JPH11143036A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide color photographic sensitive material superior in color image lightfastness and color development performance by incorporating a specified compound and a specified magenta coupler in the same photographic constituent layer. SOLUTION: The same photographic constituent layer contains one of the compounds represented by formula I and one of the magenta couplers represented by formula II and in formulae I and II, R1 is an alkyl or cycloalkyl or aryl group; R2 is an H atom or an alkyl or cycloalkyl or aryl group; each of R3 -R6 is an H atom or an alkyl or aryl group; each of R7 and R8 is an H atom or an alkyl group; R9 is an H atom or a substituent; R10 is an alkyl, cycloalkyl, alkenyl, aryl, or heterocyclic group; (m) is an H atom or a substituent; R is an H atom or a substituent; X is an H atom or a group to be released by reaction with the oxidation product of a color developing agent; and Z is a nonmetallic atomic group necessary to form an N-containing hetero ring.

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 (hereinafter referred to as "silver halide color photographic light-sensitive material") having excellent color image fastness and excellent color development. Color light-sensitive material).

[0002]

2. Description of the Related Art In the field of color light-sensitive materials, dye images obtained from couplers are exposed to light for a long time,
It is desired that they do not discolor even when stored under high temperature and high humidity.

[0003] However, it is known that these dye images are not satisfactory in fastness mainly to ultraviolet light or visible light, and are easily discolored and discolored when irradiated with such actinic light.

In order to eliminate such disadvantages, conventionally,
Proposed methods include selecting and using various couplers with little fading, using an ultraviolet absorber to protect the dye image from ultraviolet rays, or introducing a group that imparts light resistance into the coupler structure. Have been.

However, in order to provide a dye image with satisfactory light fastness using, for example, an ultraviolet absorber, a relatively large amount of the ultraviolet absorber is required. In this case, the dye image has to be formed due to coloring of the ultraviolet absorber itself. In some cases, it was significantly contaminated. Further, even if an ultraviolet absorber is used, it has no effect in preventing fading of a dye image due to visible light, and there is a limit to improvement in light resistance by the ultraviolet absorber.

Further, there is known a method using a dye image stabilizer having a phenolic hydroxyl group or a group capable of hydrolyzing to form a phenolic hydroxyl group.
No. 31256, No. 48-31625, No. 51-304
No. 62, JP-A-49-134326 and JP-A-49-13
No. 4327, phenols and bisphenols; US Pat. No. 3,069,262 discloses pyrogallol, gallic acid and esters thereof; US Pat. Nos. 2,360,290 and 4,015,990 disclose α- Tocopherols and acyl derivatives thereof; JP-B-52-27534;
JP-A-52-14751 and U.S. Pat. No. 2,735,7
No. 65, a hydroquinone derivative; US Pat.
6,300 and 3,574,627 describe 6-hydroxychromans; U.S. Pat.
-Hydroxychroman derivative; JP-B-49-20977
The use of 6,6'-dihydroxy-2,2'-spirobichromans and the like has been proposed in the publication.

However, these compounds are effective to some extent as an agent for preventing color fading and discoloration of the dye, but are still insufficient.

Further, it has been disclosed in British Patent 1,451,000 to improve the photostability of a dye image by using an azomethine quenching compound whose absorption peak is on the deeper side than the peak of the dye image. However, since the azomethine quenching compound itself is colored, there is a great disadvantage to the hue of the dye image.

Further, a method for stabilizing a dye against light by a metal complex is disclosed in Japanese Patent Application Laid-Open No. 50-87649 and Research Disclosure (Research Disclosure).
osure, hereinafter referred to as RD) 15162 (1976)
Year)), these complexes are not very effective in preventing discoloration and have poor solubility in organic solvents, so that they cannot be added in an amount sufficient to exert the effect of preventing discoloration. Furthermore, since the complex itself has a large coloring, when added in a large amount, the hue and the purity of the dye image produced by the color development processing are adversely affected.

[0010]

Accordingly, the first aspect of the present invention is as follows.
An object of the present invention is to provide a silver halide color photographic light-sensitive material in which the light fastness of a dye image is remarkably improved. A second object of the present invention is to provide a silver halide color photographic light-sensitive material which has excellent coloring properties in addition to the above-mentioned properties.

[0011]

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

(1) A silver halide color photographic light-sensitive material containing at least one compound represented by the following general formula [A].

[0013]

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In the formula, R ₁ represents an alkyl group, a cycloalkyl group or an aryl group, and R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R ₃ ,
R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an alkyl group or an aryl group, and when R ₃ and R ₅ or R ₄ and R ₆ represent an alkyl group, R ₃ and R ₅ or R ₄ R ₆ may combine with each other to form a ring. Each R ₇ and R ₈ represents a hydrogen atom or an alkyl group, R ₉ represents a hydrogen atom or a substituent, R ₁₀
Represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. m represents an integer of 0 to 4. When m is 2 or more, a plurality of R ₉ may be the same or different. n represents 0 or 1.

(2) The silver halide color photographic material as described in (1), which contains at least one magenta coupler represented by the following general formula [M].

[0016]

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In the formula, R represents a hydrogen atom or a substituent;
Represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring.

(3) The same photographic constituent layer contains at least one kind of the compound represented by the general formula [A] and at least one kind of the magenta coupler represented by the general formula [M]. 3. The silver halide color photographic light-sensitive material described in 1. above.

Hereinafter, the present invention will be described in detail.

[0020] In the general formula (A), but R ₁ represents an alkyl group, a cycloalkyl group or an aryl group, R ₁
The alkyl group represented by may be linear or branched, preferably having 1 to 32 carbon atoms, for example, methyl, ethyl,
Representative groups include propyl, i-propyl, t-butyl, hexyl, octyl, dodecyl, hexadecyl, 2-ethylhexyl and the like.

These alkyl groups may be further substituted by substituents, such as alkyl, alkenyl, cycloalkyl, cycloalkenyl,
Alkynyl group, aryl group, heterocyclic group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, acyl group, carbamoyl group, sulfamoyl group, cyano group, alkoxy group, aryloxy group,
Heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, alkylamino group, anilino group, acylamino group, sulfonylamino group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryl Examples thereof include an oxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a hydroxyl group and a halogen atom. Among these, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group are preferred.

The cycloalkyl group represented by R ₁ preferably has 3 to 12 carbon atoms and may have a branched structure. Examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, 2-methylcyclopropyl, adamantyl and the like. Are typical examples.

These cycloalkyl groups may be further substituted by a substituent, and the substituent includes the above-mentioned R ₁
And the same groups as the substituents that the alkyl group represented by may have. Among these, alkyl groups,
Aryl, alkoxy and aryloxy groups are preferred.

The aryl group represented by R ₁ has 6 to ₁ carbon atoms.
4, and typical examples thereof are phenyl, 1
-Naphthyl, 2-naphthyl group and the like.

These aryl groups may be further substituted by a substituent, and examples of the substituent include the same groups as the substituents that the alkyl group represented by R ₁ may have. . Among these, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acylamino group, a sulfonylamino group, and an alkoxycarbonyl group are preferred.

In the general formula [A], R ₂ is a hydrogen atom,
It represents an alkyl group, an cycloalkyl group or an aryl group, an alkyl group represented by R ₂ is a cycloalkyl group with an alkyl group group having the same meaning that the R ₁ represents, represented by R _2, wherein R ₁ a cycloalkyl group as defined for groups represented by, R ₂
The aryl group represented by is also the same as the aryl group represented by R ₁ .

The alkyl group, cycloalkyl group and aryl group represented by R ₂ may be further substituted with a substituent, and the substituent may be the alkyl group represented by R _1. The same groups as the substituents can be mentioned. Among these, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group are preferred.

In the general formula [A], R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an alkyl group or an aryl group, and the alkyl group represented by R _{3 to} R ₆ is It represents a group having the same meaning as the alkyl group represented by R ₁ .

The aryl group represented by R _{3 to} R ₆ is a group represented by R
Represents a group having the same meaning as the aryl group represented by ₁ .

These alkyl groups and aryl groups may be further substituted with substituents, and the substituents include
Examples include the same groups as the substituents that the alkyl group represented by R ₁ may have. Among these, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group are preferred.

When R ₃ and R ₅ or R ₄ and R ₆ represent an alkyl group, R ₃ and R ₅ or R ₄ and R ₆ may be bonded to each other to form a ring, for example, a cyclohexane ring. Can be

R ₃ , R ₄ , R ₅ and R ₆ are preferably hydrogen atoms.

In the general formula [A], R ₇ and R ₈ each represent a hydrogen atom or an alkyl group, and the alkyl group represented by R ₇ and R ₈ has the same meaning as the alkyl group represented by R ₁ . Represents a group.

This alkyl group may be further substituted with a substituent, and examples of the substituent include the same groups as those which the alkyl group represented by R ₁ may have. Among them, an alkyl group, an aryl group,
Alkoxy groups and aryloxy groups are preferred. R ₇ and R ₈ are preferably a hydrogen atom.

In the general formula [A], R ₉ represents a hydrogen atom or a substituent, and examples of the substituent include the same groups as the substituents which the alkyl group represented by R ₁ may have. And may be further substituted by similar substituents. R ₉ is preferably a hydrogen atom.

[0036] In formula (A), R ₁₀ is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, the alkyl group, cycloalkyl group and aryl group, wherein each of the R ₁ And the same groups as the alkyl group, cycloalkyl group and aryl group. Examples of the alkenyl group include a vinyl group and an allyl group, and examples of the heterocyclic group include a pyridyl group, a thiazolyl group, an oxazolyl group, and an imidazolyl group.

The alkyl group, cycloalkyl group, alkenyl group, aryl group and heterocyclic group represented by R ₁₀ may further have a substituent, and the substituent may be an alkyl group represented by R _1. And the same groups as the substituents that may have. R ₁₀ is preferably an alkyl group.

In the general formula [A], m and n are the same as those described in the formula [1].

The specific examples of the compounds represented by the formula (A) (dye image stabilizers) are shown below, but the present invention is not limited thereto.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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The following are typical examples of the synthesis of the compound represented by the general formula [A].

Synthesis Example 1 (Synthesis of Exemplified Compound A-1)

[0047]

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1.50 g of compound (a) and compound (b)
Add 1.32 g to 30 ml of ethanol and heat for 5 hours.
Refluxed. After the completion of the reaction, the reaction solution was allowed to cool, and ethyl acetate 10
0 ml and 100 ml of aqueous sodium hydrogen carbonate solution were added. The separated organic phase was separated, washed with water, and concentrated under reduced pressure. The residue was recrystallized from ethanol to obtain 1.98 g of an exemplary compound (A-1) as a white solid. Melting point 1
01.5-102.0 ° C. Identification was performed by MASS and NMR spectra, and it was confirmed that the product was the target product.

Synthesis Example 2 (Synthesis of Exemplified Compound A-27)

[0050]

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5.52 g of compound (c) and compound (b)
4.12 g was added to 50 ml of ethanol, and the mixture was heated and refluxed for 12 hours. After completion of the reaction, the reaction solution was left to cool, and ethyl acetate 1
50 ml and 150 ml of aqueous sodium hydrogen carbonate solution were added. The separated organic phase was separated, washed with water, and concentrated under reduced pressure. The residue was subjected to column chromatography (silica gel, developing solvent: ethyl acetate / n-hexane)
3. Exemplified compound (A-27) as a white solid
66 g were obtained. 81.0-81.1 ° C. Identification is MA
The analysis was carried out by SS and NMR spectra, and it was confirmed that the target compound was obtained.

Other compounds can be synthesized according to the above synthesis method.

Next, the magenta coupler represented by the general formula [M] will be described.

Examples of the substituent represented by R include an alkyl group (eg, methyl, ethyl, propyl, i-propyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl) and an alkenyl group (vinyl, allyl). ), Alkynyl group (propargyl, etc.), aryl group (phenyl, naphthyl, etc.), heterocyclic group (pyridyl, thiazolyl, oxazolyl, imidazolyl, furyl, pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl, selenazolyl, sulforanyl, piperidinyl, pyrazolyl, tetrazolyl Etc.), halogen atoms (chlorine, bromine, iodine, fluorine, etc.), alkoxy groups (methoxy, ethoxy, propyloxy, pentyloxy, cyclopentyloxy, hexyloxy, cyclohexyloxy, octyloxy, dodecylo) A), an allyloxy group (phenoxy, naphthyloxy, etc.), an alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, etc.), an aryloxycarbonyl group (phenoxycarbonyl group, naphthyloxycarbonyl) etc),
Sulfonamide group (methyl sulfonamide, ethyl sulfonamide, butyl sulfonamide, hexyl sulfonamide, cyclohexyl sulfonamide, octyl sulfonamide, dodecyl sulfonamide, phenyl sulfonamide, etc.), sulfamoyl group (sulfamoyl group,
Methylsulfamoyl, dimethylsulfamoyl, butylsulfamoyl, hexylsulfamoyl, cyclohexylsulfamoyl, octylsulfamoyl, dodecylsulfamoyl, phenylsulfamoyl, naphthylsulfamoyl, 2-pyridylsulfamo Moir etc.),
Ureido group (methylureide, ethylureide, pentylureide, cyclohexylureide, octylureide, dodecylureide, phenylureide, naphthylureide, 2-pyridylureide, etc.), acyl group (acetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl) Octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), carbamoyl group (carbamoyl, methylcarbamoyl, dimethylcarbamoyl, propylcarbamoyl, pentylcarbamoyl, cyclohexylcarbamoyl, octylcarbamoyl, 2-ethylhexylcarbamoyl) , Dodecylcarbamoyl, phenylcarbamoyl, na Tylcarbamoyl, 2-pyridylcarbamoyl, etc.), acylamino group (methylcarbonylamino, ethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, phenylcarbonylamino , 2-naphthylcarbonylamino, etc.), sulfonyl group (methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, phenylsulfonyl, 1-naphthylsulfonyl, 2-pyridylsulfonyl, etc.), amino group ( amino,
Ethylamino, dimethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, 2-naphthylamino, 2-pyridylamino), cyano group, nitro group, sulfo group, carboxyl group, hydroxyl group, and spiro Compound residue,
And a bridged hydrocarbon compound residue. These groups may be further substituted by the substituents described above.

Of these, alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamide, alkylthio, arylthio, halogen atom, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy Heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, carboxyl, etc. More preferred are alkyl groups, and particularly preferred is t-butyl group.

The group capable of leaving by reaction with an oxidized form of the color developing agent represented by X includes, for example, a halogen atom (chlorine, bromine, fluorine, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyl Oxy,
Alkoxycarbonyloxy, aryloxycarbonyloxy, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic residue linked by an N atom, Examples include alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl groups, preferably a halogen atom, particularly preferably a chlorine atom.

Examples of the nitrogen-containing heterocycle formed by Z include pyrazole, imidazole, triazole, tetrazole and the like, and these may further have a substituent.

The skeleton represented by the general formula [M] is represented by the following M-
a to Mf, among which preferred skeletons are Ma and M-
b, Mc and Md, and more preferably Ma.

[0059]

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A magenta coupler represented by the following general formula [M] (hereinafter referred to as a magenta coupler according to the present invention)
Are shown below, but the present invention is not limited to these.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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The above magenta coupler is described in J. Che
m. Soc. (Journal of the Chemical Society), Perkin I (197
7), pp. 2047-2052, U.S. Pat.
No. 67, JP-A-59-99437 and JP-A-58-4204.
No. 5, No. 59-162548, No. 59-171956
No. 60-33552, No. 60-43659, No. 60-172982, and No. 60-190779.

The compound represented by the general formula [A] and the magenta coupler represented by the general formula [M] according to the present invention can be used as an image stabilizer represented by the following general formula [B] and / or [C]. It can be used in combination with an agent.

[0075]

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In the formula, R ₁₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. Among them, examples of the alkyl group include methyl, ethyl, propyl,
Examples thereof include linear or branched alkyl groups such as octyl, t-octyl, benzyl, and hexadecyl groups.

Examples of the alkenyl group include allyl, hexenyl, octenyl and the like. Examples of the aryl group include phenyl and naphthyl groups.

Further, specific examples of the heterocyclic group include a tetrahydropyranyl group and a pyrimidyl group. These R
Each group represented by ₁₁ includes those having a substituent.

R ₁₂ , R ₁₃ , R ₁₅ and R ₁₆ each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an acylamino group. Among them, an alkyl group, an alkenyl group, for the aryl group, alkyl group described for each of the R _11, the alkenyl group include the same aryl group.

As the halogen atom, fluorine, chlorine,
Bromine and the like can be mentioned. As the alkoxy group,
Examples include methoxy, ethoxy, and benzyloxy groups. An acylamino group is represented by R ₁₇ CONH—
R ₁₇ is an alkyl group (methyl, ethyl, propyl, butyl, octyl, t-octyl, benzyl, etc.), an alkenyl group (allyl, octenyl, oleyl, etc.), an aryl group (phenyl, methoxyphenyl, naphthyl, etc.) or a heterocyclic group (Pyridyl, pyridinyl, pyrimidyl, etc.).

R ₁₄ is an alkyl group, a hydroxyl group,
Aryl group, an alkoxy group, represents an alkenyloxy group or an aryloxy group, these, alkyl group, for the aryl group include alkyl group represented by each of the R _11, those identical to the aryl group.

As for the alkoxy group, the aforementioned R ₁₂ ,
The same as the alkoxy groups described for R ₁₃ , R ₁₅ and R ₁₆ can be mentioned.

R ₁₁ and R ₁₂ may be bonded to each other to form a 5- to 6-membered heterocyclic ring, and R ₁₃ and R ₁₄ may be closed to form a 5-membered ring. These rings include those in which another ring is spiro-bonded.

The specific examples of the compounds represented by the formula [B] are shown below, but the present invention is not limited thereto.

[0085]

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[0086]

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[0087]

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[0088]

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These compounds are described in J. Chem. So
c. (Supra) pp. 415-417 (1962), 290
4-2914 (1965); Org. Chem.
(The Journal of Organic Chemistry, 23, 75-76, Tetrahedron
(Tetrahedron) 26, 4743-4751 (1
970), Chem. , Lett. (Chemical Letter), (4), pp. 315-316 (1972), The Chemical Society of Japan, No. 10, 1987-1990 (197
2), Bull. Chem. Soc. Jpn. (Britin of Chemical Society of Japan), Vol. 53, pp. 555-556 (1980).

[0090]

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In the formula, R ₂₁ is a secondary or tertiary alkyl group,
Represents a secondary or tertiary alkenyl group, a cycloalkyl group or an aryl group, and two R ₂₁ may be the same or different. R ₂₂ represents a halogen atom, an alkyl group, an alkenyl group,
Represents a cycloalkyl group or an aryl group, and m represents an integer of 0 to 3. When m is 2 or 3, a plurality of R ₂₂ may be the same or different. Y is -S -, - SO -, - SO 2
— Or an alkylene group.

The secondary or tertiary alkyl group or the secondary or tertiary alkenyl group represented by R ₂₁ is preferably those having 3 to 32 carbon atoms, particularly those having 4 to 12 carbon atoms. Represents i-propyl, t-butyl, sec-butyl, t
-Amyl, sec-amyl, t-octyl, i-propenyl, 2-hexenyl and the like.

[0093] preferably has 1 to 32 carbon atoms as the alkyl group represented by R _22, preferably those having 2 to 32 carbon atoms as the alkenyl group, both may be linear or branched. Specifically, methyl, ethyl, t-butyl, pentadecyl, 1-hexylnonyl, 2-chlorobutyl, benzyl, 2,4-di-t-amylphenoxymethyl, 1-ethoxytridecyl, allyl, i-propenyl and the like Groups.

The cycloalkyl group represented by R ₂₁ and R ₂₂ preferably has 3 to 12 carbon atoms, and includes groups such as cyclopentyl, cyclohexyl and 1-methylcyclohexyl.

The aryl group represented by R ₂₁ and R ₂₂ is preferably a phenyl or naphthyl group. Specifically, phenyl, 4-nitrophenyl, 4-t-butylphenyl,
Examples thereof include 2,4-di-t-amylphenyl, 3-hexadecyloxyphenyl, and α-naphthyl group.

The alkylene group represented by Y preferably has 1 to 12 carbon atoms, and specific examples include groups such as methylene, ethylene, propylene, butylene, and hexamethylene.

Each of the groups represented by R ₂₁ , R ₂₂ and Y may have a substituent. Examples of the substituent include a halogen atom and nitro, cyano, amide, sulfonamide, alkoxy, aryloxy , Alkylthio, arylthio, acyl and the like.

The following are typical examples of the compound represented by the general formula [C], but the present invention is not limited thereto.

[0099]

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[0100]

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[0101]

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These compounds are described in US Pat. No. 2,807,
No. 653, J.A. Chem. Soc. Perkin I
(Supra), page 1712 (1979) and the like.

The magenta coupler according to the present invention usually comprises
Per mol of silver halide 1 × 10 ^-3 ~8 × 10 ^-1 mol, preferably can be used in the range of 1 × 10 ^-2 ~8 × 10 ^-1 mol. Further, the magenta coupler according to the present invention can be used in combination with another type of magenta coupler. The compound represented by the general formula [A] can be used in combination with another type of image stabilizer.

The amounts of the compounds represented by the general formulas [A], [B] and [C] are based on the amount of the magenta coupler.
The content is preferably 5 to 400 mol%, more preferably 10 to 250 mol%.

The dye image stabilizers represented by formulas [A], [B] and [C] and the magenta coupler according to the present invention are preferably used in the same layer, but the coupler is present. It may be contained in a layer adjacent to the layer.

To incorporate the compound represented by the general formula [A], the compound represented by the general formula [B] or the general formula [C] of the present invention and the magenta coupler according to the present invention, a conventional method is used. For example, a mixture of a high-boiling solvent such as a known dibutyl phthalate or tricresyl phosphate and a low-boiling solvent such as butyl acetate or ethyl acetate, or only a low-boiling solvent, is used to prepare a magenta coupler represented by the general formula (M). After dissolving each alone or in combination, the mixture is mixed with an aqueous gelatin solution containing a surfactant, and then emulsified and dispersed using a high-speed rotary mixer or a colloid mill or an ultrasonic disperser, and then dispersed in the emulsion. A direct addition method can be employed. Alternatively, the emulsified dispersion may be set, then cut into pieces, washed with water, and then added to the emulsion.

The dye image stabilizers represented by the general formulas [A], [B] and [C] and the magenta coupler of the present invention are separately prepared by a high boiling solvent and the above-mentioned dispersion method. It may be dispersed and added to the silver halide emulsion, but both compounds are simultaneously dissolved and dispersed,
The method of adding to a silver halide emulsion is preferred.

The amount of the high boiling point solvent added is preferably 0.01 to 1 with respect to 1 g of the magenta coupler of the present invention.
0 g, more preferably in the range of 0.1 to 3.0 g.

As the silver halide emulsion used in the light-sensitive material of the present invention, any conventional silver halide emulsion can be used. The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region using a sensitizing dye.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as a binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened, and can contain a plasticizer and a dispersion (latex) of a water-insoluble or hardly soluble synthetic polymer. A coupler is used in the emulsion layer of the color light-sensitive material.

Further, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, by a coupling reaction with a colored coupler having a color correcting function, a competitive coupler and an oxidized form of a developing agent. Compounds that release photographically useful fragments can be used, such as hardeners, foggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers.

In the light-sensitive material of the present invention, an image stabilizer and an ultraviolet absorber can be used for the purpose of preventing deterioration of a dye image.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

In order to obtain a dye image using the light-sensitive material of the present invention, a generally known color photographic processing is performed after exposure.

[0116]

Next, the present invention will be described based on examples, but embodiments of the present invention are not limited to these examples.

Example 1 On a paper support, polyethylene was laminated on one side and polyethylene containing titanium oxide was laminated on the other side. Titanium oxide was applied to each layer having the structure shown in Tables 1 and 2 below. This was applied on the side of the polyethylene layer to be prepared, whereby a multilayer color photosensitive material sample 101 was prepared.

[0118]

[Table 1]

[0119]

[Table 2]

The coating solution was prepared as follows.

First layer coating solution 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), 6.67 of (ST-2)
g, 0.67 g of a stain inhibitor (HQ-1) and 6.67 g of a high boiling point organic solvent (DNP) by adding and dissolving 60 ml of ethyl acetate, and a 20% aqueous solution of a surfactant (SU-2) 7
The mixture was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution using an ultrasonic homogenizer to prepare a yellow coupler dispersion.

The above dispersion was mixed with the following blue-sensitive silver halide emulsion (containing 8.67 g of silver), and an anti-irradiation dye (AI-1) was further added to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. (H-1) was added to the second and fourth layers as a hardener, and (H-2) was added to the seventh layer. Surfactants (SU-1) and (SU-3) were added as coating aids to adjust the surface tension.

The structural formulas of the compounds used in each of the above-mentioned layers are shown below.

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) sodium salt DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4 -Dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octylhydroquinone 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) butyl] hydroquinone

[0126]

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[0127]

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[0128]

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The silver halide emulsions used for the first, third and fifth layers are as follows.

Blue-sensitive silver halide emulsion (Em-B) Monodispersed cubic silver chlorobromide emulsion having an average particle size of 0.85 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.5 mol% Sodium thiosulfate 0 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 Green-sensitive silver halide emulsion (Em-G) Monodispersed cubic silver chlorobromide having an average particle size of 0.43 μm, a coefficient of variation = 0.08, and a silver chloride content of 99.5 mol%. Emulsion Sodium thiosulfate 1.5 mg / mol AgX Chloroic 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 Red sensitivity Silver halide emulsion (Em R) Monodisperse cubic silver chlorobromide emulsion having an average particle size of 0.50 µm, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol% Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / Molar AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole

[0131]

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Next, the magenta coupler (M-23), image stabilizers (ST-3) and (C-
Sample 1 was used except that 3) was changed to the combination shown in Table 3.
Samples 102 to 112 were produced in the same manner as in Sample No. 01.

Each sample was exposed to wedges with green light according to a conventional method, and then developed according to the following processing steps.

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. 60 seconds The composition of the treatment liquid is shown below. The replenishment amount of each processing solution is 80 ml per 1 m ² of the photosensitive material.

Color developing solution tank replenisher Pure water 800 ml 800 ml triethanolamine 10 g 18 g N, N-diethylhydroxylamine 5 g 9 g potassium chloride 2.4 g -1-hydroxyethylidene-1,1-diphosphonic acid 1.0 g 8 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4 g 8.2 g Fluorescent whitening agent (4,4′-diaminostilbene disulfonic acid derivative) 1.0 g 1 8.8 g Potassium carbonate 27 g 27 g Water was added to make the total volume 1000 ml. The pH of the tank solution was 10.10 and the pH of the replenisher was 10.
Adjust to 60.

Bleaching-fixing solution (tank solution and replenisher are the same) Ferric ammonium ammonium diamine tetraacetate dihydrate 60 g Ethylene diamine tetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml In addition, the total amount is adjusted to 1000 cc, and the pH is adjusted to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (the tank solution and the replenishing solution are the same) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2 1.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 1.5 g Water was added to bring the total volume to 1000 ml, and sulfuric acid or water was added. Adjust the pH to 7.0 with potassium oxide.

After the continuous treatment, the obtained sample was irradiated with a xenon fade meter for 7 days, and the residual ratio (%) of the dye image at an initial density of 1.0 was determined. Table 3 also shows the results.

[0139]

[Table 3]

As is clear from Table 3, samples 101 to 1
12, samples 103 to 1 using the compound of the present invention
Nos. 06 and 109 to 112 were found to have significantly improved light fastness and improved color development as compared to Samples 101 and 107 using the comparative compound.

[0141]

According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material which is remarkably improved in light fastness of a dye image and excellent in color developability.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material comprising at least one compound represented by the following general formula [A]. Embedded image [In the formula, R ₁ represents an alkyl group, a cycloalkyl group or an aryl group, and R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R ₃ , R ₄ , R ₅ and R ₆
Each hydrogen atom or an alkyl group or an aryl group, when R ₃ and R ₅ or R ₄ and R ₆ represents an alkyl group, R ₃
And R ₅ or R ₄ and R ₆ may combine with each other to form a ring. R ₇ and R ₈ each represent a hydrogen atom or an alkyl group, R ₉ represents a hydrogen atom or a substituent, and R ₁₀ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. m represents an integer of 0 to 4. When m is 2 or more, a plurality of R ₉ may be the same or different. n is 0
Or represents 1. ] 2. A silver halide color photographic light-sensitive material according to claim 1, which contains at least one magenta coupler represented by the following general formula [M]. Embedded image [Wherein, R represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group which can be removed by reaction with an oxidized form of a color developing agent. Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring. ] 3. A photographic composition comprising at least one compound represented by the general formula [A] and at least one magenta coupler represented by the general formula [M] in the same photographic constituent layer. 3. The silver halide color photographic light-sensitive material according to claim 2, wherein