JPH11102050A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the light resistance of a yellow dye image without impairing color reproduction performance by incorporating a specified compound and a yellow coupler in a blue-sensitive silver halide emulsion layer. SOLUTION: At least one of the blue-sensitive silver halide emulsion layer contains one of the compounds represented by formula I and one of the yellow couplers represented by formula II and in formulae I and II, each of R1 and R2 is an H atom or a substituent; each of R3 and R4 is an H or halogen atom or an alkyl or aryl or -OR5 group or the like, and each of R3 and R4 may combine with each other to form a ring; R5 is an alkyl or aryl group; R21 is an alkyl or cycloalkyl group; R22 , is a halogen atom or an alkoxy group; R23 is a substituent; (m) is an integer of 0-4, and when m=>=2, each of plural R23 , may be same or different; and Z is an H atom or a group to be allowed to release by coupling with the oxidation product of a 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 excellent color reproducibility and improved light fastness of a yellow dye image.

[0002]

2. Description of the Related Art Silver halide color photographic materials (hereinafter also simply referred to as color photographic materials, photographic materials or photographic materials).
In the above, 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. For these couplers,
Although basic performance such as color developing property, storage stability, color reproducibility of the obtained dye image and image storability are required, especially in a color photographic light-sensitive material used for direct appreciation such as color photographic paper, It is required to have excellent image storability, especially excellent light fastness. For the purpose of improving the light fastness of the yellow image dye of a silver halide color photographic light-sensitive material, Japanese Patent Application Laid-Open No.
No. 48535 discloses adding a p-hydroxybenzoic acid compound to a layer containing a yellow coupler. However, the use of the above compound improves the light fastness of the yellow dye image, but is not yet sufficient, and the addition of the above compound affects the absorption waveform of the formed dye, so that the color reproducibility is not sufficient. Further improvements were required.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material having improved light fastness of a yellow dye image without impairing color reproducibility.

[0004]

The object of the present invention has been attained by the following items.

[0005] 1. In a silver halide color photographic light-sensitive material comprising a support, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, at least one of the blue-sensitive silver halide emulsion layers A silver halide color photograph containing at least one compound represented by the following general formula (PI) and at least one yellow coupler represented by the following general formula (YCP-I): Photosensitive material.

[0006]

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In the formula, R ₁ and R ₂ each represent a hydrogen atom or a substituent, and R ₃ and R ₄ each represent an alkyl group, an aryl group, —OR ₅ , a halogen atom, —NR ₆ R ₇ , Represents a hydroxy group, an amino group, or a heterocyclic group. R ₃ and R ₄ may be closed with each other. R ₅ , R ₆ and R ₇ each represent an alkyl group or an aryl group. The alkyl group and the aryl group may have a substituent.

[0008]

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In the formula, R ₂₁ represents an alkyl group or a cycloalkyl group, and R ₂₂ represents a halogen atom or an alkoxyl group. R ₂₃ represents a substituent, and m represents an integer of 0 to 4. However, when m is 2 or more, a plurality of R ₂₃ may be the same or different. Z represents a hydrogen atom or a group which is eliminated upon coupling with an oxidized form of the developing agent.

[0010] 2. 2. The silver halide color photographic light-sensitive material as described in 1 above, wherein the compound represented by the general formula (PI) is a compound represented by the following general formula (P-II).

[0011]

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In the formula, R ₈ represents a substituent, and R ₉ and R ₁₀ are each an alkyl group, an aryl group, —OR ₁₁ , a halogen atom, —NR ₁₂ R ₁₃ , a hydroxy group, an amino group or a heterocyclic group. Represents R ₉ and R ₁₀ may be closed with each other.
R ₁₁ , R ₁₂ and R ₁₃ each represent an alkyl group or an aryl group. The alkyl group and the aryl group may have a substituent.

Hereinafter, the present invention will be described more specifically. In a conventionally known yellow coupler, there is a possibility that an aggregate is formed as a result of an intermolecular interaction between yellow image dye molecules generated by an oxidative coupling reaction with a color developing agent. The compound of the present invention represented by the general formula (PI) or the general formula (P-II) is capable of effectively preventing the formation of the above-described dye aggregates, thereby improving the light fastness of a yellow dye image. It is believed that the color reproducibility of the entire image is improved because the yellow dye image having a sharp absorption waveform is obtained.

The general formula (PI) and the general formula (P
The compound represented by -II) will be described in detail. Examples of the substituent represented by R ₁ and R ₂ include an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, and an acyl group. Most preferably, _one of R ₁ and R ₂ is a hydrogen atom.

The alkyl groups represented by R ₁ and R ₂ may be linear or branched, and specifically include a methyl group, an ethyl group, a butyl group, an i-propyl group, a t-butyl group and a sec-butyl group. , An i-butyl group, a t-octyl group, a dodecyl group and a hexadecyl group. Further, the alkyl group may have a substituent. Examples of the substituent include a cycloalkyl group, an aryl group, a heterocyclic group, a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, a mercapto group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an alkylsulfonyl group, and an arylsulfonyl group. , An amino group, a cyano group, a nitro group and the like.

Examples of the cycloalkyl group represented by R ₁ and R ₂ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. The cycloalkyl group may have a substituent, and as the substituent, those exemplified as the substituent of the alkyl group can be used.

The aryl groups represented by R ₁ and R ₂ include
Examples include a phenyl group and a naphthyl group. The aryl group may have a substituent, and as the substituent, those exemplified as the substituent of the alkyl group can be used.

The heterocyclic group represented by R ₁ and R ₂ is 2
-Furyl, 2-thienyl, 2-imidazolyl, 2-thiazolyl, 3-isoxazolyl, 3-pyridyl, 2-pyridyl, 2-pyrimidyl, 3-pyrazolyl, 2-benzothiazolyl.

The acyl groups represented by R ₁ and R ₂ include acetyl, propionyl, butyryl, hexanoyl, benzoyl, 4-nitrobenzoyl, 4-cyanobenzoyl and 4-dimethylaminobenzoyl. , 4
-Ethanesulfonylaminobenzoyl group, 3-methylbenzoyl group, 2-ethoxycarbonylbenzoyl group and the like.

The alkyl group, aryl group and heterocyclic group represented by R ₃ , R ₄ , R ₅ , R ₆ and R ₇ have the same meanings as those described for R ₁ and R ₂ . Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

R _{8 in} formula (P-II) has the same meaning as R _{1 in} formula (PI), and R ₉ and R ₁₀ are respectively R ₃ and R ₁₀ in formula (PI). It is synonymous with R ₄ .

Hereinafter, typical specific examples of the compound represented by formula (PI) or (P-II) of the present invention will be shown.
The present invention is not limited to these.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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The general formula (PI) and the general formula (P
The compound represented by -II) can be synthesized by a conventionally known method. Hereinafter, the compound of the present invention (P-II-
3) shows the synthesis of 3).

[0031]

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Synthesis Example 1 Synthesis of Compound (P-II-3) 10.0 g of compound (1) and 6.2 g of pyridine were dissolved in 150 ml of acetonitrile, and 1 g of compound (2) was added thereto.
4.0 g was added and the mixture was refluxed for 4 hours. After completion of the reaction, 200 cc of ethyl acetate, 100 cc of water and 50 cc of 1N hydrochloric acid were added to extract the organic layer, which was dried, concentrated and then recrystallized from acetonitrile to obtain 8.2 g of a yellow crystal (3).

MASS, NMR spectrum measurement,
It was confirmed that it was the exemplary compound (P-II-3).

Next, the coupler represented by formula (YCP-I) of the present invention will be described in more detail.

The alkyl group represented by R ₂₁ is a linear or branched alkyl group such as methyl, ethyl, i
-Propyl, t-butyl, dodecyl, 1-hexylnonyl group and the like. Examples of the cycloalkyl group represented by R ₂₁ include cyclopropyl, cyclohexyl, and adamantyl group.

The alkyl group and cycloalkyl group represented by R ₂₁ may further have a substituent. Examples of the substituent include a halogen atom (chlorine atom, bromine atom, etc.), a cyano group, a nitro group, an aryl group (phenyl, pt-octylphenyl, 2,4-di-t-amylphenyl, etc.), a hydroxyl group, Alkoxyl groups (methoxy, 2-ethoxyethoxy, etc.), aryloxy groups (phenoxy, 2,
Heterocyclic oxy groups such as 4-di-t-amylphenoxy, 4- (4-hydroxyphenylsulfonyl) phenoxy, etc.), 4-pyridyloxy, 2-hexahydropyranyloxy, and alkylcarbonyloxy such as acetyloxy and pivaloyloxy Groups, arylcarbonyloxy groups such as benzoyloxy, alkylsulfonyloxy groups such as methanesulfonyloxy, trifluoromethanesulfonyloxy, dodecanesulfonyloxy, arylsulfonyloxy groups such as benzenesulfonyloxy, p-toluenesulfonyloxy, acetyl, pivaloyl, etc. Alkylcarbonyl group, benzoyl, arylcarbonyl group such as 3,5-di-t-butyl-4-hydroxybenzoyl, methoxycarbonyl, cyclohexyloxycarbonyl, dodecyloxy Alkoxycarbonyl group such as carbonyl, aryloxycarbonyl group such as 2,4-di-t-amylphenoxycarbonyl, heterocyclic oxycarbonyl group such as 2-pyridyloxycarbonyl, 1-phenylpyrazolyl-5-oxycarbonyl, dimethylcarbamoyl Alkylcarbamoyl groups such as, 4- (2,4-di-t-amylphenoxy) butylcarbamoyl; arylcarbamoyl groups such as phenylcarbamoyl and 1-naphthylcarbamoyl; alkylsulfonyl groups such as methanesulfonyl and trifluoromethanesulfonyl; Arylsulfonyl groups such as toluenesulfonyl; alkylsulfamoyl groups such as dimethylsulfamoyl and 4- (2,4-di-t-amylphenoxy) butylsulfamoyl; and aryls such as phenylsulfamoyl. Sulfamoyl groups, acetylsulfamoyl, acylsulfamoyl groups such as ethylcarbonylsulfamoyl, dimethylamino, cyclohexylamino, alkylamino groups such as dodecylamino, anilino, arylamino groups such as pt-octylanilino, Alkylsulfonamide groups such as methanesulfonamide, heptafluoropropanesulfonamide and hexadecylsulfonamide; arylsulfonamide groups such as p-toluenesulfonamide and pentafluorobenzenesulfonamide; alkylcarbonylamino groups such as acetylamino and myristoylamino , An arylcarbonylamino group such as benzoylamino, an alkylthio group such as methylthio and t-octylthio, an arylthio group such as phenylthio, and 1-phenyltetrazole-
And heterocyclic thio groups such as 5-thio and 5-methyl-1,3,4-oxadiazole-2-thio.

R ₂₁ is preferably an alkyl group, more preferably a branched alkyl group, and particularly preferably a t-butyl group.

In the general formula (YCP-I), examples of the halogen atom represented by R ₂₂ include a fluorine atom, a chlorine atom and an iodine atom, and examples of the alkoxyl group include a methoxy group, an ethoxy group, an i-propoxy group, Examples thereof include an n-butoxy group, an n-octyloxy group, and an n-dodecyloxy group.

R ₂₂ represents an alkoxyl group or a halogen atom. An alkoxyl group is preferably used, and a methoxy group is particularly preferred.

In the general formula (YCP-I), R ₂₃ has the same meaning as the group mentioned as a substituent of the alkyl group and the cycloalkyl group represented by R ₂₁ in the general formula (YCP-I). Groups.

R ₂₃ is preferably an acylamino group, a sulfonylamino group, an alkoxycarbonyl group and a sulfamoyl group. m represents an integer of 0 to 4, and is preferably 1.

In the general formula (YCP-I), the group leaving upon coupling with an oxidized form of the developing agent represented by Z is a group represented by the following general formula (YCP-II), (YCP-III) or (YCP-IV). ) Is preferred.

[0043]

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The formulas (YCP-II) and (YCP-
In III), R ₂₄ represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. The alkyl group and cycloalkyl group represented by R _{24 have the same} meanings as the alkyl group and cycloalkyl group represented by R ₂₁ in Formula (YCP-I). Examples of the aryl group represented by R ₂₄ include a phenyl group, a pt-octylphenyl group, and a 2,4-di-t-amylphenyl group. Examples of the heterocyclic group represented by R ₂₄ include 4-pyridyl and 2-hexahydropyranyl. The alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by R ₂₄ may have a substituent. As the substituent, R ₂₁ in the general formula (YCP-I) can be used.
And the groups having the same meanings as the groups exemplified as the substituents of the alkyl group and the cycloalkyl group represented by

Among the alkyl, cycloalkyl, aryl and heterocyclic groups represented by R ₂₄ , an aryl group is preferred. Examples of the substituent for R ₂₄ include an alkoxycarbonyl group such as carboxyl, methoxycarbonyl or i-propyloxycarbonyl, an acyl group such as acetyl or benzoyl, an alkylsulfonyl group such as trifluoromethanesulfonyl or 4-hydroxyphenylsulfonyl, or an aryl group. Preferred are a sulfonyl group, a nitro group, a cyano group, a halogen atom, a sulfamoyl group such as dimethylsulfamoyl, an acylamino group such as acetylamino or pentafluorobenzoyl, and an alkylsulfonamide group such as methanesulfonamide.

In the general formula (YCP-IV), Z
₂₁ represents a nonmetallic atomic group necessary for forming a 5- or 6-membered ring with a nitrogen atom. Examples of the atomic group necessary for forming a non-metallic atomic group, methylene, methine, isopropylidene -C (O) -, - N (R 25) -, (R 25 is a hydrogen atom, an alkyl group, an aryl Represents a group or a heterocyclic group),-
N =, -O- and -S (O) u- (u represents an integer of 0 to 2) and the like.

Among the compounds represented by the general formula (YCP-I), preferred are compounds represented by the following general formula (YCP-V).

[0048]

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In the formula, R ₂₁ and R ₂₂ each represent a group having the same meaning as the groups represented by R ₂₁ and R ₂₂ in formula (YCP-I). Z ₂₂ represents a group having the same meaning as the group represented by Z in the formula (YCP-I). W represents a substituent.

In the general formula (YCP-V), the substituent represented by Z ₂₂ is preferably the following general formulas (I) and (ICP)
It is a substituent represented by (I), (III), (IV), (V) or (VI).

[0051]

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The formulas (I), (II), (III) and (I
In V), (V) or (VI), R ₂₇ , R ₂₈ and R
₂₉ represents a substituent on the heterocyclic ring containing a nitrogen atom, and has the same meaning as the groups listed as the substituents of the alkyl group and the cycloalkyl group represented by R ₂₁ in Formula (YCP-I). And the group of

In the general formula (V), R ₃₀ is a group having the same meaning as the alkyl group, cycloalkyl group and aryl group represented by R ₂₄ in the general formulas (YCP-II) and (YCP-III); Group, arylcarbonyl group, alkylsulfonyl group or arylsulfonyl group.

In the general formulas (IV) and (V), Z ₂₃
Is -N (R ₃₁ )-(R ₃₁ is the above-mentioned general formula (YCP-IV)
Represents a group having the same meaning as the group represented by R ₂₅ ), —O
-Or -S (O) v- (v represents an integer of 0 to 2).

In the general formula (VI), Y ₂₁ is -N
(R ₃₂ )-(R ₃₂ represents a group having the same meaning as the group represented by R ₂₅ in the formula (YCP-IV)), —O— and —S
(O) r- heteroatom (r is an integer of 0 to 2) represented by like or -C (O) -, - C (R 33) (R 34) -
(R ₃₃ and R ₃₄ each represent a hydrogen atom or a group having the same meaning as the groups exemplified as the substituents of the alkyl group and the cycloalkyl group represented by R ₂₁ in Formula (YCP-I).) And —C (R ₃₅ ) — (R ₃₅ is a hydrogen atom or a group having the same meaning as the substituents of the alkyl group and the cycloalkyl group represented by R ₂₁ in formula (YCP-I). Represents a carbon atom.

In the general formula (VI), Z ₂₄ is -Y
Represents a group of nonmetallic atoms necessary for forming a 5- to 6-membered ring in cooperation with _21- N-CO-. Here, the atomic group necessary for forming the non-metallic atomic group includes, for example, the general formula (Y
It can be mentioned atomic atomic group as defined represented by Z ₂₁ in CP-IV).

Among the compounds represented by the general formula (YCP-V), the compound represented by the following general formula (YCP-VII) is preferable.

[0058]

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In the formula, R ₂₁ and R ₂₂ have the same meanings as the groups represented by R ₂₁ and R ₂₂ in formula (YCP-I), respectively.

[0060] In Z ₂₅ is the formula (YCP-V), Z ₂₂
Represents a group having the same meaning as the group represented by formula (VI) defined as a preferred embodiment of

In the general formula (YCP-VII), W ₂₁ is a group represented by the following general formula (IX), (X) or (XI).

[0062]

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In the general formulas (IX) and (XI), R ₃₆ represents an alkyl group or a cycloalkyl group, and has the same meaning as the alkyl group and the cycloalkyl group represented by R ₂₁ in the general formula (YCP-I). Groups. R
_The alkyl group and the cycloalkyl group represented by ₃₆ may have a substituent. Examples of the substituent include the same groups as the groups exemplified as the substituent for the alkyl group and the cycloalkyl group represented by R ₂₁ in Formula (YCP-I). Of these alkyl groups or cycloalkyl groups represented by R ₃₆ , an unsubstituted alkyl group is preferred.

In the general formula (X), Ra represents an alkyl group or a phenoxyalkyl group represented by the following general formula (Rb).

[0065]

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In the formula (Rb), R ₃₇ represents a substituent, and has the same meaning as the substituent of the alkyl group and the cycloalkyl group represented by R ₂₁ in the formula (YCP-I).

R ₃₇ is preferably an unsubstituted alkyl group, more preferably an unsubstituted branched alkyl group, and particularly preferably an unsubstituted branched alkyl group having 3 to 12 carbon atoms.

K represents an integer of 0 to 5, and when k is 2 or more, a plurality of _R37s may be the same or different.
k is preferably 2.

In the general formulas (Rb) and (XI), L ₂₁ and L ₂₂ each represent an alkylene group.

L ₂₁ is preferably an alkylene group having 3 to 7 carbon atoms, more preferably a trimethylene group, a 1,1-propanediyl group, a 1,1-pentanediyl group, and a 1,1-hexanediyl group. A 1,1-propanediyl group is particularly preferred. L ₂₂ is 3 carbon atoms
7 is preferable, and a trimethylene group, 2,2
-A propanediyl group, a 1,2-propanediyl group (propylene group) and a 1,1-propanediyl group are more preferable, and a trimethylene group and a 1,2-propanediyl group (propylene group) are particularly preferable.

Among the compounds represented by the general formula (YCP-VII), a compound represented by the following general formula (YCP-XII) is particularly preferred.

[0072]

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In the formula, R ₂₁ and R ₂₂ are represented by the general formula (YC
A group represented by R ₂₁ and R ₂₂ in the P-I), which is the same meaning.

In the general formula (YCP-XII), W ₂₂ represents the following general formula (XIII), (XIV) or (XV).

[0075]

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In the general formula (XIII), R ₃₈ represents an alkyl group having 11 to 21 carbon atoms.

In the general formula (XIV), R ₃₉ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and is preferably ethyl, butyl or hexyl. R ₄₀ and R ₄₁ each represent a hydrogen atom or a branched alkyl group having 4 to 12 carbon atoms. However, the sum of the carbon atoms of R ₄₀ and R ₄₁ is 4 to
Sixteen.

In the general formula (XV), Ra has the same meaning as Ra in the general formula (X).

In the general formula (YCP-XII), W
Preferred as ₂₂ is the general formula (XV), and the case where Ra in the general formula (XV) is an alkyl group is most preferred.

In the general formula (YCP-XII), Z
₂₆ has the same meaning as the group represented by formula (VI).

The yellow coupler represented by formula (YCP-I) may be bonded at any of the substituents to form a bis-, tris-, tetrakis- or multimer.

The yellow coupler represented by the general formula (YCP-I) uses a commercially available compound as a starting material and can be prepared by a conventionally known method, for example, JP-A-63-123.
No. 047 and Japanese Patent Application No. 245949/1990.

Specific examples of the leaving group Z in the general formula (YCP-I) of the present invention are shown below, but are not limited thereto.

[0084]

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[0085]

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Next, specific examples of the substituent R ₂₃ in the general formula (YCP-I) of the present invention are shown below, but are not limited thereto.

[0087]

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[0088]

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Next, the general formula (YCP-
Representative examples of the yellow coupler of the present invention represented by I) are shown below, but the present invention is not limited thereto.

[0090]

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[0091]

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The magenta and cyan couplers used in the silver halide color photographic light-sensitive material of the present invention may be 340 nm by a coupling reaction with an oxidized color developing agent.
A compound that forms a coupling product having a spectral absorption maximum wavelength in a longer wavelength region can be used. Generally, the spectral maximum wavelength of the coupling product is within a wavelength range of 50 nm.
A compound having a wavelength of 0 to 600 nm is used as a magenta coupler, and a compound having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm is used as a cyan coupler.

When an oil-in-water emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually necessary to use a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher. And a water-soluble organic solvent having a low boiling point is used in combination, and the mixture is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. It is preferable to include a step of removing the low-boiling organic solvent after or simultaneously with the dispersion.

In order to obtain a sufficiently high density, the coating amount of the yellow coupler is preferably 1 to 1 mol per mol of silver halide.
× 10 ^{-3 to} 5 mol is preferably used. More preferably, it is 1 × 10 ^-2 to 1 mol.

The amount of the compound represented by formula (PI) or (P-II) of the present invention is preferably 0.01 g to 10 g per 1 g of the yellow coupler (YCP-I). Can be More preferably, 0.5g-5.
The range is 0 g. Further, two or more compounds represented by formula (PI) or (P-II) can be used in combination.

As the silver halide emulsion used in the present invention, a silver halide color photographic emulsion known in the art can be used.

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

The silver halide color photographic light-sensitive material of the present invention may further contain various photographic additives. For example, an antifoggant, a development accelerator, a development retarder, a bleaching accelerator, a stabilizer, an ultraviolet absorber, a color stain inhibitor, a fluorescent brightener, a color image fading inhibitor, an antistatic agent described in RD17643, Hardening agents, surfactants, plasticizers, wetting agents and the like can be used.

Further, the development accelerator, bleaching accelerator, developer, silver halide solvent, toning agent, hardener, fogging agent, antifoggant, Compounds that release photographically useful fragments can be used, such as sensitizers, spectral sensitizers, and desensitizers.

The support of the silver halide color photographic light-sensitive material of the present invention includes, for example, baryta paper, polyethylene-coated paper,
Polyester synthetic paper, glass plate, cellulose acetate, cellulose nitrate, polyester film such as polyethylene terephthalate, polyamide film,
There are polycarbonate films, polystyrene films, and the like. 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 silver halide color photographic light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the emulsion layer and other constituent layers used in the present invention. 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. The blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer are sequentially arranged from the support side. It is preferable to use an array of

In the silver halide color photographic 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, a filter layer, an anti-curl layer, a protective layer, an antihalation layer, etc. Various layers can be appropriately combined and used as constituent layers. A hydrophilic colloid can be used as a binder in these constituent layers, and gelatin is preferably used. In addition, various photographic additives described in the description of the emulsion layer can be contained in the layer.

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

[0106]

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

Example 1 On a paper support, polyethylene was laminated on one side and polyethylene containing titanium oxide was laminated on the other side, and each layer having the following constitution was replaced with a polyethylene layer containing titanium oxide. Is coated on the side of the multilayer color photosensitive material sample No. A was prepared. The coating solution was prepared as shown below.

First Layer Coating Solution 26.7 g of yellow coupler (YCP-I-8), 0.67 g of additive (HQ-1), 0.33 g of anti-irradiation dye (AI-3), organic solvent of high boiling point ( DNP)
6.67 g of ethyl acetate (60 cc) was added and dissolved, and the solution was added to a solution containing 7 cc of 20% surfactant (SU-1).
It was emulsified and dispersed in 220 cc of a 0% aqueous gelatin solution 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 hardening agent, (H) was added to the second and fourth layers.
-1) and (H-2) were added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The amount of addition in the light-sensitive material indicates the number of grams per 1 m ² unless otherwise specified.

[0111]

[Table 1]

[0112]

[Table 2]

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

[0114]

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[0115]

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[0116]

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

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

(Solution B) 10 g of silver nitrate was added to make up to 200 cc by adding water.

(Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to make up to 600 cc.

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

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

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

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

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

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

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

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

[0129]

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Sample No. No. A. In the same manner as the multilayer sample No. A except that the compound P-II-7 of the present invention was used in place of the additive DNP of the first layer of A B was created.

Next, the sample No. In the same manner as the multilayer sample No. A, except that the image stabilizer ST-110.0 g was added to the first layer of No. A. 3 was produced.

Further, the sample No. YCP-I-4 instead of the first layer yellow coupler (YCP-I-8)
8, YCP-I-1, YCP-I-31, and YCP-
Sample No. 1 was similarly used except that I-40 was used. 1,
2, 4 and 5 were made. Next, these sample Nos. 1 to
5 in place of the DNP in the first layer, the general formula (P-
Sample No. I) or a compound represented by formula (P-II). 6 to 30 were produced.

The properties of the thus obtained sample were evaluated by the following methods.

<< Light Resistance >> A, B and 1
Sample No. 30 was exposed to white light through an optical wedge, and then processed according to the following steps. A fade test was performed on each of the obtained samples for 10 days using a fade meter, and the residual ratio (%) of the dye image at an initial density of 1.0 was determined using blue light.

<< Color Reproducibility >> First, using a color negative film (Konica Color LV-400: manufactured by Konica) and a camera (Konica FT-1: manufactured by Konica), a color checker manufactured by Macbeth was shot. Subsequently, color negative development processing (CNK-4: manufactured by Konica) was performed, and the obtained negative image was printed on each sample to a size of 82 mm × 117 mm using a Konica color printer (CL-P2000: manufactured by Konica). (Printer conditions 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 by 20 persons, and the evaluation results were shown in the following five grades.

5: All 20 persons were evaluated as good. 4: 15 to 19 persons were evaluated as good. 3: 10 to 14 persons were evaluated as good. 2: 5 to 9 persons out of 20. Is evaluated as good, and 0 to 4 out of 20 people are evaluated as good.

The processing conditions are as follows.

(Processing conditions) Processing step Temperature Time Color development 35.0 ± 0.3 ° C 45 seconds Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Drying 60- 80 ° C. for 60 seconds Color developing solution pure water 800 cc triethanolamine 10 g N, N-diethylhydroxylamine 5 g potassium bromide 0.02 g potassium chloride 2 g potassium sulfite 0.3 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-disulfonic acid disodium salt 1.0 g Diethylene glycol 10 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate (CD-3) 4.5 g Fluorescent whitening agent (4,4'-diaminostilbene sulfonic acid derivative) 1.0 g The is added to make 1 liter um 27g water, adjusted to pH = 10.10.

Bleaching / fixing solution ethylenediaminetetraacetate ammonium ferric ammonium dihydrate 60 g ethylenediaminetetraacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 cc ammonium sulfite (40% aqueous solution) 27.5 cc Adjust to pH = 5.7 with potassium or glacial acetic acid.

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

Table 3 shows the results.

[0142]

[Table 3]

Table 3 shows comparative sample Nos. A and sample N of the present invention
o. From the results of B, it can be seen that by adding the compound P-II-7 of the present invention, the color reproducibility is improved and the light fastness of the yellow dye image is significantly improved.

In Table 3, the comparison sample No. 1,
Samples Nos. 4 and 5 have insufficient color reproducibility and light fastness despite the addition of the dye image stabilizer ST-1. It can be seen that the light resistance of 2 and 3 is insufficient.

In contrast, Samples 6 to 30 of the present invention using the yellow coupler of the present invention and the compound of the present invention
It shows that good color reproducibility is exhibited and light resistance is remarkably improved.

[0146]

According to the present invention, color reproducibility is good,
In addition, a silver halide color photographic light-sensitive material excellent in light fastness of a yellow color image can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shigeto Hirabayashi 1 Konica Corporation, Sakuracho, Hino-shi, Tokyo

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a support and a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, wherein the blue-sensitive silver halide At least one of the emulsion layers contains at least one compound represented by the following general formula (PI) and at least one yellow coupler represented by the following general formula (YCP-I). Silver halide color photographic material. Embedded image [Wherein, R ₁ and R ₂ represent a hydrogen atom or a substituent;
₃ and R ₄ each represent an alkyl group, an aryl group, —OR ₅ , a halogen atom, —NR ₆ R ₇ , a hydroxy group, an amino group, or a heterocyclic group. R ₃ and R ₄ may be closed with each other.
R ₅ , R ₆ and R ₇ represent an alkyl group or an aryl group. The alkyl group and the aryl group may have a substituent. [Chemical formula 2] [Wherein, R ₂₁ represents an alkyl group or a cycloalkyl group, and R ₂₂ represents a halogen atom or an alkoxyl group. R ₂₃ represents a substituent, and m represents an integer of 0 to 4. However, when m is 2 or more, a plurality of R ₂₃ may be the same or different. Z represents a hydrogen atom or a group which is eliminated upon coupling with an oxidized form of the developing agent. ] 2. The silver halide color according to claim 1, wherein the compound represented by the general formula (PI) is a compound represented by the following general formula (P-II). Photosensitive material. Embedded image [Wherein, R ₈ represents a substituent, and R ₉ and R ₁₀ each represent an alkyl group, an aryl group, —OR ₁₁ , a halogen atom, —NR ₁₂
R _{13 represents} a hydroxy group, an amino group or a heterocyclic group. R ₉ and R ₁₀ may be closed with each other. R ₁₁ , R ₁₂ ,
R ₁₃ represents an alkyl group or an aryl group. The alkyl group and the aryl group may have a substituent. ]