JPH0943789A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance color development performance and color reproduction performance by incorporating a specified coupler in a silver halide emulsion layer. SOLUTION: A red-sensitive silver halide emulsion layer contains at least one kind of cyan coupler selected from formulae I and II and a blue-sensitive silver halide emulsion layer contains a yellow coupler represented by formula III, and in formulae I-III, each of R1 and R3 is a branched alkyl or substituted alkyl or a substituted aryl or heterocyclic group; each of R2 and R4 is a substituent; each of X1 and X2 is an H atom or a group to be released by reaction with the oxidation product of a color developing agent; RA is an alkyl or cycloalkyl group; RB is an alkyl, cycloalkyl, aryl, or acyl group; RC is a group substd. on the benzene ring; (n) is 0 or 1; XA is a group to be released by coupling with the oxidation product of a developing agent; and YA is an organic group.

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 specifically, a halogen having good color forming properties, excellent color reproducibility, good fading balance, and excellent initial developability. The present invention relates to a silver halide color photographic light-sensitive material.

[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 performance such as color reproducibility, color developability and image storability in the obtained dye image. In particular, in recent years, 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, sharpness on the short wave side of absorption 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, in order to satisfy the absorption wavelength of the color forming dye formed by any of these couplers,
Since an electron-withdrawing group and a hydrogen-bonding group are introduced,
Although it showed good color reproducibility, it was not at a sufficiently satisfactory level in terms of coupling activity, and it did not satisfy both color development and color reproducibility at the same time.

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

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 An object of the present invention is to provide a silver halide color photographic light-sensitive material having good color forming properties, excellent color reproducibility, good color fading balance, and excellent initial developability. To provide.

[0011]

The above object of the present invention is achieved by the following constitution.

1. The support has a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, the red-sensitive silver halide emulsion layer having the following general formula ( 1) or at least one of the cyan couplers represented by the general formula (2), and the blue-sensitive silver halide emulsion layer contains a yellow coupler represented by the following general formula [Y-I]. Characteristic silver halide color photographic light-sensitive material.

[0013]

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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 represent Each represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent. ]

[0015]

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In the formula, R ^A represents an alkyl group or a cycloalkyl group, R ^B represents an alkyl group, a cycloalkyl group, an aryl group or an acyl group, and R ^C represents a group capable of substituting on the benzene ring. n represents 0 or 1. X ^A represents a group capable of splitting off upon coupling with an oxidized product of a developing agent, and Y ^A
Represents an organic group.

Hereinafter, the present invention will be described in detail.

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 R1 and R3 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.

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.

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 also include ring thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, sulfo, and other groups, spiro compound residues, bridged hydrocarbon compound residues, and the like.

In the general formulas (1) and (2), the substituents represented by R ₂ and R ₄ are not particularly limited, but typically, alkyl, aryl, anilino, acylamino,
Examples thereof include sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups, but also 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, heterocyclicthio , Thioureido, carboxyl, hydroxyl, mercapto, nitro, sulfo, and other groups, as well as spiro compound residues and bridged hydrocarbon compound residues. These groups may be further substituted by 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,
It 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 group. -1,3,5-triazole-6-thio group, etc .; siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group, succinimide group, 3-heptadecylsuccinimide group , Phthalimido group, glutarimido 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-mentioned group 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. However, the cyan coupler of the present invention is not limited to these.

[0039]

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[0040]

[Chemical 6]

[0041]

[Chemical 7]

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

[Chemical 12]

[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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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.

Next, the yellow coupler represented by the general formula [Y-I] of the present invention will be described.

In the general formula [Y-I], the alkyl group represented by R ^A is, for example, a methyl group, an ethyl group,
Examples thereof include an isopropyl group, a t-butyl group and a dodecyl group. The alkyl group represented by R ^A also includes those having a substituent, and examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an acylamino group and a hydroxyl group. Is mentioned.

Examples of the cycloalkyl group represented by R ^A include a cyclopropyl group, a cyclohexyl group and an adamantyl group. R ^A is preferably a branched alkyl group, and particularly preferably a t-butyl group.

In the general formula [Y-I], examples of the alkyl group and cycloalkyl group represented by R ^B include the same groups as those described in the description of R ^A , and the aryl represented by R ^B Examples of the group include a phenyl group. The alkyl group, cycloalkyl group, and aryl group represented by R ^B include those having the same substituents as the groups described in the description of R ^A. Examples of the acyl group represented by R ^B include an acetyl group, a propionyl group, a butyryl group, a hexanoyl group and a benzoyl group. R
^B is preferably an alkyl group or an aryl group,
An alkyl group is more preferable, and a lower alkyl group having 5 or less carbon atoms is further preferable.

In the general formula [Y-I], the group capable of substituting on the benzene ring represented by R ^C is a halogen atom (eg chlorine atom), an alkyl group (eg ethyl group, i
-Propyl group, t-butyl group), alkoxy group (eg methoxy group), aryloxy group (eg phenyloxy group), acyloxy group (eg methylcarbonyloxy group, benzoyloxy group), acylamino group (eg acetamide group, phenyl) Carbonylamino group), carbamoyl group (for example, N-methylcarbamoyl group, N-phenylcarbamoyl group), alkylsulfonylamino group (for example, ethylsulfonylamino group), arylsulfonylamino group (for example, phenylsulfonylamino group),
Examples thereof include a sulfamoyl group (eg, N-propylsulfamoyl group, N-phenylsulfamoyl group) and an imide group (eg, succinimide group, glutarimide group). n represents 0 or 1.

In the general formula [Y-I], Y ^A represents an organic group and is not limited, but preferably the following general formula [Y-
II] is a group represented by

[0059] In the general formula [Y-II] -J-R ^D type, J is ^{-N (R E) -CO -,} - CON (R E) -,
^{-COO -, - N (R E} ) -SO 2 - or -SO ₂ -N
Represents ( ^RE )-. R ^D and R ^E represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

Examples of the alkyl group represented by R ^D and R ^E include a methyl group, an ethyl group, an isopropyl group, a t-butyl group and a dodecyl group. Examples of the aryl group represented by R ^D and R ^E include a phenyl group and a naphthyl group. The alkyl group or aryl group represented by R ^D and R ^E also includes those having a substituent.
The substituent is not particularly limited, but typical examples thereof include a halogen atom (chlorine atom or the like), an alkyl group (ethyl group, t-butyl group or the like), an aryl group (phenyl group, p-methoxyphenyl, etc.). Group, naphthyl group, etc.), alkoxy group (ethoxy group, benzyloxy group, etc.), aryloxy group (phenoxy group, etc.), alkylthio group (ethylthio group, etc.), arylthio group (phenylthio group, etc.), alkylsulfonyl group (β- Hydroxyethylsulfonyl group etc.), arylsulfonyl group (phenylsulfonyl group etc.), and acylamino group such as alkylcarbonylamino group (acetamido group etc.), arylcarbonylamino group (phenylcarbonylamino group etc.);
A carbamoyl group, for example, an alkyl group, an aryl group (preferably a phenyl group) or the like is substituted, and specifically, an N-methylcarbamoyl group, an N-phenylcarbamoyl group or the like; an acyl group such as an acetyl group or the like Arylcarbonyl groups such as alkylcarbonyl groups and benzoyl groups; sulfonamide groups such as alkylsulfonylamino groups, arylsulfonylamino groups, specifically methylsulfonylamino groups, benzenesulfonamide groups; sulfamoyl groups such as alkyl groups, aryl It also includes those substituted with a group (preferably a phenyl group) and the like, and specific examples thereof include an N-methylsulfamoyl group, an N-phenylsulfamoyl group and the like; a hydroxyl group; a nitrile group and the like.

Particularly preferred as the group represented by -J-R ^D is -NHCOR ' ^D. Wherein R ^'D represents an organic group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms, such as methyl group, ethyl group, n- propyl, isopropyl, t- butyl radical, n
-Pentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, linear and branched dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, Examples thereof include nonadecyl group, eicosyl group, docosyl group, tetracosyl group and hexacosyl group. Particularly preferred among these alkyl groups are alkyl groups having 8 to 20 carbon atoms.

In the general formula [Y-I], X ^A represents a group capable of leaving during the coupling reaction with the oxidized product of the developing agent.
Examples of these groups include groups represented by general formula [Y-III] or general formula [Y-IV] shown below, and groups represented by general formula [Y-IV] are preferred.

General formula [Y-III] -OR ^{F In the} general formula [Y-III], R ^F is an aryl group including those having a substituent or a heterocyclic group represented by the following general formula [Y-IV]. Represents

[0064]

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In the general formula [Y-IV], Z ^A represents a group of non-metal atoms necessary for forming a 5- or 6-membered ring in cooperation with a nitrogen atom. Here, the atomic group necessary for forming the non-metal atomic group is, for example, methylene, methine, substituted methine,-(CO)-,-(NR ^G )-(R ^G has the same meaning as R ^E above). , -N =, - O -, - S -, - SO 2 - , and the like.

The yellow coupler represented by the above general formula [Y-I] may be combined at the R ^A , R ^C or Y ^A portion to form a bis form.

Specific examples of the yellow coupler represented by the general formula [Y-I] are shown below.

[0068]

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[0069]

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[0070]

[Chemical 21]

[0071]

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[0072]

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[0073]

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[0074]

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[0075]

[Chemical formula 26]

[0076]

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[0077]

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[0078]

[Chemical 29]

The yellow couplers represented by the general formula [Y-I] of the present invention are disclosed in JP-A-63-123047,
It can be easily synthesized by the method described in JP-A-4-124661 and JP-A-4-9051.

The yellow coupler represented by the general formula [Y-I] according to the present invention can be used alone or in combination of two or more kinds, or can be used in combination with another kind of yellow coupler.

In the present invention, the yellow coupler is usually used in an amount of about 1 × 10 ^-3 mol / mol of silver halide.
It can be used in an amount of about 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1 mol.

When the photographic 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 according to 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 type coupler, a pyrazolobenzimidazole type coupler, a pyrazolotriazole type coupler and a closed acylacetonitrile type 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 comprises
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 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 thereof, after color development, a bleach-fixing treatment is carried out, and if necessary, further washing with water and / or a stabilizing treatment is carried out,
After color development, bleaching and fixing are performed separately, and if necessary, further washing with water and / or stabilizing treatment may be carried out, and any method may be used. The silver halide color photographic light-sensitive material of the present invention Is suitable for rapid processing in the steps of color development, bleach-fixing and washing (or stabilizing).

[0093]

The present invention will be described in detail below with reference to examples, 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 (YY-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (S
T-2) 6.67 g, additive (HQ-1) 0.67 g,
0.33 g of anti-irradiation dye (AI-3), 6.67 g of high boiling organic solvent (DNP), and 60 m of ethyl acetate.
1 and dissolved, and this solution was added to a 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 31]

[0102]

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[0103]

[Chemical 33]

[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.
0 and added simultaneously over 30 minutes.
Liquid) and (D liquid) were simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5. 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 was a mixed halide salt aqueous solution consisting of sodium chloride and potassium sulfide, the ratio of chloride ion to bromide ion was 99.8: 0.2, and the concentration of the control liquid was A.
When mixing liquid B and liquid B, 0.1 mol / liter, C
When the liquid and the liquid D were mixed, the amount was 1 mol / liter.

(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 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 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, the following compounds were used:
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 (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.

The following compounds were 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

[0119]

[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.

[0121]

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Next, in Sample 1, 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 comparative couplers C-1 and C-2). Alternatively, Samples 2 to 22 were prepared in exactly the same manner except that the yellow coupler in the first layer was changed as shown in Table 3.

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

The color reproducibility of each of Samples 1 to 22 was evaluated by the following method.

First, a color negative film (Konica Color LV-400: manufactured by Konica Corporation) and a camera (Konica F)
T-1 MOTOR: manufactured by Konica Corporation) was used to photograph a color checker manufactured by Macbeth. 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-P.
Sample No. 2000 (manufactured by Konica Corporation).
1 to 22 were printed in a size of 82 mm × 117 mm, 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.

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

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 carbonic acid. Adjust the pH to 5.7 with potassium or glacial acetic acid.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1 -Diphosphonic acid 2.0 g o-phenylphenol sodium 1.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% aqueous solution) 3.0 g optical brightener (4,4'-diaminostilbenesulfonic 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.

Further, the obtained sample was subjected to wedge exposure by a conventional method and then processed in the same steps except that the processing time of the color development step in the above-mentioned processing step was set to 30 seconds. The maximum density (Dmax ') of the layer was measured.

The maximum concentration (Dmax) of each of Samples 1 to 22 treated above was measured using a densitometer (Konica KD-7 type), and each treated sample was treated at high temperature with It was left in a high humidity (85 ° C., 60% RH) atmosphere for 30 days, and the discoloration balance was visually evaluated.

The results are summarized in Table 3.

[0134]

[Table 3]

[0135]

Embedded image

As is apparent from Table 3, Sample No. 1 using the yellow coupler outside the present invention and the cyan coupler outside the present invention. No. 1 to No. 1 No. 3 has insufficient color developability, color reproducibility, color fading balance and initial developability. In addition, Sample No. 1 using the cyan coupler of the present invention and the yellow coupler other than the present invention. In No. 4, although the color developing property is improved, it is difficult to say that the color reproducibility, the color fading balance and the initial developing property are sufficient. On the other hand, Sample No. 1 using the cyan coupler other than the present invention and the yellow coupler of the present invention. 5 is
Although the initial developability is improved, it is difficult to say that the color reproducibility and the fading balance are sufficient. On the other hand, the sample No. 6
~ Sample No. No. 22 has good color developability, and is very good in color reproducibility, color fading balance, and initial developability.

[0137]

INDUSTRIAL APPLICABILITY The silver halide color photographic light-sensitive material according to the present invention is capable of obtaining an image having excellent color developability, excellent color reproducibility, good color fading balance, and excellent initial developability. .

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 a yellow coupler represented by the following general formula [Y-I] in the blue-sensitive silver halide emulsion layer. 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, and R ₂ and R ₄
Represents a substituent, and 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. [Chemical formula 2] [In the formula, R ^A represents an alkyl group or a cycloalkyl group,
R ^B represents an alkyl group, a cycloalkyl group, an aryl group or an acyl group, and R ^C represents a group capable of substituting on the benzene ring. n represents 0 or 1. X ^A represents a group capable of splitting off upon coupling with an oxidized product of a developing agent, and Y ^A represents an organic group. ]