127 ° C. The compound was identified by Mass, NMR and IR spectra, and it was confirmed that the compound was Exemplified compound M-5.

The magenta coupler [MI] of the present invention is
Usually, 1 × 10 ⁻³ mol to 1 mol per mol of silver halide,
Preferably, it can be used in the range of 1 × 10 ^-2 mol to 8 × 10 ^-1 mol.

Further, the magenta coupler [M-II] of the present invention.
Is 1 × 10 ⁻³ to 1 mol per mol of silver halide,
Preferably, it can be used in the range of 1 × 10 ^-2 mol to 8 × 10 ^-1 mol.

In the present invention, the magenta coupler [M-
I "and the magenta coupler [M-II] are added together in one silver halide emulsion layer, the molar ratio of the magenta coupler [MI] and the magenta coupler [M-II] is 1".
0: 1 to 1: 5 are preferable, and 5: 1 to 1: 3 are more preferable. The couplers of this invention can be used with other types of magenta couplers.

Further, the magenta coupler [MI] of the present invention.
And magenta coupler [M-II] can be separately used in two or more silver halide emulsion layers having the same color sensitivity. For example, a high-sensitivity silver halide emulsion layer and a low-sensitivity silver halide emulsion layer can be used separately.

In the present invention, the magenta coupler [M-
I] and the magenta coupler [M-II] are preferably contained in at least one of the green-sensitive silver halide emulsion layers.

In order to incorporate the magenta coupler [M-I] and the magenta coupler [M-II] into the silver halide emulsion layer, a conventionally known method such as known dibutyl phthalate or tricresyl phosphate can be used. The magenta coupler [M-I] and the magenta coupler [M-II] are dissolved in a mixed solution of a high-boiling solvent and a low-boiling solvent such as butyl acetate and ethyl acetate, either alone or in combination, and then the surface activity is dissolved. A method of mixing with an aqueous gelatin solution containing an agent, then emulsifying and dispersing using a high speed rotating mixer, a colloid mill or an ultrasonic disperser, and then directly adding to the emulsion can be adopted. Further, after setting the above emulsified dispersion, it may be shredded, washed with water, and then added to the emulsion.

As the silver halide emulsion used in the light-sensitive material of the present invention, any ordinary silver halide emulsion can be used. The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder of the emulsion.

The emulsion layer and other hydrophilic colloid layers may be hardened, and may contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer. A coupler is used in the emulsion layer of the color photographic light-sensitive material.

Further, by coupling with colored couplers, competing couplers and oxidized products of developing agents, which have the effect of color correction, development accelerators, bleaching accelerators, developers, silver halide solvents, toning agents, hardeners and hardeners Compounds that release photographically useful fragments such as film agents, fog agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or emulsion layers,
Dyes may be included which are bleached or bleached from the light-sensitive material during the development process. For the light-sensitive material, formalin scavenger, fluorescent whitening agent, matting agent, lubricant, image stabilizer, surfactant, color fog inhibitor, development accelerator,
Development retarders and bleaching accelerators can be added.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

In order to obtain a dye image by using the light-sensitive material of the present invention, a commonly known color photographic process can be carried out after exposure.

[0067]

EXAMPLES Specific examples of the present invention will be described below.
Embodiments of the invention are not limited to these. Example 1 In Example, the addition amount in the silver halide photographic light-sensitive material
Is 1m unless otherwise specified² The hit one is shown. Also, halo
Silver genide is shown in terms of silver, sensitizing dyes and couplers
It is shown per mol of silver in the same layer.

A multi-layer color photographic light-sensitive material (Sample 101) was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support. Sample 1 (Comparison) First layer: Antihalation layer (HC) Gelatin layer containing black colloidal silver.

Dry film thickness 3 μm Second layer; Intermediate layer (IL) Gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Dry film thickness 1.0 μm Third layer; low-sensitivity red-sensitive silver halide emulsion layer (RL) Average grain size 0.3 μm, AgBrI containing 3 mol% AgI
Monodisperse emulsion consisting of (Emulsion I: 12% wide distribution) 1.8 g Sensitizing dye I 6.0 × 10 ⁻⁴ mol Sensitizing dye II 1.0 × 10 ⁻⁴ mol Cyan coupler (C-1) 0.06 mol Colored cyan coupler (CC-1) 0.003 mol DIR compound (D-1) 0.0015 mol DIR compound (D-2) 0.002 mol Dioctyl phthalate 0.6 g Dry film thickness 3.5 μm 4 layers; high-sensitivity red-sensitive silver halide emulsion layer (RH) AgBrI containing 0.5 μm average grain size and 3 mol% AgI
Monodisperse emulsion consisting of (Emulsion II: 12% distribution) 1.3 g Sensitizing dye I 3.0 × 10 ⁻⁴ mol Sensitizing dye II 1.0 × 10 ⁻⁴ mol Cyan coupler (C-1) 0.02 mol Colored cyan coupler (CC-1) 0.0015 mol DIR compound (D-2) 0.001 mol Dioctyl phthalate 0.2 g Dry film thickness 2.5 μm Fifth layer; Intermediate layer (IL) Second layer Same as the gelatin layer.

Dry film thickness 1.0 μm Sixth layer; low-sensitivity green-sensitive silver halide emulsion layer (GL) Emulsion I 1.2 g Sensitizing dye III 2.5 × 10 ⁻⁴ mol Sensitizing dye IV 1.2 × 10 ⁻⁴ mol The magenta coupler (I-5) 0.07 mol Colored magenta coupler (CM-1) 0.009 mol DIR compound (D-1) 0.0010 mol DIR compound (D-3) 0.0030 mol Tricresyl phosphate 0.5 g Dry film thickness 3.5 μm 7th layer; High-sensitivity green-sensitive silver halide emulsion layer (GH) Emulsion II 1.3 g Sensitizing dye III 1.5 × 10 ⁻⁴ mol Sensitizing dye IV 1.0 × 10 ⁻⁴ mol The magenta coupler (I-5) 0.020 mol Colored magenta coupler (CM-1) 0.002 mol DIR compound (D-3) 0.0010 mol tricresyl phosphate 0 ． g dry thickness 2.5μm eighth layer; yellow filter layer (YC) gelatin layer containing emulsified dispersion of yellow colloidal silver and 2,5-di -t- octylhydroquinone.

Dry film thickness 1.2 μm 9th layer; low-sensitivity blue-sensitive silver halide emulsion layer (BL) Average grain size 0.48 μm, AgBr containing 3 mol% of AgI
Monodisperse Emulsion Consisting of I (Emulsion III: 12% Distribution) 0.9 g Sensitizing Dye V 1.3 × 10 ⁻⁴ mol Yellow Coupler (Y-1) 0.29 mol Tricresyl Phosphate 5 g Dry film thickness 3.5 μm 10th layer; High-sensitivity blue-sensitive silver halide emulsion layer (BH) Average grain size 0.8 μm, AgBrI containing 3 mol% AgI
Monodisperse emulsion consisting of (Emulsion IV: 12% wide distribution) 0.5 g Sensitizing dye V 1.0 × 10 ⁻⁴ mol Yellow coupler (Y-1) 0.08 mol DIR compound (D-2) 0 .0015 mol tricresyl phosphate 0.10 g dry film thickness 2.5 μm 11th layer; first protective layer (PRO-1) silver iodobromide emulsion (AgI 2 mol%, average particle size 0.07 μm)
m,) 0.5 g A gelatin layer containing ultraviolet absorbers (UV-1) and (UV-2). Dry film thickness 2.0 μm 12th layer; Second protective layer (PRO-2) Polymethylmethacrylate particles (diameter 1.5 μm) and formalin scavenger (HS-1), (HS-2)
A gelatin layer containing.

Dry film thickness 1.5 μm In addition to the above composition, a gelatin hardening agent (H-
1), (H-2) and a surfactant were added. Sensitizing Dye I Anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing Dye II Anhydro-9-ethyl-3,3'- The-
(3-Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III Anhydro-5,5'-diphenyl-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide Sensitizing dye IV Anhydro-9-ethyl-3,3'-di-
(3-Sulfopropyl) -5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide Sensitizing dye V Anhydro-3,3'-di- (3-sulfopropyl) -4,5-benzo-5 ′ -Methoxythiacyanine hydroxide

[0074]

[Chemical formula 24]

[0075]

[Chemical 25]

[0076]

[Chemical formula 26] Next, in Sample 1, the magenta couplers (I-5) of the sixth and seventh layers were replaced as shown in Table 1, and Sample 10 was replaced.
2-118 were created.

The photographic material prepared as described above was subjected to wedge exposure by a usual method, and then developed by the following steps. Processing process

[0078]

[Table 1] The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used. Color developer Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl -N-Ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to 1 liter and potassium hydroxide or 20% was added.
Adjust to pH 10.06 with sulfuric acid. Color development replenisher water 800 ml potassium carbonate 35 g sodium hydrogen carbonate 3 g potassium sulfite 5 g sodium bromide 0.4 g hydroxylamine sulfate 3.1 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline Sulfate 6.3g Potassium hydroxide 2g Diethylenetriaminepentaacetic acid 3.0g Water to make 1 liter, potassium hydroxide or 20%
Adjust to pH 10.18 with sulfuric acid. Bleaching solution Water 700 ml 1,3-Diaminopropanetetraacetic acid ferric ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Water is added to make 1 liter, and pH is 4.4 using ammonia water or glacial acetic acid. Adjust to. Bleaching replenisher Water 700 ml 1,3-Diaminopropanetetraacetic acid Ferric ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting the pH to 4.0 using ammonia water or glacial acetic acid, add water. Set to 1 liter. Fixing solution Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using glacial acetic acid or ammonia water, add water to make 1 liter. Fixing replenisher Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using glacial acetic acid or ammonia water, add water to make 1 liter. Stabilizing solution and stabilizing replenishing solution Water 900 ml Chemical 27 2.0 g

[0079]

[Chemical 27] Dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UC-L-77) 0.1 g Ammonia water 0.5 ml After adding water to make 1 liter, Ammonia water or 50
Adjust to pH 8.5 with% sulfuric acid.

For each sample obtained by the development processing, X
The transmission density was measured using a Status M filter with a densitometer 310 type manufactured by -rite, and a D-(-logE) characteristic curve was created. The sensitivity of each sample was obtained from the reciprocal of the exposure amount required to give a density of fog +0.3, and shown in Tables 1 and 2 as relative sensitivity with the sensitivity of Sample 101 being 100.
Regarding each characteristic curve of the measured green light density (G) of each sample, from the point of density 1.0, ΔlogE = 1.0, the slope (γ ₁ ) from the density point on the high exposure region side, and from the point of density 1.5, Δ log
E = 1.0 Slope (γ ₂ ) with respect to the density point on the high exposure area side,
Tables 2 and 3 show each data of the slope (γ ₃ ) with respect to the density point on the high exposure region side from the point of the density of 2.0 to ΔlogE = 1.0.

[0081]

[Chemical 28]

[0082]

[Table 2]

[0083]

[Table 3]As is clear from the results of Tables 2 and 3, Comparative Sample 10
1 to 105, the sensitivity is low, and the characteristic curve has low exposure.
There is a gradational swell from the area to the high exposure area.
Not good. On the other hand, samples 106 to 118 of the present invention
Is sensitive and γ ₁, Γ₂, Γ₃Equal and smooth
It has a linear tone and shows that it is excellent
It

[0084]

The silver halide color photographic light-sensitive material of the present invention has high sensitivity, smooth gradation from the low-exposure region to the high-exposure region of the characteristic curve, and excellent linearity.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer has the following general formula [M-
I], at least one of magenta couplers represented by
A silver halide color photographic light-sensitive material containing at least one magenta coupler represented by the following general formula [M-II]. [Chemical 1] [In the formula, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a substituent which is released by the reaction with the oxidized product of the color developing agent. R represents a hydrogen atom or a substituent. ] [Chemical 2] [In the formula, R _A represents a halogen atom or an alkoxy group, and R _B represents an acylamino group, a sulfonamide group, an imide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an alkoxycarbonylamino group, or an alkoxy group. l represents an integer of 0 to 4. ]