JPH0934067A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material low in fog and high in color developing density and superior in color reproduction performance and processable at a high speed by incorporating a specified cyan coupler in a red-sensitive silver halide emulsion layer and a specified magenta coupler in a green-sensitive silver halide emulsion layer. SOLUTION: The red-sensitive silver halide emulsion layer contains a cyan coupler represented by formula I or II and the green-sensitive silver halide emulsion layer contains a magenta coupler represented by formula III, and in the formulae I-III, each of R1 and R3 is a branched alkyl or substituted alkyl or aryl or heterocyclic group; each of R2 and R4 is a substituent; each of X1 and X2 is H atom or a group to be released by the reaction with the oxidation product of a color developing agent; R is H atom or a substituent; Z is a nonmetallic atomic group necessary to form an optionally substituted N-containing hetero ring; and X is H atom or a group to be released by the reaction with the oxidation product of the 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 rapid processing. Regarding

[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.

[0007] 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 it has become more and more required that the rapid processing is possible. There is.

However, the actual situation is that no silver halide photographic light-sensitive material satisfying this requirement has been found yet.

[0009]

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 rapid processing. .

[0010]

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. And the red-sensitive silver halide emulsion layer contains at least one cyan coupler represented by the following general formula (1) or (2), and the green-sensitive silver halide emulsion layer has the following general formula: It is achieved by a silver halide color photographic light-sensitive material characterized by containing at least one magenta coupler represented by [MI].

[0011]

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[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. ]

[0013]

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[Wherein R represents a hydrogen atom or a substituent, Z represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z has a substituent. May be. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent. The present invention will be described in detail below. First, 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-
Examples thereof include a propyl group, a t-butyl group, a sec-butyl group, an i-butyl group and a t-octyl group.

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.

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

The substituents are not particularly limited, but typically include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl groups, and the like. 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.

The sulfonyl group is an alkylsulfonyl group, an arylsulfonyl group or the like; the sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group or the like;
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 oxidized product of the color developing agent include halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, and heterocyclic oxy. , Acyloxy, sulfonyloxy, alkoxycarbonyloxy,
Aryloxy carbonyl, alkyl oxalyl oxy, alkoxy oxalyl oxy, alkyl thio, aryl thio, heterocyclic thio, alkyloxy thiocarbonyl thio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom, alkyloxy carbonylamino, aryloxy Examples thereof include carbonylamino and carboxyl groups. 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 couplers represented by the general formulas (1) and (2) are shown below, but the invention is not limited thereto.

[0035]

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[0036]

[Chemical 6]

[0037]

[Chemical 7]

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

[Chemical 12]

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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Next, the magenta coupler represented by the general formula [MI] of the present invention will be described. In the general formula [MI], the substituent represented by R is not particularly limited, but is typically each group such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl. In addition to these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide,
Examples also include ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, and heterocyclic thio groups, as well as spiro compound residues and bridged hydrocarbon compound residues.

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

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

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

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

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

The alkenyl group represented by R has 2 to 32 carbon atoms, and the cycloalkyl group has 3 carbon atoms.
-12, especially 5-7 are preferable, and the alkenyl group may be linear or branched.

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

The sulfonyl group represented by R is an alkylsulfonyl group, an arylsulfonyl group, etc .; The sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .; The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, Aryloxyphosphonyl group, arylphosphonyl group, etc .; Acyl group as alkylcarbonyl group, arylcarbonyl group, etc .; Carbamoyl group as alkylcarbamoyl group, arylcarbamoyl group, etc .; Sulfamoyl group as alkylsulfamoyl group, arylsulfur A famoyl group, an arylsulfamoyl group, etc .; as an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .;
The ureido group is preferably an alkylureido group, an arylureido group or the like; the sulfamoylamino group is an alkylsulfamoylamino group, an arylsulfamoylamino group or the like; and the heterocyclic group is preferably a 5- to 7-membered group. Specifically, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group or the like; a heterocyclic oxy group having a 5- to 7-membered heterocycle is preferable, 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 .; as siloxy groups, trimethylsiloxy group, triethyl group Siloxy group, dimethylbutyl siloxy like; succinimide imide group as a group, 3-heptadecyl succinic acid imide group, a phthalimide group, a glutarimide group and the like; spiro [3 as a spiro compound residue.
3] heptane-1-yl and the like. Examples of the bridged hydrocarbon compound residue bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1 ^3.7] decan-1-yl,
7,7-Dimethyl-bicyclo [2.2.1] heptane-
1-yl and the like can be mentioned.

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

[0058]

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(R ₁ ′ has the same meaning as R above, Z ′ has the same meaning as Z above, and R ₂ ′ and R ₃ ′ represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group), etc. Each group is mentioned, but a halogen atom, particularly a chlorine atom is preferable.

The nitrogen-containing heterocyclic ring formed by Z or Z'includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, and the like. The ones mentioned are mentioned.

Typical specific examples of the compound represented by formula [MI] of the present invention are shown below.

[0062]

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[0063]

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[0064]

[Chemical 21]

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

[Chemical formula 26]

[0070]

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[0071]

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[0072]

[Chemical 29]

[0073]

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[0074]

[Chemical 31]

To incorporate the cyan coupler or magenta coupler according to the present invention into the photographic light-sensitive material of the present invention,
Known techniques used in ordinary cyan couplers or magenta 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, the cyan coupler, magenta coupler and yellow coupler according to the present invention are used. The yellow coupler is not particularly limited and known ones can be used.

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

The silver halide emulsion in the present invention may be either a polydisperse emulsion or a monodisperse emulsion, but a monodisperse emulsion having uniform grain size is preferred.

In the monodisperse emulsion preferred in the present invention, the weight of silver halide contained in the grain size range of ± 20% centering on the weight average grain size d accounts for 70% or more of the weight of all silver halides. And more preferably 80% or more, and particularly preferably 90% or more.

The grain shape of the silver halide used in the present invention has a regular crystal form such as a cube, octahedron or tetradecahedron, or an irregular crystal form such as a sphere or a plate. Those having a crystal defect such as a twin plane or a twin plane, or a composite form thereof may be used. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

In the present invention, when a silver halide emulsion containing tabular silver halide grains is used, the tabular silver halide grains having a diameter / thickness ratio of 2 to 8 have a projected area as a whole. It is preferable to exist in a proportion of 70% or more of the grains, and 70% of all grains are tabular silver halide grains having a diameter / thickness ratio of 3 to 7 in terms of projected area.
It is preferably present in the above proportion.

The substance having adsorptivity on the surface of the silver halide grain can be added at an arbitrary temperature, but the amount of 30 to
It is preferably added at 80 ° C., and for the purpose of enhancing the adsorptivity, it is preferably added within the range of 50 to 80 ° C.
The pH and pAg values may be arbitrary, but at the time of chemical sensitization, pH 6-9 and pAg 8-9 are preferable.

Any substance can be used as the substance having adsorptivity on the surface of the silver halide grain, but it is necessary in the emulsion preparation process such as a sensitizing dye, an antifoggant and a photographic performance stabilizer. Preference is given to using substances.

When a photographic performance stabilizer is used, its addition amount is 500 to 3,000 per mol of silver halide.
mg is preferable, and 1,000 to 2,500 mg is more preferable. When a sensitizing dye is used, its addition amount is preferably 500 to 2,000 mg, and more preferably 600 to 1,000 mg, per mol of silver halide.

As the photographic performance stabilizer, Research Disclosure (RD) No. 308119, page 998 VI, ibid. 17643, pages 24-25, ibid. 18716, page 649 can be mentioned. Research sensitizing dyes
Disclosure (RD) No. 308119, 9th
Page 96 VI-A-A, B, C, D, H, I, J Section, N
o. 17643, pages 23-24, ibid. 1871
6, those described on pages 648 to 649 can be mentioned.

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, cellulose acetate, cellulose nitrate, polyester film such as 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 depending on 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 various layers such as a filter layer, an anti-curl 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.

[0093]

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 solution Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, 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.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

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[0101]

[Chemical 33]

[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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(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 up to 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.

(Liquid D) Silver nitrate 300 g 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 diameter of 0.85 μm, a variation coefficient of 0.07, and a silver chloride content of 99.5 mol. % Of a monodispersed cubic emulsion EMP-1.

The 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 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 chemically ripened at 55 ° C. for 120 minutes using the following compound 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 (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 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. EMP-3 was chemically ripened at 60 ° C. for 90 minutes using the following compounds 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 The coefficient of variation is the number obtained by dividing the standard deviation of the particle size by the average particle size.

[0117]

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Next, in the sample 1, the cyan couplers C-1 and C-2 of the fifth layer are shown in Table 3 (the addition amount is the same molar amount as the total number of moles of the comparative couplers C-1 and C-2).
Samples 2 to 22 were prepared in exactly the same manner except that the magenta coupler MM-1 in the third layer was changed to the coupler shown in Table 3 (the addition amount was the same molar amount as that of the comparative coupler MM-1). did.

The obtained sample 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.

After subjecting the obtained sample to wedge exposure by a conventional method, the treatment time of the treatment step is set to 30.
Development was performed in the same process except that the second was set, and the fog (Fog) and the maximum density (Dmax ') of the red-sensitive photosensitive layer were 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.

Treatment process 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 carbonate 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.

[0128]

[Table 3]

[0129]

Embedded image

As is apparent from Table 3, Sample No. 1 using the cyan coupler outside the present invention and the magenta coupler outside the present invention. No. 1 to No. 1 No. 3 has high fog, insufficient color developability, color reproducibility and rapid processability. In addition, in Sample No. 1 using the cyan coupler of the present invention and the magenta coupler of the present invention. No. 4 has some improvement in fog and color developability, but it cannot be said that the color reproducibility is sufficient. On the other hand, Sample No. 1 using the cyan coupler other than the present invention and the magenta coupler of the present invention. No. 5 has high fog, insufficient rapid processability, and color reproduction cannot be said to be sufficient. On the other hand, the sample No. 6-Sample No. No. 22 has low fog, good color developability, and very good rapid processability and color reproducibility.

[0131]

According to the present invention, a silver halide color photographic light-sensitive material having low fog, high color density, excellent color reproducibility and capable of rapid processing can be provided.

Claims (1)

[Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is represented by the following general formula (1) or general formula (2). A silver halide color photographic light-sensitive material containing at least one cyan coupler and at least one magenta coupler represented by the following general formula [MI] in the green-sensitive silver halide emulsion layer. material. 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. [Chemical formula 2] [In the formula, R represents a hydrogen atom or a substituent, Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and
The ring formed by may have a substituent. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent. ]