JPH11218883A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material containing a novel 2-equivalent yellow coupler superior in color developing performance and high in solubility to a low-boiling solvent and superior in dispersion stability in a solvent by incorporating a specified yellow coupler. SOLUTION: The photosensitive material contains the yellow coupler represented by the formula, in which R1 is an alkyl or cycloalkyl or aryl group or the like; R2 is a >=2C straight or branched unsubstituted alkyl group; X is a halogen atom or an alkoxy group or the like; Y is an acylamino group or a halogen atom, when R1 is an alkyl or cyclalkyl group or the like, and when R1 is an aryl group, it is a sulfonylamino group or a halogen atom or the like; and (n) is an integer of 0-4, and when (n) is >=2, each of plural Y is same or different, thus permitting the obtained photosensitive material to have the novel 2-equivalent coupler superior in color developing performance and high in solubility in a low-boiling solvent and superior in dispersion stability in a solvent.

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 halogenation method using a novel yellow coupler which has excellent coloring properties, high solubility in a low boiling point solvent and excellent dispersion stability. It relates to a silver color photographic material.

[0002]

2. Description of the Related Art In recent years, in silver halide color photographic materials (hereinafter, also simply referred to as color photographic materials), 1
Instead of the conventional 4-equivalent coupler, which required 4 atoms of silver to form a molecular dye, introduce a suitable substituent at the coupling position (active site) of the coupler that reacts with the oxidized form of the developing agent. Accordingly, there is a tendency that a two-equivalent coupler, in which silver for forming one molecule of the dye is sufficient with two atoms, is often used.

Among such 2-equivalent couplers, examples of the active site substituent employed in the yellow coupler include, for example, JP-A-50-87650 and US Pat.
8,194, an aryloxy group described in JP-A-51-1.
Oxazolyloxy group described in No. 31325, 51-1
No. 39333, chroman-4-oxy group;
No. 43420, tetrazolyloxy group, and 52-1
5-pyrazolyloxy group described in No. 50631, and 5-
No. 115219, nitrogen-containing heterocyclic group, JP-B-51-3
No. 3410, a hydantoin group described in JP-A-51-110783, an oxazolidinedione group described in JP-A-48-68635, and U.S. Pat. No. 3,227,5.
No. 54 are known, and some of them are already in practical use.
The oxazolidinedione group described in 8-66835 has an advantage that it is a leaving group having excellent coloring properties.

[0004] However, with the development of color photographic materials, the demand for couplers is becoming more and more severe.
Further improvement in color-forming efficiency is required for 2-equivalent yellow couplers.

The coupler having an oxazolidinedione group as a leaving group has the above-mentioned advantages. However, when dispersed in a solvent having a low boiling point such as ethyl acetate, the coupler has a poor solubility in the solvent. The use of a solvent causes inconvenience in the production of a photosensitive material, and furthermore, it is liable to cause precipitation after being once dispersed in the solvent, and there is also a problem that the dispersion stability is poor in a low boiling point solvent. There was also a strong demand for a solution.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a silver halide color photographic light-sensitive material containing a novel 2-equivalent yellow coupler having excellent color developing properties. Is to provide. A second object of the present invention is to provide a silver halide color photographic light-sensitive material containing a novel 2-equivalent yellow coupler having high solubility in a low boiling point solvent and exhibiting excellent dispersion stability in the solvent. It is in.

[0007]

The above objects of the present invention have been attained by a silver halide color photographic light-sensitive material containing a yellow coupler represented by the following general formula [I].

[0008]

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In the formula, R ₁ represents an alkyl group, a cycloalkyl group, an amino group, a heterocyclic group or an aryl group, R ₂ represents a linear or branched unsubstituted alkyl group having 2 or more carbon atoms, and X represents Represents a chlorine atom, an alkoxy group or an aryloxy group. Y is such that R ₁ is an alkyl group, a cycloalkyl group,
When it is an amino group or a heterocyclic group, it represents an acylamino group or a chlorine atom, and when R ₁ is an aryl group, it represents a sulfonylamino group, a chlorine atom or an oxycarbonyl group. n is 0
Represents an integer of 4. When n is 2 or more, a plurality of Ys may be the same or different.

Hereinafter, the present invention will be described in more detail. First, the yellow coupler represented by formula (I) will be described in detail.

In the general formula [I], examples of the alkyl group represented by R ₁ include groups such as methyl, ethyl, i-propyl, t-butyl and dodecyl. These alkyl groups may further have a substituent, and examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an acylamino group, and a hydroxyl group.

Examples of the cycloalkyl group represented by R ₁ include cyclopropyl, cyclohexyl and adamantyl.

The amino group represented by R ₁ includes a substituted amino group, and includes groups such as diethylamino, di-i-octylamino, and anilino. These amino groups may further have a substituent, examples of the substituent include the same substituents as the substituents for the alkyl group represented by R ₁ can be mentioned.

Examples of the heterocyclic group represented by R ₁ include a morpholino group and an indoline-1-yl group.

The aryl group represented by R ₁ includes groups such as phenyl and naphthyl. These aryl groups may further have a substituent, and as the substituent,
The same substituents as the substituents of the alkyl group represented by R ₁ can be mentioned.

R ₁ is preferably an alkyl group, a cycloalkyl group, an amino group, or a heterocyclic group, more preferably an alkyl group, and particularly preferably a t-butyl group.

Examples of the unsubstituted linear or branched alkyl group having 2 or more carbon atoms represented by R ₂ include groups such as ethyl, propyl, i-propyl, butyl and hexyl.

R ₂ is preferably a straight-chain unsubstituted alkyl group, more preferably a straight-chain unsubstituted alkyl group having 4 or more carbon atoms.

Examples of the alkoxy group represented by X include methoxy, ethoxy, i-propoxy, butoxy, decyloxy, dodecyloxy and the like, and a typical example of the aryloxy group is a phenoxy group.

The acylamino group represented by Y includes palmitoylamino, stearoylamino, 2- (2,4
-Di-t-pentylphenoxy) butanoylamino and the like.

Examples of the sulfonylamino group represented by Y include dodecylsulfonylamino and 4-dodecyloxybenzenesulfonylamino.

Examples of the oxycarbonyl group represented by Y include dodecyloxycarbonyl, hexadecyloxycarbonyl and the like.

In the general formula [I], one of R ₁ , X and Y is a diffusion-resistant group, and the total number of carbon atoms of R ₁ , X and Y is preferably 12 or more.

In the following, representative examples of the yellow coupler represented by the general formula [I] are shown, but the present invention is of course not limited thereto.

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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These yellow couplers can be easily synthesized by a conventionally known method. A typical synthesis example is shown below.

Synthesis Example: Exemplified compound (7) was synthesized according to the following scheme.

[0032]

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120 g (0.254 mol) of the compound (7a) was dissolved in 360 ml of acetone, and the compound (7b) 5
1.9 g (0.330 mol) and 45.6 g of potassium carbonate
(0.330 mol), and reacted under heating and reflux for 5 hours. After completion of the reaction, acetone was recovered under reduced pressure, and ethyl acetate and water were added to extract an organic layer. The organic layer was further washed twice with aqueous sodium carbonate, once with dilute hydrochloric acid, and then with water three times. Thereafter, the solvent was recovered under reduced pressure, and the residue was recrystallized from 300 ml of methanol to obtain 127 g of the exemplary compound (7).
(84% yield). 83-86 ° C.

The structure was confirmed by NMR, IR and mass spectrum.

Illustrative couplers other than (7) were also synthesized according to the above synthesis examples, starting from the corresponding raw materials.

The yellow couplers of the present invention may be used alone or in combination.
More than one species can be used in combination. Further, it can be used in combination with any known pivaloylacetanilide-based or benzoylacetanilide-based yellow coupler.

In order to incorporate the yellow coupler of the present invention into a silver halide photographic emulsion of a color light-sensitive material, a high boiling organic solvent having a boiling point of 175 ° C. or more, such as tricresyl phosphate or dibutyl phthalate, and ethyl acetate, methanol, After dissolving, alone or in combination, in one or more low-boiling organic solvents conventionally used in preparing coupler dispersions, such as acetone, chloroform, methyl chloride or butyl propionate After mixing with an aqueous solution of gelatin containing a surfactant and then emulsifying and dispersing the mixture with a high-speed rotating mixer or a colloid mill,
The obtained emulsified dispersion is directly added to the silver halide emulsion, or after setting the emulsified dispersion, shredded, and then the low boiling organic solvent is removed by washing with water or the like. What is necessary is just to add to a silver halide emulsion.

The yellow coupler of the present invention is preferably added in an amount of about 1 × 10 ⁻³ to about 1 mol per mol of silver halide, but the addition amount may be changed to other amounts depending on the application purpose. Is also good.

The color light-sensitive material of the present invention may be of any type and use. Examples of the silver halide include silver chloride, silver bromide, silver iodide, silver chlorobromide, and silver iodobromide. And silver chloroiodobromide.

The color light-sensitive material of the present invention may contain, in addition to the yellow coupler of the present invention, another color coupler for forming a multicolor image.

Color light-sensitive materials include color antifoggants, image stabilizers, hardeners, plasticizers, polymer latexes, formalin scavengers, mordants, development accelerators, development retarders, fluorescent brighteners, matting agents, solvents , An antistatic agent, a surfactant and the like can be optionally used.

The durability of the formed yellow image can be further improved by adding an ultraviolet absorber to the color light-sensitive material containing the yellow coupler of the present invention.

[0043]

Next, the present invention will be described with reference to examples, but the embodiments of the present invention are not limited to these examples.

Example 1 Polyethylene was laminated on one side of a paper support and polyethylene oxide containing titanium oxide was laminated on the other side. On the support, each layer having the following structure was replaced with a polyethylene layer containing titanium oxide. This was coated on the side to prepare a multilayer color photosensitive material sample 101. However, the coating solution was prepared as follows.

Yellow coupler dispersion: 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), 6.67 of (ST-2)
g, 0.67 g of a color mixture inhibitor (HQ-1), 0.34 g of an anti-irradiation dye (AI-3), and 0.67 g of a high-boiling organic solvent (DNP) by adding and dissolving 60 ml of ethyl acetate. 7 ml of 20% surfactant (SU-1)
Was dispersed and emulsified in 220 ml of a 10% aqueous gelatin solution using an ultrasonic homogenizer to prepare a yellow coupler dispersion (A).

The turbidity of this dispersion (A) was measured with a Poic integrating sphere turbidity meter (manufactured by Nippon Seimitsu Optical Co., Ltd.). The turbidity of the dispersion (A) kept at 40 ° C. for 24 hours was measured as dispersion (B). The results are shown in Table 1.

First Layer Coating Solution Next, the separately prepared dispersion (A) was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) under the conditions described below to prepare a first layer coating solution. .

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardening agent, (H) was added to the second and fourth layers.
-1) and (H-2) were added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

The amount of addition in the constitution is shown in g / m ² . However, silver halide emulsions were shown in terms of silver.

Layer Structure Coating Amount 7th Layer Gelatin 1.0 (Protective Layer) Silica (Average Particle Size 3 μm) 0.03 Color Mixing Prevention Agent (HQ-2) 0.002 Color Mixing Prevention Agent (HQ-3) 0 0.002 color mixture inhibitor (HQ-4) 0.004 color mixture inhibitor (HQ-5) 0.02 high boiling point organic solvent (DIDP) 0.005 compound (DI-1) 0.002 sixth layer gelatin 0.4 (Intermediate layer) UV absorber (UV-1) 0.1 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Color mixing inhibitor (HQ-5) 0.04 High boiling point Organic solvent (DNP) 0.2 High boiling organic solvent (PVP) 0.03 Anti-irradiation dye (AI-2) 0.02 Anti-irradiation dye (AI-4) 0.01 Fifth layer Gelatin 1. 3 (Red Sensitive Layer) Sensitizing Dye (RS-1) Photosensitized red-sensitive silver chlorobromide emulsion (Br 5 mol%, Cl 95 mol%) 0.21 cyan coupler (C-1) 0.17 cyan coupler (C-2) 0.25 color-mixing inhibitor (HQ- 1) 0.02 HBS-1 0.2 High boiling organic solvent (DOP) 0.2 Anti-irradiation dye (AI-1) 0.01 4th layer Gelatin 0.94 (Interlayer) UV absorber (UV) -1) 0.28 UV absorber (UV-2) 0.09 UV absorber (UV-3) 0.38 Color mixture inhibitor (HQ-5) 0.10 High boiling organic solvent (DNP) 0.4 3-layer gelatin 1.2 (green-sensitive layer) Green-sensitive silver chlorobromide emulsion spectrally sensitized with a sensitizing dye (GS-1) (Br 5 mol%, Cl 95 mol%) 0.35 magenta coupler (M-1) ) 0.23 color image stabilizer (ST-3) 0.20 color image Stabilizer (ST-4) 0.17 High-boiling organic solvent (DIDP) 0.13 High-boiling organic solvent (DBP) 0.13 Anti-irradiation dye (AI-3) 0.01 Second layer gelatin 1. 2 (Intermediate layer) Color mixture inhibitor (HQ-2) 0.03 Color mixture inhibitor (HQ-3) 0.03 Color mixture inhibitor (HQ-4) 0.05 Color mixture inhibitor (HQ-5) 0.23 High Boiling point organic solvent (DIDP) 0.13 Compound (F-1) 0.002 First layer Gelatin 1.2 (Blue-sensitive layer) Blue-sensitive silver chlorobromide spectrally sensitized with sensitizing dye (BS-1) Emulsion (Br 5 mol%, Cl 95 mol%) 0.26 Yellow coupler (Y-1) 0.80 Color image stabilizer (ST-1) 0.30 Color image stabilizer (ST-2) 0.20 Color mixture Inhibitor (HQ-1) 0.02 Irradiation prevention dye (AI-3) 0.01 High boiling organic solvent (DNP) 0.02 Back layer Gelatin 6.0 Silica (average particle size 3 μm) 0.1 The silver halide emulsions used in the present invention each have a distribution width of 10% or less. Was obtained. Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and sensitizing dyes and stabilizers (STAB-1) and (STAB-2) were added.

The structure of the compound used is shown below.

PVP: polyvinylpyrrolidone DBP: dibutyl phthalate DOP: dioctyl phthalate DNP: dinonyl phthalate DIDP: di-i-decyl phthalate HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5- Di-s-dodecylhydroquinone HQ-3: 2,5-di-s-tetradecylhydroquinone HQ-4: 2-s-dodecyl-5-s-tetradecylhydroquinone HQ-5: 2,5-bis (1, 1-dimethyl-4-hexyloxycarbonylbutyl) hydroquinone SU-1: sodium i-propyl-naphthalene-sulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate SU-3: di (2, sulfosuccinate) 2,3,3,4,4,4
5,5-octafluoropentyl) sodium STAB-1: 4-hydroxy-6-methyl-1,3,3
3a, 7-Tetrazaindene STAB-2: 1- (3-Acedamido) phenyl-5
- mercaptotetrazole _{H-1: O (CH 2} SO 2 CH = CH 2) 2 H-2: 2,4- dichloro-6-hydroxy -s- triazine sodium

[0054]

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[0055]

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[0056]

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[0057]

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Then, Comparative Samples 102 to 106 and Samples 107 to 112 of the present invention were prepared in the same manner as in Sample 101 except that the yellow coupler of the first layer was changed as shown in Table 1 in the preparation of Sample 101. The addition amount of the yellow coupler was adjusted so as to be the same as the addition amount in Sample 101.

Each sample was exposed to a wedge with white light for 0.2 seconds, developed in accordance with the following processing steps, and then measured in density with blue light using an optical densitometer PDA-65 (manufactured by Konica Corporation) to obtain the maximum color development. Density (Dmax) and minimum color density (Dm)
in) was measured.

The above sample was exposed to sunlight for 4 weeks, and the residual concentration at an initial concentration of 1.0 was measured to determine light resistance. Table 1 shows the results.

The processing conditions are as follows.

Processing Step Temperature Time Color Development 35.0 ± 0.3 ° C. 45 seconds Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Drying 60-80 ° C. 60 seconds Color developing solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1 0.0 g catechol-3,5-disulfonic acid disodium salt 1.0 g diethylene glycol 10 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g fluorescent brightener (4 , 4'-diaminostilbenesulfonic acid derivative) 1.0 g Potassium carbonate 27 g The amount was 1 liter, adjusted to pH = 10.10.

Bleaching-fixing solution Ethylenediaminetetraacetic acid ammonium ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water was added to bring the total volume to 1 liter. Adjust to pH = 5.7 with potassium or glacial acetic acid.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1 -Diphosphonic acid 2.0 g o-Phenylphenol sodium 1.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Fluorescent brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.5 g The total volume is adjusted to 1 liter by adding water, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

[0065]

[Table 1]

[0066]

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[0067]

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From the results shown in Table 1, the sample using the coupler of the present invention was superior to the comparative sample using the comparative couplers Y-1 and Y-4 in color development, and the comparative couplers Y-2 and Y-2.
It can be seen that the dispersion stability is superior to the comparative sample using Y-3, Y-5, and Y-6. In addition, it can be seen that the samples of the present invention using the couplers (4), (7), and (15) of the present invention are particularly excellent in color development.

Example 2 One Side (Surface) of Triacetyl Cellulose Film Support
Was subjected to an undercoating process, and then, on the surface (back surface) opposite to the surface on which the undercoating process was performed with the support interposed therebetween, each layer having the following composition was sequentially applied from the support side. The amount of addition in the light-sensitive material is shown in g / m ² as in Example 1, unless otherwise specified.
Further, silver halide and colloidal silver are values in terms of silver.

Backside First Layer Alumina Sol AS-100 (Nissan Chemical Industries, Ltd .: Aluminum Oxide) 0.1 Diacetylcellulose 0.2 Backside Second Layer Diacetylcellulose 0.1 Stearic acid 0.01 Silica fine particles (average particle size 0) .2 μm) 0.05 A multilayer color photosensitive material sample 201 was prepared by sequentially forming the layers having the following compositions from the support side on the surface of the triacetyl cellulose film support subjected to the above-mentioned subbing.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 UV absorber (UV-4) 0.20 Colored cyan coupler (CC-1) 0.02 High boiling solvent (Oil-1) 0 .20 high boiling point solvent (Oil-2) 0.20 gelatin 1.6 second layer; intermediate layer (IL-1) gelatin 1.3 third layer; low-sensitivity red-sensitive emulsion layer (RL) iodobromide Silver emulsion (average particle diameter 0.3 μm, average iodine content 2.0 mol%) 0.4 Silver iodobromide emulsion (average particle diameter 0.4 μm, average iodine content 8.0 mol%) 0.3 increase Sensitizing dye (S-1) 3.2 × 10 ⁻⁴ mol / mol Ag Sensitizing dye (S-2) 3.2 × 10 ⁻⁴ mol / mol Ag Sensitizing dye (S-3) 0.2 × 10 ^-4 mol / mol Ag cyan coupler (C-3) 0.50 cyan coupler (C-4) 0.13 colored cyan coupler (CC-1) 0.07 DIR compound (D-1) 0.006 DIR compound (D-2) 0.01 High boiling solvent (Oil-1) 0.55 Gelatin 1.0 Fourth layer; Sensitive emulsion layer (R-H) Silver iodobromide emulsion (average particle diameter 0.7 μm, average iodine content 7.5 mol%) 0.9 Sensitizing dye (S-1) 1.7 × 10 ^-4 mol / Mol Ag sensitizing dye (S-2) 1.6 × 10 ^-4 mol / mol Ag sensitizing dye (S-3) 0.1 × 10 ^-4 mol / mol Ag cyan coupler (C-4) 23 colored cyan coupler (CC-1) 0.03 DIR compound (D-2) 0.02 high boiling point solvent (Oil-1) 0.25 gelatin 1.0 fifth layer; intermediate layer (IL-2) gelatin 0 .8 sixth layer; low-sensitivity green-sensitive emulsion layer (GL) silver iodobromide emulsion (average grain size: 0.4 μm, average iodine content: 8.0 mol) %) 0.6 Silver iodobromide emulsion (average particle size 0.3μm average iodide content of 2.0 mol%) 0.2 Sensitizing dye (S-4) 6.7 × 10 -4 mol / mol Ag Sensitizing dye (S-5) 0.8 × 10 ^-4 mol / mol Ag Magenta coupler (M-2) 0.17 Magenta coupler (M-3) 0.43 Colored magenta coupler (CM-1) 0.10 DIR compound (D-3) 0.02 High boiling point solvent (Oil-2) 0.7 Gelatin 1.0 7th layer; High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average particle size 0) 0.7 μm average iodine content 7.5 mol%) 0.9 sensitizing dye (S-6) 1.1 × 10 ⁻⁴ mol / mol Ag sensitizing dye (S-7) 2.0 × 10 ⁻⁴ mol / mol Ag sensitizing dye (S-8) 0.3 × 10 -4 mol / mol Ag magenta coupler (M-2) 0.30 magenta coupler (M- 0.13 colored magenta coupler (CM-1) 0.04 DIR compound (D-3) 0.004 high boiling point solvent (Oil-2) 0.35 gelatin 1.0 8th layer; yellow filter layer (YC) Yellow colloidal silver 0.1 Additive (HS-1) 0.07 Additive (HS-2) 0.07 Additive (SC-1) 0.12 High boiling solvent (Oil-2) 0.15 Gelatin 1. 0 Ninth layer; low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size: 0.3 μm, average iodine content: 2.0 mol%) 0.25 Silver iodobromide emulsion (average grain: 0.4 μm diameter average iodine content 8.0 mol%) 0.25 sensitizing dye (S-9) 5.8 × 10 ⁻⁴ mol / mol Ag yellow coupler (Y-7) 0.95 DIR compound ( D-1) 0.003 DIR compound (D-2) 0.006 High boiling solvent (Oi 1-2) 0.18 gelatin 1.3 10th layer; high-sensitivity blue-sensitive emulsion layer (BH) silver iodobromide emulsion (average particle diameter 0.8 μm, average iodine content 8.5 mol%) 0 5.5 Sensitizing dye (S-10) 3 × 10 ⁻⁴ mol / mol Ag Sensitizing dye (S-11) 1.2 × 10 ⁻⁴ mol / mol Ag Yellow coupler (Y-7) 0.20 High boiling point Solvent (Oil-2) 0.05 Gelatin 1.0 Eleventh layer; First protective layer (PRO-1) Silver iodobromide (average particle size 0.08 μm) 0.3 Ultraviolet absorber (UV-4) 0 0.07 UV absorber (UV-5) 0.10 Additive (HS-1) 0.2 Additive (HS-2) 0.1 High boiling solvent (Oil-1) 0.07 High boiling solvent (Oil- 3) 0.07 gelatin 0.8 twelfth layer; second protective layer (PRO-2) slip agent (WAX-1) 0.04 surfactant (S -4) 0.004 Polymethyl methacrylate (average particle diameter 3 μm) 0.02 Methyl methacrylate: ethyl methacrylate: methacrylic acid = 3: 3: 4 (weight ratio) copolymer (average particle diameter 3 μm) 0 .13 All of the silver halide emulsions used above were core / shell monodisperse emulsions having a distribution width of 20% or less. Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to give a sensitizing dye, a stabilizer (STAB-1) and an antifoggant (AF
-1) was added.

AF-1: 1-phenyl-5-mercaptotetrazole Oil-1: dioctyl phthalate (= DOP) Oil-2: tricresyl phosphate Oil-3: dibutyl phthalate (= DBP) HS-1: Hydantoin HS- 2: 4-ureidohydantoin SU-4: sulfosuccinate di (2,2,3,3,4,4,
5,5,6,6,7,7-dodecylfluoroheptyl)
sodium

[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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The above-mentioned photosensitive material sample 201 was obtained by further adding surfactants SU-1 and SU-5, a viscosity modifier, and a hardener H-.
1, H-2, stabilizer STAB-1, antifoggant AF-
1, AF-2 (weight average molecular weight of 10,000 and polyvinylpyrrolidone of 1,100,000), anti-irradiation dyes AI-5 and AI-6 and fungicide DI
-1 (9.4 mg / m ² ).

SU-5: dioctyl sodium sulfosuccinate

[0081]

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Further, Samples 202 to 207 of the present invention were produced in the same manner as in Sample 201 except that the yellow couplers in the ninth and tenth layers of Sample 201 were changed as shown in Table 2. The addition amount of the yellow coupler was adjusted to be the same as the addition amount in Sample 201.

Samples 201 to 205 were exposed to white light at 1/10
After 0 second wedge exposure and color development in accordance with the following processing steps, D was measured using an optical densitometer PDA-65 (described above).
The max and Dmin were measured. Table 2 shows the results.

The processing conditions are as follows.

Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2.0 ° C. 830 ml Low Constant 60 seconds 38 ± 5.0 ° C. 830 ml Drying 1 minute 55 ± 5.0 ° C.-* The replenishment amount is a value per 1 m ² of the photosensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions, and replenishers were used.

Color developing solution and replenishing solution for color developing solution Replenishing solution for developing solution Water 800 ml 800 ml potassium carbonate 30 g 35 g sodium hydrogen carbonate 2.5 g 3.0 g potassium sulfite 3.0 g 5.0 g sodium bromide 1.3 g 0.4 g iodide Potassium 1.2 mg-hydroxylamine sulfate 2.5 g 3.1 g sodium chloride 0.6 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g 6.3 g diethylenetriamine Pentaacetic acid 3.0 g 3.0 g potassium hydroxide 1.2 g 2.0 g Water was added to make 1 liter, and potassium hydroxide or 20%
Using sulfuric acid, the developer is adjusted to pH 10.06 and the replenisher is adjusted to pH 10.
Adjust to 10.18.

Bleach and Bleach Replenisher Bleach Replenisher Water 700 ml 700 ml 1,3 diaminopropanetetraacetic acid iron (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g 56 g Add 1 liter and adjust the pH of the bleaching solution to 4.4 and the pH of the replenisher to 4.0 using ammonia water or glacial acetic acid.

Fixer and Fixer Replenisher Fixer Replenisher Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Aqueous solution using ammonia water or glacial acetic acid, pH 6.2
Then, the pH of the replenisher is adjusted to 6.5, and then water is added to make 1 liter.

Stabilizing Solution and Stabilizing Replenisher Water 900 ml p-octylphenoxy-deca (ethyleneoxy) hydrogen 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, ammonia water or 50
The pH was adjusted to 8.5 using% sulfuric acid.

[0091]

[Table 2]

From the results shown in Table 2, it can be seen that all the samples using the coupler of the present invention have higher maximum color density and less fog than the comparative sample using Y-7. I understand.

Example 3 One Side (Surface) of Triacetyl Cellulose Film Support
Was subjected to an undercoating process, and then a layer having the following composition was sequentially applied to the surface (back surface) opposite to the surface on which the undercoating process was performed with the support interposed therebetween. The amount of the additive to the light-sensitive material is the same as in Example 2.

Back first layer Alumina sol AS-100 (aluminum oxide: as described above) 0.8 Back second layer Diacetylcellulose 0.1 Stearic acid 0.01 Silica fine particles (average particle size 0.2 μm) 0.5 Subtraction On the surface of the processed triacetylcellulose film support, layers having the following compositions were sequentially formed from the support side to prepare a multilayer color photosensitive material sample 301.

First layer (antihalation layer) Black colloidal silver 0.24 UV absorber (U-1) 0.14 UV absorber (U-2) 0.072 UV absorber (U-3) 0.072 Ultraviolet absorber (U-4) 0.072 High boiling point solvent (O-1) 0.31 High boiling point solvent (O-2) 0.098 Poly-N-vinylpyrrolidone 0.15 Gelatin 2.02 Second layer ( Intermediate layer) High boiling solvent (O-3) 0.011 Gelatin 1.17 Third layer (Low-sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes S-12 and S-13 (3.0 mol% of silver iodide, average particle size 0.30 μm) 0.60 Cyan coupler (C-5) 0.37 High boiling point solvent (O-2) 0.093 Poly-N-vinylpyrrolidone 0.074 Gelatin 1.35 4th layer (high-sensitivity red-sensitive layer) Red sensitizing dye Silver iodobromide emulsion spectrally sensitized with S-12 and S-13 (silver iodide 3.0 mol%, average grain size 0.80 μm) 0.60 cyan coupler (C-5) 0.85 high boiling point Solvent (O-2) 0.21 Poly-N-vinylpyrrolidone 0.093 Gelatin 1.56 Fifth layer (intermediate layer) Color mixture inhibitor (SC-1) 0.20 High boiling solvent (O-3) 25 Matting agent (MA-1) 0.0091 Gelatin 1.35 6th layer (low-sensitivity green-sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye S-14 (silver iodide 3. 0 mol%, average particle size 0.30 μm) 0.70 Magenta coupler (M-4) 0.31 Magenta coupler (M-5) 0.076 High boiling solvent (O-3) 0.059 Poly-N-vinyl Pyrrolidone 0.074 Gelatin 1.29 7th layer (highly sensitive green-sensitive layer) Green sensitizing color Silver iodobromide emulsion spectrally sensitized in S-14 (silver iodide 3.0 mol%, average grain size 0.80 μm) 0.70 Magenta coupler (M-4) 0.80 Magenta coupler (M-5) 0.19 Color mixing inhibitor (SC-1) 0.055 High boiling point solvent (O-3) 0.16 Poly-N-vinylpyrrolidone 0.12 Gelatin 1.91 Eighth layer (Intermediate layer) Gelatin 0.90 Ninth layer (yellow filter layer) Yellow colloidal silver 0.11 Color mixture inhibitor (SC-1) 0.068 High boiling point solvent (O-3) 0.085 Matting agent (MA-1) 0.012 Gelatin 0. 68 10th layer (low-sensitivity blue-sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye S-15 (silver iodide 3.0 mol%, average particle size 0.30 μm) 0.70 yellow Coupler (Y-8) 0.86 Image stabilizer (G-1) 0 012 High boiling point solvent (O-3) 0.22 Poly-N-vinylpyrrolidone 0.078 Compound (HS-1) 0.040 Compound (HS-2) 0.020 Gelatin 1.09 11th layer (high sensitivity blue) (Sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye S-15 (silver iodide 3.0 mol%, average particle size 0.85 μm) 0.70 Yellow coupler (Y-8) 24 Image stabilizer (G-1) 0.017 High boiling point solvent (O-3) 0.31 Poly-N-vinylpyrrolidone 0.10 Compound (HS-1) 0.077 Compound (HS-2) 0.039 Gelatin 1.73 12th layer (protective layer-1) Non-photosensitive fine grain silver iodobromide (silver iodide 1.0 mol%, average particle size 0.08 μm) 0.075 UV absorber (U-1) 0 0.048 UV absorber (U-2) 0.024 UV absorber ( U-3) 0.024 UV absorber (U-4) 0.024 High boiling solvent (O-1) 0.13 High boiling solvent (O-2) 0.13 Compound (HS-1) 0.15 Compound (HS-2) 0.075 Gelatin 1.2 13th layer (Protective layer-2) Slip agent (WAX-1) 0.041 Matting agent (MA-2) 0.0090 Matting agent (MA-3) 051 Surfactant (SU-4) 0.0036 Gelatin 0.55 (Note: The weight average molecular weight of the poly-N-vinylpyrrolidone used in each layer is 350,000. Gelatin hardeners H-1, H-2, H-3, water-soluble dyes AI-5, AI-
6, AI-7, an antifungal agent DI-1, a stabilizer STAB-1,
Antifoggant AF-1 was added as needed.

The silver halide emulsions used for each photosensitive layer were all monodisperse emulsions having a distribution width of 20% or less. Each emulsion is desalted and washed, and then subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to spectrally sensitize the silver halide emulsion used for each photosensitive layer. Each sensitizing dye, STAB-1, AF-1 was added.

The width of the distribution is defined by the following equation.

Area of distribution (%) = standard deviation of particle size / average particle size × 100 MA-1: colloidal silica particles (average particle size of 3.5 μm)
m) MA-2: polymethyl methacrylate particles (average particle size: 3.0 μm) O-1: di-2-ethylhexyl phthalate O-2: dibutyl phthalate (= Oil-3) O-3: tricresyl phosphate (= Oil-2) G-1: Dodecyl gallate H-3: [(CH ₂ ＣＨCHSO ₂ CH ₂ ) ₃ CCH ₂ SO ₂ C
_{H 2 CH 2] 2 NCH 2} CH 2 SO 3 K

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

Next, the tenth layer and the eleventh layer
Samples 302 to 30 of the present invention were prepared in the same manner as in Sample 301 except that the yellow coupler in the layer was changed as shown in Table 3.
3 was produced. The addition amount of the yellow coupler was adjusted to be the same molar amount as that of the sample 301.

The samples 301 to 303 were subjected to white light at 1/10
After a 0 second wedge exposure and color development in accordance with the following processing steps, the maximum color density and the minimum color density were measured using an optical densitometer PDA-65 (described above).

As a result, similarly to Examples 1 and 2, it was found that all of the samples using the coupler of the present invention formed a dye image having a higher maximum color density and less fog than the comparative sample. .

[0105]

[Table 3]

Processing Step Processing Time Processing Temperature First Development 6 minutes 38 ° C. Rinse 2 minutes 38 ° C. Inversion 2 minutes 38 ° C. Color Development 6 minutes 38 ° C. Adjustment 2 minutes 38 ° C. Bleaching 6 minutes 38 ° C. Fixing 4 minutes 38 ° C. Water washing 4 minutes 38 ° C. Stable 1 minute Room temperature Drying The treatment liquid composition used in the above treatment step is as follows.

First developer solution Sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water was added to adjust the pH to 9.60 and the total amount to 1,000 ml.

Reversal solution Nitrilotrimethylene phosphonic acid hexasodium salt 3 g Stannous chloride (dihydrate) 1 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to the mixture to adjust the pH to 5.75. Finished to 1000 ml.

Color developing solution Sodium tetrapolyphosphate 3 g Sodium sulfite 7 g Sodium tertiary phosphate (dihydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazinic acid 1.5 g N-ethyl -N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline / sulfate 11g 2,2-ethylenedithiodiethanol 1g Water was added to adjust the pH to 11.70 and the total amount to 1,000 ml.

Adjustment solution Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 mL Glacial acetic acid 3 mL Water was added to adjust the pH to 6.15 and the total volume to 1000 mL.

Bleaching solution Sodium ethylenediaminetetraacetate (dihydrate) 2 g Ammonium iron (III) ethylenediaminetetraacetate (dihydrate) 120 g Ammonium bromide 100 g Water was added to adjust the pH to 5.65 and the total volume to 1,000 ml.

Fixer 80 g of ammonium thiosulfate 5 g of sodium sulfite 5 g 5 g of sodium bisulfite Water was added to adjust the pH to 6.60 and the total volume to 1,000 ml.

Stabilizing solution Formalin (37% by weight) 5 ml KONIDAX (manufactured by Konica) 5 ml Water was added to adjust the pH to 7.00 and the total amount to 1,000 ml.

[0114]

As described in detail above, according to the present invention, a silver halide color photographic light-sensitive material containing a novel yellow coupler having excellent coloring properties and excellent dispersion stability can be provided.

Claims (3)

[Claims] 1. A silver halide color photographic material comprising a yellow coupler represented by the following formula [I]. Embedded image [Wherein, R ₁ represents an alkyl group, a cycloalkyl group, an amino group, a heterocyclic group or an aryl group, R ₂ represents a linear or branched unsubstituted alkyl group having 2 or more carbon atoms, and X represents a chlorine atom. , An alkoxy group or an aryloxy group. Y
Represents an acylamino group or a chlorine atom when R ₁ is an alkyl group, a cycloalkyl group, an amino group or a heterocyclic group,
When R ₁ is an aryl group, it represents a sulfonylamino group, a chlorine atom or an oxycarbonyl group. n represents the integer of 0-4. When n is 2 or more, a plurality of Ys may be the same or different. ] 2. In the general formula [I], R ₁ represents an alkyl group, a cycloalkyl group, an amino group or a heterocyclic group, and R ₂ represents a linear or branched unsubstituted alkyl group having 2 or more carbon atoms. And X represents a chlorine atom, an alkoxy group or an aryloxy group, Y represents an acylamino group or a chlorine atom, and n represents an integer of 0 to 4.
The silver halide color photographic light-sensitive material described in the above. 3. In the above general formula [I], R ₁ represents an aryl group, R ₂ represents a linear or branched unsubstituted alkyl group having 2 or more carbon atoms, and X represents a chlorine atom, an alkoxy group or an aryl group. Represents an oxy group, Y is a sulfonylamino group,
2. A silver halide color photographic light-sensitive material according to claim 1, wherein said material represents a chlorine atom or an oxycarbonyl group, and n represents an integer of 0 to 4.