JPH0934070A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material low in fog and high in color developing density and superior in color reproduction performance and stability to processing fluctuation. SOLUTION: The photographic constituent layers on the support of the photosensitive material comprise blue-, green-, and red-sensitive silver halide emulsion layers and at least one of the emulsion layers contains silver halide grains containing >=90mol% high chloride silver halide and the red-sensitive silver halide emulsion layer contains at least one kind of cyan coupler represented by formulae I and II in which each of R1 and R3 is a branched alkyl group or a substituted alkyl or aryl group or a heterocyclic group; each of R2 and R4 is a substituent; and each of X1 and X2 in H atom or a group to be released by reaction with the oxidation product of a color developing agent.

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 low fog, high color density, excellent color reproducibility and little process variation.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material for direct viewing, such as color photographic 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 properties such as color reproducibility, color developability and image storability in dye images to be obtained. In recent years, in particular, color reproduction is performed to faithfully reproduce the original color of the object. There is a growing demand from users to improve the quality.

To date, phenols or naphthols have been widely used as cyan image forming couplers.

However, the cyan image obtained from the conventionally used phenols and naphthols has a serious problem in color reproduction. That is, the sharpness of absorption on the short wave side is poor, and unnecessary absorption, that is, irregular absorption, is also present in the green region. As a result, it is unavoidable to correct irregular absorption due to masking or the like in the negative, and in the case of paper, there is no means for correction, and color reproducibility is considerably deteriorated at present.

For the purpose of improving color reproducibility, Japanese Patent Laid-Open No. Sho 64-64
-554, 63-250649, 63-250.
No. 650 and the like propose a pyrazoloazole type cyan coupler.

However, these couplers show good color reproducibility because electron-withdrawing groups and hydrogen-bonding groups are introduced in order to satisfy the absorption wavelength of the color-forming dye formed. However, the level of coupling activity was not sufficiently satisfactory, and color development and color reproducibility were not simultaneously satisfied.

Further, in recent years, the printing process and the developing process of the light-sensitive material for color photographing and printing have been shortened and accelerated, and the stability of the process is more and more required. .

In particular, the change in photographic performance associated with the change in the concentration of processing liquid components during continuous processing has become an increasingly serious problem in rapid processing.

However, the reality is that a silver halide photographic light-sensitive material satisfying this requirement has not yet been found.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material having low fog, high color density, excellent color reproducibility, and little processing variation.

[0011]

The above object of the present invention is to provide a photographic constituent 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 silver halide emulsion layers contains high chloride silver halide grains having a silver chloride content of 90 mol% or more, and the red-sensitive silver halide emulsion layer has the following general formula (1) or It is achieved by a silver halide color photographic light-sensitive material characterized by containing at least one cyan coupler represented by the general formula (2).

[0012]

Embedded image

[Wherein R ₁ and R ₃ each represent a branched alkyl group, a substituted alkyl group, a substituted aryl group or a heterocyclic group, R ₂ and R ₄ each represent a substituent, and X ₁ and X ₂
Each represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. The present invention will be described in detail below.

First, the high chloride silver halide grains having a silver chloride content of 90 mol% or more according to the present invention will be described in detail.

In the present invention, it is necessary that at least one of the light-sensitive silver halide emulsion layers contains silver halide grains consisting essentially of silver chloride.

The silver halide grains contained in the silver halide emulsion layer other than the above may be any silver halide grains such as silver chlorobromide grains and silver chloroiodobromide grains, and there is no particular limitation. .

The silver halide grains substantially consisting of silver chloride used in the present invention (hereinafter referred to as "silver halide grains of the present invention") have a silver chloride content of 90 mol% or more. High chloride silver halide grains. The silver bromide content in the silver halide grains is 10
It is preferable that the content of the silver iodide is 0.5 mol% or less and the content of silver iodide is 0.5 mol% or less. More preferably, the silver bromide content is 0.1.
２2 mol% of silver chlorobromide.

The silver halide grains of the present invention may be used alone or in combination with other silver halide grains having different compositions. Further, it may be used as a mixture with silver halide grains having a silver chloride content of 10 mol% or less.

In the silver halide emulsion layer containing the silver halide grains of the present invention, the ratio of the silver halide grains of the present invention to the total silver halide grains contained in the emulsion layer is 60% by weight. % Or more, preferably 80% by weight or more.

The composition of the silver halide grain of the present invention may be uniform from the inside to the outside of the grain,
The composition inside and outside the particle may be different. When the composition inside and outside the particle is different, the composition may continuously change or may be discontinuous.

The grain size of the silver halide grains of the present invention is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0. It is in the range of 25 to 1.2 μm. The particle diameter can be measured by various methods generally used in the technical field. As a typical method, Lapland's “particle size analysis method” (AS.
T. M. Symposium on Right Microscopy, 1955, pp. 94-122) or "The Theory of Photographic Processes" (Mies and James, 3rd edition, Chapter 2 published by Macmillan, Inc. (1966)). There is.

The particle diameter can be measured by using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.
Preferably, they are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, in the particle size distribution of the silver halide grains.

The silver halide grains of the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halogen salt may be any one of a forward mixing method, a back mixing method, a simultaneous mixing method and a combination thereof, but a method obtained by the simultaneous mixing method is preferable. Further, as one form of the simultaneous mixing method, p described in JP-A-54-48521, etc.
It is also possible to use the Ag-controlled-double jet method.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound or a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.

The silver halide grains of the present invention may have any shape. One preferred example is {1
It is a cube having a {00} plane as a crystal surface.

Further, particles having a shape of octahedron, tetrahedron, dodecahedron or the like can be used. Further, particles having a twin plane may be used.

The silver halide grain of the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

The silver halide grain of the present invention uses a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt, an iron salt or a complex salt in the grain formation process and / or the growth process. Metal ions can be added to the metal particles and included in the particles and / or on the surface of the particles.
Further, the reduction sensitizing nuclei can be imparted to the inside of the grain and / or the surface of the grain by placing in an appropriate reducing atmosphere.

In the emulsion containing the silver halide grains of the present invention (hereinafter referred to as the emulsion of the present invention), unnecessary soluble salts may be removed after the growth of the silver halide grains is completed.
Alternatively, it may be kept contained. The removal of the salts can be carried out according to the method described in Research Disclosure 17643.

The silver halide grain of the present invention is preferably a grain in which a latent image is mainly formed on the surface, but it may be a grain in which a latent image is formed inside the grain.

In the present invention, a chalcogen sensitizer can be used. Chalcogen sensitizer is sulfur sensitizer,
It is a general term for selenium sensitizers and tellurium sensitizers, but sulfur sensitizers and selenium sensitizers are preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. In addition, U.S. Pat. Nos. 1,574,944 and 2,410,689,
2,278,947, 2,728,668, 3,501,313, 3,656,955, West German Application Publication (OLS) 1,422,869, JP-A-56
The sulfur sensitizers described in JP-A-24937 and JP-A-55-45016 can also be used. The addition amount of the sulfur sensitizer varies over a considerable range depending on various conditions such as pH, temperature and size of silver halide grains, but as a guide, it is 10 ^-7 mol to 10 ^-1 per mol of silver halide. A molar amount is preferable.

The emulsion of the present invention can be used in combination with a reduction sensitization method using a reducing substance and a noble metal sensitization method using a noble metal compound.

Next, the cyan couplers represented by the general formulas (1) and (2) of the present invention will be described in detail.

In the general formulas (1) and (2), the branched alkyl group represented by R ₁ and R ₃ is i
-Propyl group, t-butyl group, sec-butyl group, i-
A butyl group, a t-octyl group, etc. can be mentioned.

As the alkyl component of the substituted alkyl group,
It may be linear, branched or cyclic alkyl group, such as methyl group, ethyl group, butyl group, i-propyl group, t-butyl group, sec-butyl group, i-butyl group, t-octyl group, cyclohexyl group and the like. Can be mentioned.

As the aryl component of the substituted aryl group,
A phenyl group etc. can be mentioned.

As the heterocyclic group, 2-furyl group, 2-thienyl group, 2-imidazolyl group, 2-thiazolyl group, 3
-Isoxazolyl group, 3-pyridyl group, 2-pyridyl group, 2-pyrimidyl group, 3-pyrazolyl group, 2-benzothiazolyl group and the like can be mentioned.

However, when R ₁ and R ₃ represent a substituted alkyl group or a substituted aryl group, these alkyl and aryl components always have a substituent.

When R ₁ and R _{3 each} represent a branched alkyl group or a heterocyclic group, these groups may have a substituent if necessary.

There are no particular restrictions on these substituents, but typical examples include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, and other groups. A halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, 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.

In the general formulas (1) and (2), R ₂
The substituent represented by and R ₄ is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups. A halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy,
Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, sulfo and other groups, In addition, spiro compound residues, bridged hydrocarbon compound residues and the like are also included. These groups may be further substituted with the above substituents.

In the above-mentioned substituents for the branched alkyl group represented by R ₁ and R ₃ , the substituted alkyl group, the substituted aryl group or the heterocyclic group, and the substituents represented by R ₂ and R ₄ , The alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched.

The aryl group is preferably a phenyl group.

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.

Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include the alkyl group and the aryl group in the substituents represented by R ₂ and R ₄ .

The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 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;
The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; The acyl group is an alkylcarbonyl group, an arylcarbonyl group, etc .; The carbamoyl group is an alkylcarbamoyl group, an arylcarbamoyl group. Etc .; as sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, etc .; as acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc .; as sulfonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, etc. A carbamoyloxy group as an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; a ureido group as an alkylureido group, an arylureido group, etc .; sulfamoylamino As alkylsulfamoyl group, an aryl sulfamoylamino group such as, is preferably a 5- to 7-membered as heterocyclic group, specifically 2-
Furyl, 2-thienyl, 2-pyrimidinyl, 2-
A benzothiazolyl group, a 1-pyrrolyl group, a 1-tetrazolyl group, etc .; a heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group , 1-phenyltetrazole-5-oxy group and the like; the heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy. -1,3,5-triazole-6-thio group, etc .; siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group, succinimide group, 3-heptadecylsuccinimide group , Phthalimide group, glutarimide group, etc .; spiro [3.3] heptan-1-yl, etc. as spiro compound residue; bridged hydrocarbon compound Examples of the group bicyclo [2.
2.1] heptan-1-yl, tricyclo [3.3.
1.1 ³⁷ ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

The substituent represented by R ₂ and R ₄ is preferably an alkyl group or an aryl group, and particularly preferably an aryl group.

The above 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 represented by X ₁ and X ₂ which can be split off by the reaction with the oxidation product of the color developing agent include halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, and heterocyclic oxy. , Acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio,
Examples include acylamino, sulfonamide, nitrogen-containing heterocycle linked by an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl. X ₁ and X ₂ are preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a nitrogen-containing heterocyclic group bonded by an N atom and the like.

Among the cyan couplers represented by the general formulas (1) and (2), those represented by the general formula (1) are preferable.

Specific examples of the cyan coupler represented by formulas (1) and (2) are shown below, but the invention is not limited thereto.

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

[Chemical 6]

[0061]

[Chemical 7]

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

[Chemical 12]

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

The cyan coupler of the present invention is usually 1 × 10 ^-3 to 1 mol, preferably 1 ×, per mol of silver halide.
It can be used in the range of 10 ⁻² to 8 × 10 ⁻¹ mol.

In order to incorporate the cyan coupler of the present invention into the photographic light-sensitive material of the present invention, known techniques used in ordinary cyan 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 photographic light-sensitive material of the present invention is used as a full-color light-sensitive material, a magenta coupler and a yellow coupler are used in addition to the cyan coupler of the present invention. The magenta coupler and the yellow coupler are not particularly limited, and known ones can be used.

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

As the yellow coupler, for example, an open chain ketomethylene type coupler can be used.

The silver halide photographic light-sensitive material of the present invention includes:
A water-soluble dye may be contained in the hydrophilic colloid layer 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 can be used. (RD1
See 7643. ) Furthermore, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a fog agent, an antifoggant, by coupling with a competing coupler and an oxidized product of a developing agent,
Compounds that release photographically useful fragments can be used, such as chemical sensitizers, spectral sensitizers, and desensitizers.

The support of the silver halide photographic light-sensitive material of the present invention is, 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. There are films, polystyrene films, 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 layers 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 a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer are sequentially provided from the support side. The arrangement is preferably

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, and further various layers such as a filter layer, a curl preventing layer, a protective layer and an antihalation layer are constituted. The layers can be appropriately combined and used. 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 processing method of the photographic light-sensitive material using the silver halide emulsion of the present invention is not particularly limited, and any generally known processing method can be applied. For example, as a typical example, a method of performing bleach-fixing treatment after color development and further performing washing and / or stabilizing treatment if necessary, and performing bleaching and fixing separately after color development, and further washing with water as necessary. And / or stabilization treatment may be carried out, and 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 stabilizing). Suitable to be processed.

[0083]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 On a support having polyethylene laminated on one side of a paper support and polyethylene containing titanium oxide on the other side, a polyethylene layer containing titanium oxide was added to each layer having the following constitution. Sample 1 of a multilayer silver halide color photographic light-sensitive material was prepared by coating on the side of. The coating liquid was prepared as follows.

First layer coating liquid 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (ST
-2) 6.67 g, additive (HQ-1) 0.67 g, anti-irradiation dye (AI-3) 0.33 g, high boiling organic solvent (DNP) 6.67 g, and ethyl acetate 60 ml.
To dissolve the solution, and add 20% surfactant (SU-
1) 220 ml of 10% gelatin aqueous solution containing 7 ml
The mixture was 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 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 hardener, the second and fourth layers (H
-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 added in the silver halide photographic light-sensitive material indicates the number of grams per 1 m ² unless otherwise specified.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

[Chemical 21]

[0096]

Embedded image

(Preparation method of blue-sensitive silver halide emulsion) 4
The following (solution A) and (solution B) were pAg = 6.5 and pH = 3 in 1000 ml of a 2% aqueous gelatin solution kept at 0 ° C.
The solution was added simultaneously over 30 minutes while controlling to 0, and the following (Solution C) and (Solution D) were further pAg = 7.3 and pH = 5.
5 and simultaneously added over 180 minutes. The pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide. For control of pAg, a control solution having the following composition was used. The composition of the control liquid is a mixed halide salt aqueous solution consisting of sodium chloride and potassium sulfide, the ratio of chloride ion to bromide ion is 99.8: 0.2, and the concentrations of the control liquid are A liquid and B liquid. The amount was 0.1 mol / liter when the liquids were mixed, and 1 mol / liter when the liquids C and D were mixed.

(Liquid A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to make up to 200 ml.

(Solution B) Silver nitrate 10 g Water was added to make a final volume of 200 ml.

(Liquid C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to make a final volume of 600 ml.

(Solution D) 300 g of silver nitrate Water was added to make 600 ml.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
a Desalting was performed using a 5% aqueous solution and a 2.0% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to have an average particle size of 0.85 μm, a coefficient of variation (σ / F) = 0.07, and containing silver chloride. Cubic Emulsion EMP with 99.5 mol%
-1 was obtained.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound 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 thickness of 3 μm, a coefficient of variation (σ / F) = 0.08 and a silver chloride content of 99.5 mol% was obtained.
For EMP-2, 120 at 55 ° C. using the following compounds
Chemical ripening is carried out to obtain a green-sensitive silver halide emulsion (Em-
G) was obtained.

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 (Preparation method of 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 monodisperse cubic emulsion EMP-3 having a thickness of 0 μm, a coefficient of variation (σ / F) = 0.08 and a silver chloride content of 99.5 mol% was obtained.
EMP-3 was chemically ripened at 60 ° C. for 90 minutes using the following compound to give a red-sensitive silver halide emulsion (Em-
R) was obtained.

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

[0107]

[Equation 1]

A comparative emulsion Em-R 'was prepared in the same manner as Em-R except that the halogen composition of the Em-R was silver chlorobromide containing 20 mol% of AgBr.

[0109]

Embedded image

Next, in Sample 1, the fifth layer cyan couplers C-1 and C-2 are shown in Table 3 (the addition amount is the same molar amount as the total number of moles of comparative couplers C-1 and C-2). Alternatively, Samples 1 to 22 were prepared in the same manner except that the silver halide emulsion was changed as shown in Table 2.

The sample thus obtained was subjected to wedge exposure by a conventional method and then developed, and the fog (Fog) and maximum density (Dmax) of the red-sensitive photosensitive layer were measured.

Further, the obtained sample was subjected to wedge exposure by a conventional method, and then the amount of CD-3 as a color developing agent in the color developing solution in the processing step was 3.5 g / l. Processing was performed by the same process, and the maximum density (Dmax ') of the red-sensitive photosensitive layer was measured.

The color reproducibility of each of Samples 1 to 22 was evaluated by the following method. First, a color checker manufactured by Macbeth 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 processed by using Konica Color Printer CL-P2000 (manufactured by Konica Corporation). 82 mm x 11 from 1 to 22
Printing was performed in a size of 7 mm, and a practical print was obtained in the same manner as 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.

The color reproducibility of the obtained practical prints was visually evaluated.

The results are summarized in Table 3.

The processing conditions are as follows.

Processing step Temperature Time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Dry 60-80 ° C. 60 seconds Color development Developer 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 g catechol-3,5-disulfonic acid disodium salt 1.0 g diethylene glycol 10 g N-ethyl-N-β-methanesulfonamide ethyl-3-methyl-4-aminoaniline sulfate (CD-3) 4.5 g fluorescence enhancement Whitening agent (4,4'-diaminostilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.10.

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

Stabilizing liquid 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 optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

[0120]

[Table 3]

[0121]

Embedded image

As is apparent from Table 3, the sample No. using the cyan coupler other than the present invention was used. No. 1 to No. 1 3 is
Fog is high, color development is insufficient, color reproducibility and processing variability are insufficient. On the other hand, Sample No. using silver halide which is not in the present invention. 4 to sample No. No. 6 shows a slight improvement in fog, but no improvement in color developability, processing variability and color reproducibility. On the other hand, the sample No. 7 to sample no. No. 22 has low fog, good color developability, and very good process variability and color reproducibility.

[0123]

According to the present invention, a silver halide color photographic light-sensitive material having a low fog, a high color density, an excellent color reproducibility and a small process variation can be provided.

Claims (1)

[Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
A high chloride silver halide having a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and at least one silver halide emulsion layer having a silver chloride content of 90 mol% or more. And a red-sensitive silver halide emulsion layer containing at least one cyan coupler represented by the following general formula (1) or (2). . Embedded image [In the formula, R ₁ and R ₃ each represent a branched alkyl group, a substituted alkyl group, a substituted aryl group or a heterocyclic group, R ₂ and R ₄ each represent a substituent, and X ₁ and X ₂ each represent a hydrogen atom. Alternatively, it represents a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]