JPH10142761A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To industrially and inexpensively produce a silver halide color photographic sensitive material having high sensitivity and high coloring property, less liable to cause bleach fog and excellent in color reproducibility by incorporating a specified coupler into one of silver halide emulsion layers. SOLUTION: At least one kind of coupler represented by the formula is incorporated into at least one of silver halide emulsion layers. In the formula, R1 is alkyl or aryl, R2 is alkyl or aryl, preferably aryl, R3 is alkyl, aryl or NHR, (R. is alkyl or aryl), R4 is a substituent, (m) is an integer of 0-4, in the case of m>=2, plural, R4 's may be different from each other, R5 is an arom. group, preferably trichlorophenyl and R4 at the o-position to N is alkoxy or halogen.

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 high sensitivity, high color development, low bleaching fog and excellent color reproducibility.

[0002]

2. Description of the Related Art At present, a color reduction method is used for a silver halide color photographic light-sensitive material (hereinafter also simply referred to as a light-sensitive material), and a combination of three dyes derived from a yellow coupler, a magenta coupler and a cyan coupler. Thus, a color image is formed.

As magenta couplers used in conventional silver halide color photographic light-sensitive materials, pyrazolone, pyrazolinobenzimidazole or indanone couplers are known. Among them, various 5-pyrazolone derivatives are widely used. ing.

Examples of the substituent at the 3-position of the 5-pyrazolone ring of the 5-pyrazolone derivative include an alkyl group, an aryl group, an alkoxy group described in US Pat. No. 2,439,098, and a US Pat. 2,369,48
An acylamino group described in JP-A No. 9 and 2,600,788 and a ureido group described in JP-A No. 3,558,319 are used. However, the above couplers have a low coupling activity with the oxidation product of the developing agent, so that a high-density magenta dye image cannot be obtained, and a large fluctuation in color density (developing pH fluctuation) due to a fluctuation in the pH of the developing solution. However, there are disadvantages such as that the secondary absorption in the blue light region of the magenta dye image obtained by color development is large, and the main absorption is poor on the long wavelength side.

[0005] Representative couplers conventionally used are described below.

[0006]

Embedded image

[0007] 3-acylamino-5-pyrazolone couplers have been widely used since ancient times because the spectral absorption of image-forming dyes obtained by development is relatively inexpensive and is consistent with the requirements of color negative films. Comparative compound M which is a representative 3-acylamino-5-pyrazolone coupler
-1 has the above-mentioned features, but has the problems that it is difficult to obtain a photosensitive material with high sensitivity and that the amount of silver halide and coupler required for obtaining an image forming dye having a constant density is large. Was.

3-anilino-5, such as comparative compound M-2
-Pyrazolone couplers have a higher coupling speed with oxidized developing agents and are easier to obtain high-sensitivity photosensitive materials than 3-acylamino-5-pyrazolone couplers, but have short-wavelength spectral absorption of image-forming dyes formed by development. And the color reproducibility of the print deteriorates. Further, the problem that the amounts of silver halide and coupler required for obtaining an image-forming dye having a constant density are not solved.

Comparative compound M-3 having a specific substituent
3-anilino-5-pyrazolone couplers such as those described above have a high coupling speed with an oxidized developing agent, so that a photosensitive material having high sensitivity is easily obtained, and the spectral absorption of an image-forming dye formed by development is a comparative compound M-1. And had favorable characteristics as a magenta coupler for color negative. However, the problem of a large amount of silver halide and coupler required to obtain an image forming dye having a constant density has not been solved.

A 4-arylthio-3-anilino-5-pyrazolone coupler such as a comparative compound M-4 having a group capable of coupling and leaving with the oxidized developing agent has a very high coupling rate with the oxidized developing agent. It was easy to obtain a photosensitive material with high sensitivity at high speed, and, like M-3, the spectral absorption of the image-forming dye produced by development was close to that of Comparative Compound M-1, and had favorable characteristics. The amount of silver halide and coupler required to obtain an image-forming dye having a low density is small, which contributes to cost reduction, and also enables thinning of a light-sensitive material, and has an advantage in sharpness.

However, the comparative compound M-4 and similar couplers having an acylamino-substituted phenylthio group have the problem of causing the so-called bleaching fogging phenomenon which causes non-image-like fogging in the bleaching bath. The increase in fog is not preferable for the light-sensitive material, and the amount of bleached fog varies depending on the processing conditions, which makes it difficult to obtain the same quality.

Thus, there has been a strong demand for eliminating the bleaching fog of 4-arylthio-3-anilino-5-pyrazolone couplers. Furthermore, Comparative Compound M-4 and similar couplers having an acylamino-substituted phenylthio group had significantly poor crystallinity and were difficult to purify by recrystallization. It is difficult to industrially produce couplers that cannot be purified by recrystallization at low cost, and improvement in crystallinity has been awaited.

4-phenylthio- having a sulfonamino group on the phenylthio group at the 4-position such as the comparative compound M-5
A 3-anilino-5-pyrazolone coupler is preferable in terms of low bleaching fog, but it is difficult to obtain a photosensitive material having high sensitivity, and a large amount of coupler is required to obtain an image forming dye having a constant density. Met.

As described above, the spectral absorption of the image-forming dye obtained by development is appropriate, a high-sensitivity light-sensitive material can be easily obtained, and the silver halide and the coupler necessary for obtaining the image-forming dye having a certain density can be obtained. An ideal coupler which is small in quantity, does not cause bleaching fog, and can be produced industrially at low cost has not been known, and its development has been awaited.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity, high color development and low bleaching fog.

A second object of the present invention is to provide a silver halide color photographic material having excellent color reproducibility.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material which can be industrially manufactured at low cost.

[0018]

[Means for Solving the Problems]

(1) In a silver halide color photographic light-sensitive material having a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, In at least one of the silver emulsion layers,
A silver halide color photographic material comprising at least one coupler represented by the following general formula [I].

[0019]

Embedded image

In the formula, R ₁ represents an alkyl group or an aryl group, R ₂ represents an alkyl group or an aryl group, and R ₃ represents an alkyl group, an aryl group or a group represented by NHR ₆ . R ₆ represents an alkyl group or an aryl group. R ₄ represents a substituent, and m represents an integer of 0 to 4. When m is 2 or more, a plurality of R ₄ may be the same or different. R ₅ represents an aromatic group.

(2) The silver halide color photographic light-sensitive material as described in (1), wherein in the general formula [I], R ₂ is an aryl group.

(3) The silver halide color photographic material as described in (1) or (2), wherein in the general formula [I], R ₅ is a trichlorophenyl group.

(4) In the above formula (I), at least one of the substituents at the position ortho to the nitrogen atom in R ₄ is an alkoxy group or a halogen atom. The silver halide color photographic light-sensitive material according to 2) or 3).

(5) A silver halide color photographic light-sensitive material having a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, A silver halide color photographic light-sensitive material characterized in that at least one of the silver halide emulsion layers contains at least one kind of coupler represented by the following general formula [II].

[0025]

Embedded image

In the formula, R ₁₁ represents an alkyl group, R ₁₂ represents an aryl group, and R ₁₃ represents an alkyl group or a group represented by NHR ₁₄ . R ₁₄ represents an alkyl group or an aryl group.

Hereinafter, the present invention will be described specifically.

R _{1 in the} general formula [I] and R _{11 in the} general formula [II] represent an alkyl group or an aryl group. Specifically, a butyl group, a hexyl group, an acetyl group, a 2-ethylhexyl group, a 2-methoxyethyl group, a phenyl group, a tolyl group,
-Chlorophenyl group, benzyl group and the like. R _{1 in the} general formula [I] and R _{11 in the} general formula [II] are preferably an alkyl group for ease of synthesis.

R _{2 in the} general formula [I] and R _{12 in the} general formula [II] represent an alkyl group or an aryl group. In particular,
The same groups as those for R ₁ and R ₁₁ can be exemplified. R ₂ of the general formula [I] and R ₁₂ of the general formula [II] are preferably an aryl group from the viewpoint of good crystallinity.

R _{4 in the} general formula [I] represents a substituent. In terms of color reproducibility and crystallinity, R ₄ is preferably substituted at the ortho position with respect to the nitrogen atom, and R ₄ is more preferably a halogen atom or an alkoxy group.

R _{5 in the} general formula [I] is preferably a 2,4,6-trichlorophenyl group from the viewpoint of color reproducibility and inexpensiveness.

Next, typical specific examples of the magenta coupler used in the present invention will be shown, but the present invention is not limited thereto.

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

Next, specific synthesis examples of the magenta coupler represented by the general formula [I] of the present invention will be described. General synthesis methods, for example, US Pat. Nos. 2,369,489 and 2 No. 2,376,380, No. 2,472,581, No. 2,600,788, No. 2,933,391,
Nos. 3,615,506 and 3,907,571
No., UK Patent Nos. 956,261 and 1,134,3
No. 29, JP-B-45-20636, JP-A-2-391
The compound can be synthesized with reference to the synthesis method described in No. 48 or the like.

Specific examples of the synthesis of the magenta coupler represented by the general formula [I] are shown below.

Synthesis Example 1 Synthesis of Exemplified Compound 1

[0040]

Embedded image

To 12.42 g of 2,2-dithiodianiline, 150 ml of acetonitrile and 10.90 g of pyridine are added and dissolved. Subsequently, 21.93 g of p-toluenesulfonyl chloride dissolved in 73 ml of acetonitrile is added, the mixture is heated to 60 ° C., and reacted for 1 hour. After adding 7 g of p-toluenesulfonyl chloride, the reaction is further performed for 1 hour. The reaction solution is poured into 150 g of ice water to which 5 g of hydrochloric acid is added, and the precipitate is collected by filtration, washed with 300 ml of water, and dried. 26.06 g of a pale yellow solid of Compound 1 was obtained. (Yield 93%) The structure of Compound 1 was confirmed by NMR spectrum and mass spectrum.

Next, to 5.57 g of the compound 1 were added 7.72 g of a 28% methanol solution of sodium methoxide and 45 ml of methanol, and the mixture was heated under reflux for 1 hour. To this, 7.73 g of 1-bromooctane is added, and after refluxing for 7 hours, 4.0 g of 1-bromooctane is added, followed by further refluxing for 12 hours. Ethyl acetate was added to the reaction solution, and the mixture was washed with diluted hydrochloric acid.
After adjusting to 2, wash with water. The solvent was distilled off and hexane 10m
When recrystallized from 1, Compound 6.3 was obtained as white crystals.
6 g were obtained. The structure of Compound 2 was confirmed by NMR spectrum and mass spectrum. (Yield 81%) To 0.7 g of the compound 2, 3 ml of ethyl acetate and 0.12 g of sulfuryl chloride are added, and the mixture is heated to 50 ° C. and stirred for 10 minutes. 0.95 g of compound 3 and 4 ml of DMF were added, and 50
The mixture was reacted at ℃ for 1 hour, ethyl acetate was added, and the mixture was washed with water. The solvent was distilled off, and this was recrystallized from a mixed solvent of ethyl acetate-acetonitrile to give Exemplified Compound 1 (0.77 g).
Was obtained (yield 50%). The structure of the exemplified compound was confirmed by NMR spectrum and mass spectrum.

Other exemplified compounds can be synthesized in the same manner as described above.

The magenta coupler of the present invention is generally used in an amount of 1 × 10 ^-3 mol to 8 × 10 ^-1 mol per mol of silver halide.
1, preferably 1 × 10 ⁻² mol to 8 × 10 ⁻¹ mol.

The magenta coupler of the present invention can be used in combination with another type of magenta coupler.

In order to incorporate the magenta coupler of the present invention, a conventional method, for example, a mixed solution of a known high-boiling solvent such as dibutyl phthalate or tricresyl phosphate and a low-boiling solvent such as butyl acetate or ethyl acetate is used. Alternatively, after dissolving the magenta coupler of the present invention alone or in combination in a solvent having only a low boiling point solvent,
A method of mixing with a gelatin aqueous solution containing a surfactant, emulsifying and dispersing using a high-speed rotating mixer, a colloid mill or an ultrasonic dispersing machine, and then directly adding the resulting emulsion to the emulsion can be adopted. Alternatively, the emulsified dispersion may be set, then cut into pieces, washed with water, and then added to the emulsion.

The magenta coupler of the present invention may be separately dispersed in a high-boiling solvent and the above-mentioned dispersion method and added to the silver halide emulsion. However, both compounds are dissolved simultaneously, dispersed and added to the emulsion. The method is preferred.

The amount of the high boiling point solvent to be added is preferably from 0.01 to 10 per gram of the magenta coupler of the present invention.
g, more preferably in the range of 0.1 to 3.0 g.
Instead of using a high boiling point solvent, it may be dissolved in only a low boiling point solvent, dispersed, and added to the emulsion.

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

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as a binder for the emulsion.

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

Further, a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, by a coupling reaction with a colored coupler, a competing coupler, and an oxidized form of a developing agent having a color correcting effect. Compounds which release photographically useful fragments such as toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

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

In order to obtain a dye image using the light-sensitive material of the present invention, generally known color photographic processing can be performed after exposure.

[0055]

EXAMPLES The present invention will now be described with reference to specific examples, but the embodiments of the present invention are not limited thereto.

Example 1 In the following, the amount added in a silver halide photographic light-sensitive material indicates the number of grams per 1 m ² unless otherwise specified. Incidentally, silver halide and colloidal silver are shown in terms of silver,
The sensitizing dye was represented by the number of moles per mole of silver.

One side (front side) of the triacetylcellulose film support is subjected to a subbing process, and then the support is sandwiched between the triacetylcellulose film support and a surface opposite to the subscribed surface (back surface).
Then, a layer of the following composition was sequentially applied from the support side to prepare a support which was subjected to an undercoating process. The amount of addition is shown per 1 m ² .

Back surface first layer Alumina sol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.1 g Diacetyl cellulose 0.2 g Back surface second layer diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) A multilayer color photographic light-sensitive material 1 was prepared by sequentially forming layers having the following compositions from the support side on the surface of a 50 mg-subtracted triacetyl cellulose film support.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Compound (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g High boiling solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer: Intermediate layer (IL-1) Gelatin 1.3 g Third layer: Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Average particle diameter 0.3 μm, average iodine content 2.0 mol%) 0.4 g silver iodobromide emulsion (average particle diameter 0.4 μm, average iodine content 8.0 mol%) 0.3 g sensitizing dye (S-1) 3.2 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-3) 0 .2 × 10 ^-4 (mol / mole of silver) cyan coupler (C-1) 0.50 g cyan coupler (C-2) 0 13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g DIR compound (D-2) 0.01 g High boiling solvent (Oil-1) 0.55 g Gelatin 1.0 g Fourth layer : High-sensitivity red-sensitive emulsion layer (R-H) Silver iodobromide emulsion (average particle diameter 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ⁻⁴ (mol / (1 mol of silver) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling solvent (Oil-1) 0.25 g Gelatin 1.0 g Fifth layer: Intermediate layer (IL-2) Gelatin 0.8 g Sixth layer: Low sensitivity green feeling Emulsion layer (GL) Silver iodobromide emulsion (average particle size 0.4 μm, average iodine content 8.0 mol%) 0.6 g Silver iodobromide emulsion (average particle size 0.3 μm, average iodine content) 2.0 mol%) 0.2 g Sensitizing dye (S-4) 6.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-5) 0.8 × 10 ^-4 (mol / silver) 1 mol) Magenta coupler (M-1) 0.35 g Colored magenta coupler (CM-1) 0.05 g DIR compound (D-3) 0.02 g Additive 1 0.10 g High boiling point solvent (Oil-2) 7 g Gelatin 1.0 g Seventh layer: high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average particle size 0.7 μm, average iodine content 7.5 mol%) 0.9 g sensitizing dye ( ^{S-6) 1.1 × 10 -4} ( mol / mole of silver) sensitizing dye (S-7) 2.0 × 10 -4 ( mol / mole of silver) Sensitive dye (S-8) 0.3 × 10 -4 ( mol / mole of silver) Magenta coupler (M-1) 0.20 g Colored magenta coupler (CM-1) 0.02 g DIR compound (D-3) 0 0.004 g High boiling solvent (Oil-2) 0.35 g Additive 1 0.07 g Gelatin 1.0 g Eighth layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive (SC-1) 0.12 g High Boiling point solvent (Oil-2) 0.15 g Gelatin 1.0 g Ninth layer: low-sensitivity blue-sensitive emulsion layer (B-L) Silver iodobromide emulsion (average particle size 0.3 μm, average iodine content 2.0 mol) %) 0.25 g silver iodobromide emulsion (average particle size 0.4 μm, average iodine content 8.0 mol%) 0.25 g sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver) 1 mol) Yellow coupler (Y-1) 0.6 g yellow Puller (Y-2) 0.32 g DIR compound (D-1) 0.003 g DIR compound (D-2) 0.006 g High boiling solvent (Oil-2) 0.18 g Gelatin 1.3 g Tenth layer: High sensitivity Blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average particle size 0.8 μm, average iodine content 8.5 mol%) 0.5 g Sensitizing dye (S-10) 3.0 × 10 ^-4 (Mol / silver 1 mol) Sensitizing dye (S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g high Boiling point solvent (Oil-2) 0.05 g Gelatin 1.0 g Eleventh layer: first protective layer (PRO-1) Silver iodobromide emulsion (average particle size 0.08 μm) 0.3 g Ultraviolet absorber (UV-1) ) 0.07 g UV absorber (UV-2) 0.10 g High boiling solvent (Oil- 1) 0.07 g High boiling solvent (Oil-3) 0.07 g Gelatin 0.8 g 12th layer: 2nd protective layer (PRO-2) Compound (Compound A) 0.04 g Compound (Compound B) 0.004 g Poly Methyl methacrylate (average particle size: 3 μm) 0.02 g Methyl methacrylate: ethyl methacrylate: methacrylic acid = 3: 3: 4 (weight ratio) copolymer (average particle size: 3 μm) 0.13 g Gelatin 0.5 g Sample 1 further comprises a dispersing aid SU-1, a coating aid SU-2, a hardener H-1, a stabilizer ST-1, and a preservative DI.
-1, antifoggants AF-1 and AF-2, dye AI-
1. Contains AI-2.

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

Next, samples 2 to 10 were prepared by changing the magenta couplers to be added to the silver halide emulsions of the sixth and seventh layers in the above sample 1 as shown in Table 2 below.

The amount of the magenta coupler added to Samples 2 and 3 was equimolar to the amount of the magenta coupler used in Sample 1.

The amount of the magenta coupler added to Samples 4 to 10 was モ ル mole of the magenta coupler used in Sample 1. The additive 1 was not added to the sample of the present invention.

The samples 1 to 10 prepared as described above were exposed to green light through a step wedge for sensitometry and processed under the following conditions.

[Processing Step]

[0074]

[Table 1]

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers 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-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and add potassium hydroxide or 20
The pH is adjusted to 10.06 with% sulfuric acid.

Color developing 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-hydroxyl Ethyl) aniline sulfate 6.3 g potassium hydroxide 2 g diethylenetriaminepentaacetic acid 3.0 g water was added to make 1 liter, and potassium hydroxide or 20
The pH is adjusted to 10.18 with% sulfuric acid.

Bleaching solution Water 700 ml Ferric ammonium 1,3-diaminopropanetetraacetate 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Add water to make 1 liter, and use ammonia water or glacial acetic acid. Adjust to pH 4.4.

Bleaching replenisher Water 700 ml Ferric ammonium ammonium 1,3-diaminopropanetetraacetate 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 to make 1 liter.

Fixer 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 aqueous ammonia,
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 aqueous ammonia,
Add water to make 1 liter.

Stabilizing Solution and Stabilizing Replenisher Water 900 ml p-C ₈ H ₁₇ -C ₆ H ₄ -O- (CH ₂ CH ₂ O) ₁₀ H 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1, 2-Benzisothiazolin-3-one 0.1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml After adding water to make 1 liter, add ammonia water or 5
Adjust to pH 8.5 with 0% sulfuric acid.

After the treatment, the sensitometric characteristics of green light measurement were measured for each of the above samples. The bleaching fog was evaluated by the difference (ΔDmin) between the density of the unexposed portion of the sample when the above-mentioned bleaching solution was used and the case where the following bleaching solution was used.

The sensitivity is obtained from the reciprocal of the exposure required to give a density of fog + 0.3, and is shown in the following Table 2 as a relative sensitivity with the sensitivity of Sample 1 being 100.

The color reproducibility was determined by subjecting a sample obtained by photographing a Macbeth color chart to development processing by the above-described processing, and then using a Konica color developing machine, Konica color paper QA.
-A6 was printed, and the color of the paper and the color of the Macbeth color chart were visually compared. Good was evaluated as ○, and poor was evaluated as ×.

A deteriorated bleach solution for evaluating bleach fog was prepared by adjusting the pH of the bleach solution to 5.5 and diluting it 1.5 times with water.

Difference ΔDmin between minimum density Dmin when standard bleaching solution of pH 4.0 and deteriorated bleaching solution of pH 5.5 were used
Indicated bleached fog.

ΔDmin = Dmin (degraded bleaching solution) −D
min (standard bleaching solution) A low pH color developing solution for evaluating development pH fluctuation resistance was prepared by adjusting the pH of the color developing solution to 9.88 using potassium hydroxide or 20% sulfuric acid.

The crystalline compound was treated with various organic solvents, ie, hexane, acetonitrile,
A sample that could be recrystallized from toluene, ethyl acetate, chloroform, methanol, ethanol, acetone or a mixed solvent thereof was evaluated as ○, and a sample that was not recrystallized was evaluated as ×.

[0090]

[Table 2]

As is clear from Table 2, Comparative Samples 1 to 5
Has low sensitivity, low color development, large bleach fog (ΔDmin), and poor color reproducibility.

On the other hand, Samples 6 to 10 using the coupler of the present invention have high sensitivity, high color development, and bleach fog (ΔDm
in) is small, the color reproducibility is good, and it has very favorable performance.

Further, the coupler of the present invention did not require the use of the additive 1 unlike the comparative sample, and the cost was reduced.

[0094]

According to the present invention, firstly, there is provided a silver halide color photographic light-sensitive material having high sensitivity, high color development and low bleaching fog. Secondly, a halogenated material having excellent color reproducibility. Thirdly, it was possible to provide a silver color photographic light-sensitive material which could be industrially manufactured at low cost.

Claims (5)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a support having thereon a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material, characterized in that at least one of the silver halide emulsion layers contains at least one coupler represented by the following general formula [I]. Embedded image [Wherein, R ₁ represents an alkyl group or an aryl group, R ₂ represents an alkyl group or an aryl group, R ₃ represents an alkyl group,
Represents an aryl group or a group represented by NHR ₆ . R ₆ represents an alkyl group or an aryl group. R ₄ represents a substituent;
Represents an integer of 0 to 4. When m is 2 or more, a plurality of R ₄
May be the same or different. R ₅ represents an aromatic group. ] 2. The silver halide color photographic light-sensitive material according to claim 1, wherein in the general formula [I], R ₂ is an aryl group. 3. A silver halide color photographic light-sensitive material according to claim 1, wherein R ₅ in the formula [I] is a trichlorophenyl group. 4. In the general formula [I], at least one of the substituents at the position ortho to the nitrogen atom at R ₄ is selected.
4. A silver halide color photographic light-sensitive material according to claim 1, wherein one of them is an alkoxy group or a halogen atom. 5. A silver halide color photographic light-sensitive material having a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. A silver halide color photographic light-sensitive material, characterized in that at least one silver halide emulsion layer contains at least one coupler represented by the following general formula [II]. Embedded image [Wherein, R ₁₁ represents an alkyl group, R ₁₂ represents an aryl group, and R ₁₃ represents an alkyl group or a group represented by NHR ₁₄ . R ₁₄ represents an alkyl group or an aryl group. ]