JPH11160839A - Photographic coupler and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the photographic coupler superior in color developing performance and color reproducibility by using a coupler having a cyclic molecular structure prepared by condensing optional 2 substituents not adjacent to each other and situated on except active points. SOLUTION: The photographic couplers to be used has a cyclic molecular structure prepared by condensing optional 2 substituents situated not adjacently and not on active points. The photographic coupler to be used is embodied by acylacetanilide type yellow couplers, phenolic cyan couplers, and the like, and it is used usually in an amount of 1000-1 mol/mol, preferably, 100-80 mol/ mol of silver halide. It is added to the photosensitive material, preferably, by dissolving it in a high-boiling solvent, and when needed, together with a low- boiling solvent in addition, and dispersing it into fine particles, and at that time, an ultraviolet absorber and the like may be added, if necessary.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic coupler and a silver halide color photographic light-sensitive material containing a cyan coupler (hereinafter, also simply referred to as a light-sensitive material). More specifically, the present invention relates to a novel pyrazolotriazole-based cyan coupler. The present invention relates to a silver halide photographic light-sensitive material capable of obtaining a dye image having excellent color developability and color reproducibility by being contained.

[0002]

2. Description of the Related Art In general, when a color photograph is produced, a silver halide color photographic light-sensitive material is exposed to light and then subjected to a color development process.
The oxidized aromatic primary amine color developing agent reacts with the dye-forming coupler to form a dye and form a color image.In such a photographic method, a color reproduction method using a subtractive color method is used. Thus, each color image of yellow, magenta and cyan is formed.

Conventional photographic couplers include, for example, an acylacetanilide coupler for forming a yellow image, a pyrazolone and a pyrazolotriazole coupler for forming a magenta image, and phenol and naphthol. , Pyrazolotriazole and pyrrolotriazole couplers have been used to form cyan images. These couplers are desired to have a sharp spectral absorption spectrum when a color image is generated.

However, as the coupler for forming a yellow image, the acylacetanilide-based coupler, which has been studied and put to practical use, has a spectral absorption characteristic of the formed yellow image, especially a long-wavelength tail. Cutting was insufficient. Also, phenolic couplers,
The spectral absorption characteristic of the cyan image formed from the naphthol coupler was insufficient particularly at the short-wave side.

Accordingly, various proposals have hitherto been made with the aim of improving these, including selection and search for substituents in the coupler, but couplers satisfying the requirements relating to these properties are still available. Not found.

On the other hand, in a silver halide color photographic light-sensitive material used for direct viewing, for example, color printing paper, a combination of a yellow coupler, a magenta coupler and a cyan coupler is usually used as a color forming agent for forming a dye image. Used. These couplers are required to have basic performance such as color reproducibility, color development and storage durability of the obtained dye image.In particular, in recent years, in order to faithfully reproduce the original color of the target object, color reproduction is required. There is a growing demand from users for improvements.

For the purpose of improving color reproducibility, Japanese Patent Application Laid-Open
250649, 63-250650, 64-5
No. 54 has proposed a pyrazolotriazole type cyan coupler. However, these couplers have an electron-withdrawing group and a hydrogen-bonding group in order to satisfy the absorption wavelength of the color-forming dye to be formed. Was not satisfactory.

Japanese Patent Application Laid-Open No. 9-034069 describes that the use of a pyrazolotriazole type cyan coupler and a sulfonamide-based additive in combination improves the color development and the color reproducibility of a dye image. . However, the effect of improving the color reproducibility of the dye image was not sufficient.

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a photographic coupler and a silver halide color photograph which are excellent in color development and color reproducibility. Provided is a photosensitive material.

[0010]

The above objects of the present invention have been attained by the following constitutions.

1. A photographic coupler having a cyclic molecular structure in which any two substituents other than the active site are condensed with each other at a site not adjacent to each other in the coupler skeleton.

2. 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; At least one of the emulsion layers has the following general formula (I) or general formula (I
A silver halide color photographic material comprising a cyan coupler represented by I).

[0013]

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[In the formula, X ₁ and X ₂ each represent a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. J represents a divalent linking group, and these divalent linking groups may have a substituent. ] 3. 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 material comprising at least one emulsion layer containing a cyan coupler represented by the following formula (III) or (IV).

[0015]

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[In the formula, R ₁ and R ₂ each represent a substituted or unsubstituted alkylene group, an arylene group, or a divalent heterocyclic group. J represents a divalent linking group, and these divalent linking groups may have a substituent. Hereinafter, the present invention will be described more specifically.

Examples of the photographic coupler of the present invention include an acylacetanilide yellow coupler, a phenol cyan coupler, a naphthol cyan coupler, a pyrazolotriazole cyan coupler, and a pyrrolotriazole cyan coupler.

In the present invention, the coupler skeleton is defined by the following structure. Here, * represents a site to which a substituent can bind.

[0019]

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X represents a hydrogen atom or a group which can be eliminated by reaction with an oxidized form of a color developing agent.

Further, in the conventionally known pyrazolotriazole type cyan coupler, a dye aggregate is easily formed due to strong intermolecular interaction between dyes formed by the oxidative coupling reaction with the color developing agent. as a result,
In the spectral absorption spectrum of the dye image, an unnecessary secondary absorption peak appears on the short wavelength side of the maximum absorption peak, so that color reproducibility deteriorates.

The compounds represented by the general formulas (I) to (IV) according to the present invention are capable of forming a pyrazoloazole type cyan coupler dye molecule at the 2-position or 3-position and 6-position in the coupler skeleton. Substituents are condensed with each other to form a cyclic molecular structure, which effectively prevents the formation of dye aggregates of the dye molecules and, as a result, improves the color reproducibility of the dye image. Conceivable. Further, it was also confirmed that the use of the coupler having the structure as in the present invention also improved the coloring property.

Next, the couplers represented by formulas (I) and (II) will be described in detail.

Examples of the divalent linking group represented by J include alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamide, alkylthio, arylthio, halogen atom, heterocycle, sulfonyl, sulfinyl, phosphono, acyl, carbamoyl, A divalent group derived from each group of sulfamoyl, cyano, alkoxy, aryloxy, acyloxy, amino, alkylamino, ureido, alkoxycarbonyl, aryloxycarbonyl, carboxyl and the like, and a combination of these divalent groups Represents a divalent group capable of forming, and these divalent linking groups may have a substituent.

The substituent substituted on J is not particularly limited, but typically includes alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. In addition to this, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphono, acyl, carbamoyl, sulfamoyl, cyano,
Alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, hetero Examples include groups such as ring thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, and sulfo, as well as spiro compound residues and bridged hydrocarbon compound residues. These groups may be further substituted by the above substituents.

Hereinafter, each substituent will be described in detail.

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

As the aryl group, a phenyl group is preferable.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl component and the aryl component in the alkylthio group and the arylthio group include an alkyl group and an aryl group, respectively.

The alkenyl group 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.

The cycloalkenyl group may have 3 to 3 carbon atoms.
12, especially 5-7 are preferred.

Examples of the sulfonyl group include an alkylsulfonyl group and an arylsulfonyl group; examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group;
As a phosphono group, an alkylphosphono group, an alkoxyphosphono group, an aryloxyphosphono group, an arylphosphono group, etc .; as an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .; as a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group And the like; a sulfamoyl group as an alkylsulfamoyl group, an arylsulfamoyl group, and the like; an acyloxy group as an alkylcarbonyloxy group, an arylcarbonyloxy group, and the like;
Examples of the sulfonyloxy group include an alkylsulfonyloxy group and an arylsulfonyloxy group; examples of the carbamoyloxy group include an alkylcarbamoyloxy group and an arylcarbamoyloxy group; examples of the ureido group include an alkylureido group and an arylureido group; Groups such as an alkylsulfamoylamino group and an arylsulfamoylamino group;
7-members are preferable, and specifically, 2-furyl, 2-
Thienyl, 2-pyrimidinyl, 2-benzothiazolyl,
1-pyrrolyl, 1-tetrazolyl group, etc .; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy, 1-phenyltetrazole 5 to 7-membered heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio, 2-benzothiazolylthio, 2,4-diphenoxy-1,3,5- Triazole-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide, 3-heptadecylsuccinimide group, phthalimide group and glutarimide group; As a group, spiro [3.3] heptane-1-yl and the like; as a bridged hydrocarbon compound residue, bicyclo [2.2. ] 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.

The above-mentioned groups may further have a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

Examples of the group capable of leaving by reaction with the oxidized form of the color developing agent represented by X, X ₁ and X ₂ include, for example, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.) and an alkoxy, aryl Oxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyloxalyloxy, alkoxyoxalyloxy,
Examples include alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring linked by an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl. Preferred are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a nitrogen-containing heterocyclic group linked by an N atom, and the like.

Next, the cyan couplers represented by the general formulas (III) and (IV) will be described in detail.

The alkylene group represented by R ₁ and R ₂ may be linear or branched. For example, methylene group, ethylene group, propylene group, butylene group, i-propylene group, t-butylene group, sec-butylene group, i-butylene group, t-octylene group, cyclohexylene group, dodecylene group, hexadecylene group, And the like.
The alkylene group includes those having a substituent, and examples of the substituent include a cycloalkyl group, an aryl group, a heterocyclic group, a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkoxycarbonyl group, and an aryloxycarbonyl. Groups, acyl groups, sulfonyl groups, amino groups, cyano groups, nitro groups, and the like. Examples of the arylene group represented by R ₁ and R ₂ include a phenylene group. The arylene group includes those having a substituent, and examples of the substituent include those described above as the substituent of the alkylene group.

The divalent heterocyclic groups represented by R ₁ and R ₂ include 2-furyl, 2-thienyl, 2-imidazolyl,
-Thiazolyl, 3-isoxazolyl, 3-pyridyl,
Examples thereof include divalent groups derived from each group such as 2-pyridyl, 2-pyrimidyl, and 3-pyrazolyl. Said 2
The valent heterocyclic group includes those having a substituent, and examples of the substituent include those described above as the substituent of the alkylene group.

Among the couplers represented by formulas (I) and (II), those represented by formula (I) are preferred.

Among the cyan couplers represented by the general formulas (III) and (IV), those represented by the general formula (III) are preferable.

In the following, typical examples of the photographic coupler of the present invention are shown in (1-1) to (1-12), and typical examples of the cyan coupler represented by formulas (I) and (II). Examples are changed from (2-1) to (2-10), general formula (III),
Representative specific examples of the cyan coupler represented by (IV) are (3)
Although shown in -1) to (3-24), the present invention is not limited to these.

[0043]

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[0044]

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[0045]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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The coupler of the present invention can be synthesized by a conventionally known method. As examples thereof, synthesis examples of the compounds (3-1) and (3-5) are shown below.

Synthesis Example A: Synthesis of Compound (3-1)

[0055]

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Compound (A-1) (10.0 g) was dissolved in chloroform (100 ml), 4.8 g of thionyl chloride was added, the mixture was refluxed for 3 hours, and concentrated to give compound (A).
-2) was obtained. Next, 3.7 g of the compound (A-3) was dissolved in 100 ml of tetrahydrofuran, and 1.8 g of pyridine was dissolved.
Was added and ice-cooled. The compound (A-
A solution of 2) dissolved in 100 ml of tetrahydrofuran was added over 30 minutes, and the mixture was stirred at room temperature for 1 hour. Then, 29%
30 ml of aqueous ammonia was added, the mixture was stirred at room temperature for 2 hours, washed with diluted hydrochloric acid, concentrated, and the obtained residue was purified by column chromatography (silica gel, developing solvent: acetonitrile) to give oily exemplary coupler (3-1). 5.8g
Obtained.

Synthesis Example B: Synthesis of Compound (3-5)

[0058]

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9.8 g of the compound (B-1) was reduced with hydrogen using Pd / C as a catalyst to obtain 8.0 g of the compound (B-2). (B
-2) 8.0 g, (B-3) 16.3 g and pyridine 3.
0 g was dissolved in 200 ml of tetrahydrofuran and refluxed for 2 hours. After completion of the reaction, 200 cc of ethyl acetate and 10
The organic layer was extracted by adding 0 cc and 1N hydrochloric acid (50 cc), dried, concentrated under reduced pressure, and recrystallized from acetonitrile to obtain 19.7 g of a compound (B-4).

(B-4) was converted to tetrahydrofuran (100 m).
and cooled the reaction vessel in an ice-water bath. After adding 6.6 g of pyridine to this, 3.3 g of acetyl chloride was added.
Was slowly added dropwise. The ice water bath was removed from the end of the dropwise addition, and the mixture was stirred at room temperature for 2 hours. After the reaction solution was concentrated, 50 ml of ethyl acetate was added to dissolve the obtained residue, which was washed with diluted hydrochloric acid, then with water, and then concentrated to obtain a compound (B-5).

100 ml of chloroform and 3.3 g of thionyl chloride were added to (B-5) obtained above, and the mixture was refluxed for 4 hours and concentrated to obtain a compound (B-6).

Compound (B-6) was reduced with Pd / C as a catalyst to give (B-7).

(B-7) obtained above was dissolved in 100 ml of tetrahydrofuran, 2.8 g of pyridine was added, and the mixture was ice-cooled. After stirring for 1 hour at room temperature, 30 ml of 29% aqueous ammonia was added, and the mixture was stirred for 2 hours at room temperature, washed with diluted hydrochloric acid, concentrated, and the obtained residue was subjected to column chromatography (silica gel, developing solvent: acetonitrile). Purification yielded 12.0 g of the exemplified coupler (3-5).

The photographic coupler of the present invention and the pyrazoloazole-based cyan coupler are generally used in an amount of 1 × 10 ^-3 to 1 mol, preferably 1 × 10 ^-2 to 1 mol per mol of silver halide.
It can be used in the range of 8 × 10 ^-1 mol.

The coupler of the present invention can be used in combination with other types of couplers.

In order to incorporate the photographic coupler of the present invention into the photographic material of the present invention, known techniques used in ordinary photographic couplers can be applied. It is preferable to dissolve the coupler in a high-boiling solvent and, if necessary, in combination with a low-boiling solvent, to disperse the fine particles, and to add them to the silver halide emulsion of the present invention. At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, an anti-fading agent and the like may be used in combination.

When the light-sensitive material of the present invention is used as a full-color light-sensitive material, a magenta coupler is used in addition to the cyan coupler and the yellow coupler of the present invention. The magenta coupler is not particularly limited, and a known one can be used.

As the magenta coupler, for example, a 5-pyrazolone coupler, a pyrazorobenzimidazole coupler, a pyrazolotriazole coupler, or a closed acylacetonitrile coupler can be used.

The silver halide emulsion used in the present invention is a silver halide color photographic emulsion known in the art.

The silver halide photographic light-sensitive material of the present invention includes:
The hydrophilic colloid layer may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation.

The silver halide photographic light-sensitive material of the present invention may further contain various photographic additives. For example, antifoggants, development accelerators, development retarders, bleaching accelerators, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants Agents, plasticizers, wetting agents and the like (RD17
643).

Further, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a fogging agent, an antifogging agent and a chemical sensitizer are obtained by coupling with a competitive coupler and an oxidized form of a developing agent. Compounds that release photographically useful fragments can be used, such as sensitizers, spectral sensitizers, and desensitizers.

The support of the silver halide photographic light-sensitive material of the present invention includes, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, polyester film such as cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyamide film, polycarbonate Film, polystyrene film, etc.
In the case of a transparent support, a reflective layer may be used in combination.

These supports are appropriately selected according to the purpose of use of the light-sensitive material.

For coating the emulsion layer and other constituent layers used in the present invention, various coating methods such as dipping coating, air doctor coating, curtain coating and hopper coating can be used. U.S. Pat. No. 2,781,7
No. 91, 2, 941, 898
A simultaneous coating method of more than two layers can be used.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined, but from the support side, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are sequentially arranged. It is preferable to use an array of

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose. Further, various layers such as a filter layer, an anti-curl layer, a protective layer and an antihalation layer are formed. The layers can be used in appropriate combination. A hydrophilic colloid can be used as a binder in these constituent layers, and gelatin is preferably used. In addition, various photographic additives described in the description of the emulsion layer can be contained in the layer.

The method for processing a photographic material using the silver halide emulsion used in the present invention is not particularly limited, and any generally known processing methods can be applied.
For example, typical examples thereof include a method of performing bleach-fixing after color development, and further performing washing and / or stabilization if necessary. After color development, performing bleaching and fixing separately, and further washing with water as necessary. The silver halide color photographic light-sensitive material of the present invention can be rapidly processed in the steps of color development, bleach-fixing, and washing (or stabilization). Suitable to be processed.

[0079]

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

Example 1 On a support in which polyethylene was laminated on one side of a paper support and polyethylene containing titanium oxide was laminated on the other side, each layer having the following constitution was replaced with a polyethylene layer containing titanium oxide. And a sample 1 of a multilayer silver halide color photographic light-sensitive material was prepared. The coating solution was prepared as follows.

First layer coating solution 30.1 g of yellow coupler (Y-1), 4.68 g of dye image stabilizer (ST-1), dye image stabilizer (ST-1)
-2) 6.03 g, 0.67 g of additive (HQ-1), 0.34 g of anti-irradiation dye (AI-3), 9.0 ml of high boiling organic solvent (DBP) and 60 ml of ethyl acetate
Was added and dissolved. A 10% aqueous gelatin solution containing 7 ml of a 20% aqueous solution of a surfactant (SU-1) was added to this solution.
20 ml was added and emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a coating solution for the first layer.

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

Further, (H) was added to the second and fourth layers as a hardening agent.
-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 light-sensitive material indicates the number of grams per 1 m ² unless otherwise specified.

[0084]

[Table 1]

[0085]

[Table 2]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) · sodium salt DBP: dibutyl phthalate DOP: dioctyl phthalate DNP: dinonyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone HQ-1: 2,5-di-t-octyl hydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butylhydroquinone H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium

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(Method for Preparing Blue-Sensitive Silver Halide Emulsion) 4
In 1000 cc of a 2% aqueous gelatin solution kept at 0 ° C,
The following (solution A) and (solution B) were subjected to pAg = 6.5, pH =
At the same time over 30 minutes while controlling to 3.0,
Solution) and (Solution D) were added simultaneously over 180 minutes while controlling pAg = 7.3 and pH = 5.5. The pH is controlled using an aqueous solution of sulfuric acid or sodium hydroxide, and pAg
For the control, a control liquid having the following composition was used. The composition of the control liquid is a mixed halide salt aqueous solution composed of sodium chloride and potassium sulfide, the ratio of chloride ion to bromide ion is 99.8: 0.2, and the concentration of the control liquid is solution A,
When mixing liquid B, 0.1 mol / liter, liquid C,
When mixing the liquid D, it was 1 mol / l.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide Water was added to make 200 cc.

(Solution B) Silver nitrate (10 g) was added to water to make 200 cc.

(Solution C) 102.7 g of sodium chloride 1.0 g of potassium bromide Water was added to make up to 600 cc.

(Solution D) Silver nitrate 300 g Water was added to finish to 600 cc.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
After desalting using a 5% aqueous solution and a 2.0% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to have an average particle diameter of 0.85 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (Preparation method of green-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) in the same manner as in EMP-1 except that the average particle diameter was 0.4.
A monodispersed cubic emulsion EMP-2 having a size of 3 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.

EMP-2 was prepared by using the following compound.
Chemical ripening was performed at 5 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (Method for Preparing Red-Sensitive Silver Halide Emulsion) (Solution A) and (B)
Liquid) and the addition time of (liquid C) and (liquid D) were changed in the same manner as in EMP-1 except that the average particle diameter was 0.5.
A monodispersed cubic emulsion EMP-3 having a thickness of 0 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.

The following compound was used for EMP-3.
Chemical ripening was performed at 0 ° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX Chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- (3-acetamido) phenyl-5-mercaptotetrazole

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Next, samples 102 and 10 were prepared in the same manner as in sample 101 except that the coupler Y-1 in the first layer was replaced with a yellow coupler shown in Table 3 (the amount added was an equimolar amount of Y-1).
3 was created. Samples 104 to 10 were prepared in the same manner as in Sample 101, except that the coupler C-1 in the fifth layer was replaced with a cyan coupler shown in Table 3 (the amount added was an equimolar amount of C-1).
No. 6 was created.

The samples thus obtained were subjected to wedge exposure with blue light for samples 101 to 103 and wedge exposure with red light for samples 101 and 104 to 106 according to a conventional method. Developed according to the conditions.

<Processing Conditions> 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 60 ° C. <Color developing solution> Pure water 800 cc 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 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 (CD-3 4.5 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.0 g Charcoal The is added to make 1 liter Potassium 27g water, adjusted to pH = 10.10.

<Bleaching-fixing solution> Ammonium ferric ethylenediaminetetraacetate dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc Ammonium sulfite (40% aqueous solution) 27.5 cc Water was added to bring the total volume to 1 liter. PH is adjusted to 5.7 with potassium carbonate 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 1,1-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 whitening agent (4,4'-diaminostilbene sulfonic acid derivative) 1 Add 0.5 g of water to make the total volume 1 liter, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

The color reproducibility and the maximum density (Dmax) of the obtained sample were measured as follows.

<Color Reproducibility> A Macbeth draft color checker was photographed using a color negative film (Konica Color LV-400: manufactured by Konica Corporation) and a camera (Konica FT-1 MOTOR: manufactured by Konica Corporation). Subsequently, color negative development processing (CNK-4: manufactured by Konica Corporation) was performed, and the obtained negative image was converted to a Konica Color Printer CL-
Using P2000 (manufactured by Konica Corporation)
o. Prints were made to a size of 82 mm × 117 mm on Nos. 1 to 24, and practical prints were obtained in the same manner as described above. Printer conditions at the time of printing were set for each sample so that the gray on the color checker became gray on the print.

With respect to the obtained practical prints, the color reproducibility was visually evaluated by five persons on a five-point scale. The evaluation scores are as follows: Evaluation 5: When 18 to 20 humans out of 20 evaluated that color reproducibility was good Evaluation 4: 14 to 17 humans out of 20 had color reproducibility Evaluation 3: When 10 to 13 humans out of 20 evaluated color reproducibility good Evaluation 2: 6 to 9 humans out of 20 evaluated good color reproducibility Evaluation 1: When 0 to 5 humans out of 20 evaluated that color reproducibility was good <Maximum density> The maximum density (Dmax) of each sample was measured using a Konica Corporation PDA-65 densitometer. It was measured.

Table 3 shows the results.

[0113]

[Table 3]

As is clear from Table 3, the samples using the comparative couplers are extremely insufficient in color reproducibility and coloring. On the other hand, the sample containing the yellow coupler and the cyan coupler of the present invention has color reproducibility,
In addition, improvement in coloring was observed.

Example 2 Next, in the sample 101 prepared in Example 1, the coupler C-1 in the fifth layer was replaced with a cyan coupler shown in Table 4 (the amount added was 50 mol% of C-1). In the same manner as in Sample 101, Samples 201 to 208 were prepared, and the same processing as in Example 1 was performed.

The color reproducibility and the maximum density (Dmax) of the obtained sample were measured in the same manner as in Example 1. Table 4 shows the results.

[0117]

[Table 4]

[0118]

Embedded image

As is clear from Table 4, the samples 101 and 201 using the comparative couplers are extremely insufficient in color reproducibility and coloring. On the other hand, the sample containing the cyan coupler of the present invention showed improved color reproducibility and color development as compared with the comparative sample.

[0120]

According to the present invention, a photographic coupler and a silver halide color photographic light-sensitive material excellent in color developability and color reproducibility can be provided.

Claims (3)

[Claims] 1. A photographic coupler having a cyclic molecular structure in which any two substituents other than the active site are condensed with each other at a site not adjacent to each other in the coupler skeleton. 2. 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. At least one layer of the red-sensitive silver halide emulsion layer has the following general formula (I) or general formula (I)
A silver halide color photographic material comprising a cyan coupler represented by I). Embedded image [Wherein, X ₁ and X ₂ each represent a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. J represents a divalent linking group, and these divalent linking groups may have a substituent. ] 3. 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. At least one layer of the red-sensitive silver halide emulsion layer has the following general formula (III) or general formula (I
A silver halide color photographic light-sensitive material containing a cyan coupler represented by V). Embedded image [In the formula, R ₁ and R ₂ each represent a substituted or unsubstituted alkylene group, an arylene group, or a divalent heterocyclic group. J represents a divalent linking group, and these divalent linking groups may have a substituent. ]