JPH05307241A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To accelerate color forming speed and to improve color development performance, and fastness and hue of a formed dye by incorporating a specified coupler in at least one of hydrophilic colloidal layers on a base. CONSTITUTION:At least one of hydrophilic colloidal layers on a base contains the coupler represented by formula I or II, in which R1 is an alkyl, or a cycloalkyl; R2 is an aryl; R3 is an aryl or a heterocyclic group; R4 is a substituent; m is 0, 1, 2, or 3; Y is an atomic group necessary to form an N-containing heterocyclic group; X is a group to be released by coupling with the oxidation product of an aromatic primary amine color developing agent; and when each of R2 and R3 is an aryl, each is >=6C, preferably, a 6-10 C aryl optionally substituted.

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 (hereinafter sometimes simply referred to as a light-sensitive material) containing a novel coupler. The present invention relates to a silver halide color photographic light-sensitive material containing a novel yellow coupler having high fastness and high reactivity with an oxidized product of a developing agent.

[0002]

In a color photographic light-sensitive material, the material is exposed to light and then color-developed, whereby an oxidized aromatic primary amine developing agent reacts with a coupler to form an image. In this method, a color reproduction method by a subtractive color method is used, and in order to reproduce blue, green, and red, yellow, magenta, and cyan color images having complementary colors are formed. Above all, a yellow dye forming coupler (hereinafter referred to as a yellow coupler) is used for forming a yellow color image.
Acylacetanilide couplers and malondianilide couplers are widely known as. These couplers are generally used as 2-equivalent couplers having a leaving group at the active site in order to obtain maximum dye density and photographic sensitivity with a small amount of silver. In recent years, it has been required to further improve the coloring efficiency of these 2-equivalent couplers.
-115219, 54-48541 and 56-
A coupler having a sulfamoyl group as a ballast component, which is described in Japanese Patent No. 74250, has been proposed.
However, the color forming properties of these couplers are not sufficient, and the azomethine dyes obtained by the coupling reaction between these couplers and the oxidized product of the color developing agent are
The image fastness was low, and the magenta component was large in the yellow image, which was not preferable for color reproduction.

In particular, in recent years, there has been an increasing demand for faithful color reproduction, and development of couplers having a sharp visible absorption spectrum of a dye obtained from the coupler has been underway. From this point of view, JP-A-63-12
A coupler having an alkoxy group or an aryloxy group at the ortho position of the anilide portion as described in Japanese Patent No. 3047 has been proposed. However, the azomethine dye obtained by this coupler has a problem that the image fastness, particularly the wet and heat fastness is low.

[0004]

An object of the present invention is to solve the above problems. That is, it is intended to provide a light-sensitive material having a high dye formation rate, excellent color development, and excellent fastness and hue of the formed dye.

[0005]

The above-mentioned object is characterized in that at least one hydrophilic colloid layer on a support contains a coupler represented by the following general formula (I) or (II). Achieved by a silver halide color photographic light-sensitive material.

[0006]

[Chemical 2]

(In the formula, R ₁ represents an alkyl group or a cycloalkyl group, R ₂ represents an aryl group, R ₃ represents an aryl group or a heterocyclic group, R ₄ represents a substituent, and m represents 0. Represents an integer of from 3 to Y, represents an organic residue necessary for forming a nitrogen-containing heterocycle with a nitrogen atom, and X is eliminated in a coupling reaction with an oxidation product of an aromatic primary amine color developing agent. Represents the group

First, the coupler represented by formula (I) or (II) will be described. When R ₂ and R ₃ in the general formulas (I) and (II) represent aryl groups, they are substituted or unsubstituted aromatic groups having 6 or more carbon atoms, preferably 6 to 10 carbon atoms. Particularly preferred is phenyl or naphthyl. In the general formulas (I) and (II), when R ₃ represents a heterocyclic group, it has 1 or more carbon atoms, preferably 1 to 10, particularly preferably 2 to 5, saturated or unsaturated, substituted or unsubstituted heterocyclic ring. It is a base. Preferably as a heteroatom,
Examples are nitrogen atoms, sulfur atoms or oxygen atoms.
The number of ring members is preferably a 5- or 6-membered ring, but may be any other number. It may be either a monocyclic ring or a condensed ring. R ₃
When represents a heterocyclic group, specific examples thereof include 2-pyridinyl, 1-pyrimidinyl, 2-thiazolyl, 3-isoxazolyl, 3-triazolyl and the like. In the general formulas (I) and (II), the substituent of R ₄ and R ₂ and R
Examples of the substituent when the group represented by ₃ each have a substituent, a halogen atom (e.g. fluorine atom, iodine atom, chlorine atom, bromine atom), a cyano group, a nitro group,
Carboxyl group, hydroxy group, sulfo group, mercapto group, alkyl group (having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms)
Straight, branched, cyclic. For example, methyl, ethyl, isopropyl, cyclopropyl, cyclopentyl, dodecyl,
2-hexyloctyl), an aryl group (having 6 or more carbon atoms,
Preferably 6-10. For example, phenyl, naphthyl),
Heterocyclic group (having 1 or more carbon atoms, preferably 1-10, particularly preferably 2-5. Either saturated or unsaturated, either monocyclic or condensed ring, preferably heteroatom) , A nitrogen atom, a sulfur atom or an oxygen atom, and the number of ring members is preferably a 5- or 6-membered ring.
For example, 2-pyridyl, 4-pyrimidinyl, 5-pyrazolyl, 8-quinolyl, 2-furyl, 2-pyrrolyl, succinimide), an alkoxy group (having 1 to 30, preferably 1 to 24 carbon atoms, for example, methoxy, dodecyloxy), Aryloxy group (6 to 20 carbon atoms, preferably 6 to 10 carbon atoms.
For example, phenoxy, 4-chlorophenoxy), an alkylthio group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, methylthio, dodecylthio), an arylthio group (having 6 to 20 carbon atoms, preferably 6 to 10. For example, phenylthio), acyl. A group (having 1 to 30 carbon atoms, preferably 2 to 2 carbon atoms)
0. For example, acetyl, benzoyl), a sulfonyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, methanesulfonyl, octanesulfonyl, dodecanesulfonyl, benzenesulfonyl), an alkoxycarbonyl group (having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms). . For example, methoxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl), alkoxysulfonyl group (C1-C3)
0, preferably 1-20. For example, methoxysulfonyl,
Dodecyloxysulfonyl, hexadecyloxysulfonyl), aryloxycarbonyl group (C7-C3)
0, preferably 7-20. For example, phenoxycarbonyl), an aryloxysulfonyl group (having 6 to 30 carbon atoms,
Preferably 6-20. Phenoxysulfonyl),
Acylamino group (having 2 to 30 carbon atoms, preferably 2 to 2 carbon atoms)
0. For example, acetamide, tetradecanamide, 2-
(2,4-di-t-amylphenoxy) butanamide,
Benzamide), sulfonamide group (having 1 to 30 carbon atoms,
Preferably 1 to 20, for example methanesulfonamide, dodecanesulfonamide, hexadecanesulfonamide,
Benzenesulfonamide), carbamoyl group (2 carbon atoms
-30, preferably 2-20. For example, N-butylcarbamoyl, N, N-diethylcarbamoyl), sulfamoyl group (having 1 to 30, preferably 1 to 20 carbon atoms. For example, N-butylsulfamoyl, N-phenylsulfamoyl, N-dodecylsulfamoyl) , N-hexadecylsulfamoyl, N-3- (2,4-di-t-amylphenoxy) butylsulfamoyl), an alkoxycarbonylamino group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, methoxycarbonyl Amino, tetradecyloxycarbonylamino), an aryloxycarbonylamino group (having 7 to 30 carbon atoms, preferably 7 to 20. For example, a phenoxycarbonylamino group), an N-acylsulfamoyl group (having 2 to 30 carbon atoms, preferably 2 to 20. For example, N-
Propanoylsulfamoyl, N-tetradecanoylsulfamoyl), N-acylcarbamoyl group (C2
-30, preferably 2-20. For example, N-propanoylcarbamoyl, N-docanoylcarbamoyl), N-sulfonylcarbamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-hexadecanesulfonylcarbamoyl group, N-octanesulfonylcarbamoyl group, N-
Benzenesulfonylcarbamoyl, N- (2-octyloxy-5-t-octylbenzenesulfonyl) carbamoyl), N-sulfonylsulfamoyl group (having 0 carbon atoms)
-30, preferably 1-20. For example, N-octanesulfonylsulfamoyl group, N-dodecanesulfonylsulfamoyl, N-benzenesulfonylsuspamoyl), N-carbamoylsulfamoyl group (having 1 to 1 carbon atoms).
30, preferably 1-20. For example, N- (N-ethylcarbamoyl) sulfamoyl), N- {3-(2,
4-di-t-amylphenoxy) propylcarbamoyl} sulfamoyl)), N-sulfamoylcarbamoyl group (having 1 to 30, preferably 1 to 20 carbon atoms. For example, N- (ethylsulfamoyl) carbamoyl, N-
(N-butylsulfamoyl) carbamoyl) N- {3
(2,4-di-t-amylphenoxy) propylsulfamoyl} carbamoyl), N- (N-sulfonylcarbamoyl) sulfamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N- (dodecanesulfonyl). Carbamoyl) sulfamoyl, N- (2-octyloxy-5-t-octylbenzenesulfonylcarbamoyl)
Sulfamoyl), 3-sulfonylureido group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, 3-hexadecanesulfonylureido, 3-benzenesulfonylureido), 3-acylureido (having 2 to 30 carbon atoms, preferably 2) 20. For example, 3-acetylureido, 3-
Benzoylureido), 3-acylsulfamide group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, 3-propionylsulfamide, 3- (2,4-dichlorobenzoyl) sulfamide), 3-sulfonyl. Sulfamide group (0 to 30 carbon atoms, preferably 0 to 20. For example,
3-methanesulfonylsulfamide, 3- (2-methoxyethoxy-5-t-octylbenzenesulfonyl) sulfamide), acyloxy group (having 1 to 30, preferably 1 to 20 carbon atoms. For example, propanoyloxy, tetra Decanoyloxy), sulfonyloxy group (0 carbon atoms
-30, preferably 1-20. For example, decanesulfonyloxy, 2-octyloxy-5-t-octylbenzenesulfonyloxy), a carbamoylamino group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-butylcarbamoylamino), sulfamoylamino. A group (having 0 to 30 carbon atoms, preferably 0 to 20. For example, N-butylsulfamoylamino, N-dodecylsulfamoylamino), an N-alkoxycarbonylsulfamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-
Butoxycarbonylsulfamoyl), N-aryloxycarbonylsulfamoyl group (C7-30, preferably 7-20. For example, N-butoxycarbonylsulfamoyl), N-hydroxycarbamoyl group, N-
Examples thereof include a hydroxysulfamoyl group.

Preferred substituents when the group represented by R ₂ has a substituent include halogen atoms, sulfonyl groups, acylamino groups, carbamoyl groups, alkyl groups, sulfonamide groups, sulfamoyl groups among those enumerated above. Group, an alkoxycarbonyl group or an alkoxy group. When the group represented by R ₃ has a substituent, preferred substituents are a halogen atom, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, a sulfonamide group, an alkyl group, an acylamino group, and an N-acyl sulfa group. Examples thereof include moyl group, acyl group, alkoxy group, cyano group, carboxyl group, hydroxy group and nitro group.

In the general formula (I), R ₁ is preferably a tertiary alkyl group having 4 to 30 carbon atoms and may contain a cyclic structure such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. R ₁ may have a substituent, and examples of these substituents include the substituents enumerated as the substituents which the group represented by R ₂ may have. Preferred are a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, an acylamino group and a sulfonamide group. Preferred R ₁ in the general formula (I) is represented by the following general formula ( _RA ).

[0011]

[Chemical 3]

(In the formula, R ₀₁ , R ₀₂ and R _{03, which} may be the same or different, each represents an alkyl group having 1 to 4 carbon atoms. R ₀₁ and R ₀₂ are bonded to each other to form a cycloalkylene group. R ₀₃ and R ₀₁ or R ₀₂ are not bonded to each other.) Among the preferred R ₁ , more preferred one is that R ₀₁ and R ₀₂ are bonded to each other to form a cycloalkylene group. It is a 1-alkylcycloalkyl group represented by the following general formula (R _B ).

[0013]

[Chemical 4]

(In the formula, R ₀₃ has the same _{meaning as} that in the above general formula (R _A ). L ₁ is an alkylene group for forming a cycloalkylene group.) Particularly preferred R ₁
Is a 1-alkylcyclopropyl group in which L ₁ is a propylene group.

Specific examples of the heterocyclic group represented by Y and> N- represented by the general formula (II) include morpholino and 1
-Imidazolidinyl, 1-pyrazolyl, 1-piperazino, 1-indolinyl, 1,2,3,4-tetrahydroquinoxalin-1-yl, 1-pyrrolinyl, pyrazolidin-1-yl, 2,3-dihydro-1-indazolyl,
Isoindoline-2-yl, 1-pyrrolyl, 2-pyrazolin-1-yl, benzothiazin-4-yl, 4-thiazinyl, perhydro-1,1-dioxo-1,4-thiazin-4-yl, benzodiazin-1 -Yl, aziridin-1-yl, benzoxazin-4-yl, 2,3
4,5-tetrahydroquinolyl or phenoxazine-
10-yl and the like can be mentioned. Y in the general formula (II)
As the heterocyclic group formed by and> N-, a nitrogen-containing heterocyclic group containing at least one unsaturated carbon is preferable. Examples of such heterocyclic groups include indolinyl, 2,3,4,5-tetrahydroquinolyl, isoindolino or 4-oxopiperidino. The heterocyclic group formed by Y and> N- in the general formula (II) is particularly preferably an indolinyl group.

The group represented by X in the general formulas (I) and (II) may be any conventionally known coupling-off group. Preferable X is a nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom, an aromatic oxy group, an aromatic thio group, a heterocyclic oxy group, a heterocyclic thio group, an acyloxy group, a carbamoyloxy group, an alkylthio group or A halogen atom is mentioned. These leaving groups are photographic useful groups or precursors thereof (for example, development inhibitors, development accelerators, desilvering accelerators, fogging agents, dyes, hardeners, couplers, developing agent oxidant scavengers, fluorescent dyes, It may be either a developing agent or an electron transfer agent) or a non-photographic useful group.

When X represents a nitrogen-containing heterocyclic group, it is specifically a monocyclic or condensed ring substituted or unsubstituted heterocyclic group. Examples thereof include succinimide, maleimide, phthalimide, diglycolimide, pyrrino,
Pyrazolyl, imidazolyl, 1,2,4-triazol-2-yl (or 4-yl), 1-tetrazolyl, indolyl, benzopyrazolyl, benzimidazolyl, benzotriazolyl, imidazolidine-2,4-dione-
3-yl (or 1-yl), oxazolidine-2,4
-Dione-3-yl, thiazolidine-2,4-dione-
3-yl, imidazolin-2-one-1-yl, oxazolin-2-one-3-yl, thiazolin-2-one-
3-yl, benzoxazolin-2-one-3-yl,
1,2,4-triazolidine-3,5-dione-4-yl, 2-pyridon-1-yl, morpholin-3,5-dione-4-yl, 1,2,3-triazol-1-yl or 2-Imidazolin-5-one may be mentioned. When these heterocyclic groups have a substituent, examples of the substituent include the substituents listed as R ₄ above.

When X represents a nitrogen-containing heterocyclic group, it is preferably 1-pyrazolyl, imidazolyl, 1,2,3-triazol-1-yl, benzotriazolyl, 1,2,2.
4-triazol-1-yl, oxazolidine-2,4
-Dione-3-yl, 1,2,4-triazolidine-
3,5-dione-4-yl, or imidazolidine-
It is 2,4-dione-3-yl. These include cases where they have a substituent.

When X represents an aromatic oxy group, it is preferably a substituted or unsubstituted phenoxy group. When it has a substituent, examples of the substituent include those mentioned above as R ₄ . The preferred substituent which the phenoxy group has is a case where at least one substituent is an electron-withdrawing substituent, and for example, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group, an acyl group or a nitro group. Is an example.

When X represents an aromatic thio group, it is preferably a substituted or unsubstituted phenylthio group. When it has a substituent, examples of the substituent include those mentioned above as R ₄ . The preferred substituent which the phenylthio group has is a case where at least one of the substituents is an alkyl group, an alkoxy group, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group or a nitro group.

When X represents a heterocyclic oxy group, the heterocyclic group moiety has the same meaning as when R ₃ represents a heterocyclic group. When X represents a heterocyclic thio group, 5
6-membered unsaturated heterocyclic thio groups are preferred examples. For example, tetrazolylthio group, 1,3,4-thiadiazolylthio group, 1,3,4-oxadiazolylthio group, 1,3,4-triazolylthio group, benzimidazolylthio group, benzothiazolylthio group or 2- Examples thereof include a pyridylthio group. When these have a substituent, examples thereof include the substituents listed as R ₄ . Among these, a particularly preferable substituent is an aromatic group, an alkyl group, an alkylthio group, an acylamino group, an alkoxycarbonyl group or an aryloxycarbonyl group.

When X represents an acyloxy group, specifically, it is an aromatic acyloxy group (having 7 to 11 carbon atoms, preferably benzoyloxy group) or an aliphatic acyloxy group (having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms). Yes, it may have a substituent. Specific examples of the substituent include the above R
Substituents listed as ₄ are mentioned. A preferable substituent is a case where at least one substituent is a halogen atom, a nitro group, an aryl group, an alkyl group or an alkoxy group.

When X represents a carbamoyloxy group,
It is an aliphatic, aromatic, heterocyclic or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Examples thereof include N, N-diethylcarbamoyl, N-phenylcarbamoylmorpholinocarbonyloxy, 1-imidazolylcarbonyloxy or N, N-dimethylcarbamoyloxy. Here, a detailed description of an alkyl group, an aromatic group and a heterocyclic group is given in the above R ₂
And R _{3 have} the same meanings as defined in the description. X
Represents an alkylthio group, it is an alkylthio group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. The detailed description of the alkyl group has the same meaning as defined in the description of R ₂ and R ₃ .

Preferred as the group represented by X in the general formula (I) are a 5- or 6-membered nitrogen-containing heterocyclic group (bonded to the coupling position at a nitrogen atom), an aromatic oxy group, 5
And a 6-membered heterocyclic oxy group or a 5- or 6-membered heterocyclic thio group. X is more preferably the following general formula (X ₁ )
Alternatively, it is a group represented by (X ₂ ).

[0025]

[Chemical 5]

In the formula, P is the remaining --CON (-) CO--.
It represents a group of non-metal atoms necessary for forming a 5- or 6-membered heterocycle with a group. X ₁ , X ₂ , X ₃ and X ₄ each represent a non-metal atom group necessary for forming a 5-membered aromatic heterocycle with a nitrogen atom. P, X ₁ , X ₂ , X ₃
And X ₄ may be substituted with a substituent such as those mentioned for R ₄ . P is preferably represented by the following formula.

[0027]

[Chemical 6]

Here, R ₆ , R ₇ , R ₁₀ and R ₁₁ each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfonyl group or an amino group. R ₈ and R ₉
Each represent a hydrogen atom, an alkyl group, an aryl group, a sulfonyl group or an alkoxycarbonyl group. R ₁₂
And R ₁₃ each represent a hydrogen atom, an alkyl group or an aryl group. Each of X ₁ , X ₂ , X ₃ and X ₄ is specifically -N =, = C (R ₁₄ )-, -S-, -O-.
Represents each group of. R ₁₄ represents a hydrogen atom or a substituent. Examples of the substituent of R ₁₄ include the substituents of R ₄ . When two ═C (R ₁₄ ) — are adjacent to each other, these R _{14 s} may be bonded to each other or may form a condensed ring with benzene. X is particularly preferably 1
-Pyrazolyl, imidazolyl, 1,2,3-triazol-1-yl, benzotriazolyl, 1,2,4-triazol-1-yl, oxazolidin-2,4-dione-3-yl, 1,2, 4-triazolidine-3,5-dione-4-yl or imidazolidin-2,4-dione-3-yl. These include cases where they have a substituent.

Among the couplers represented by the general formula (I) or (II) in the present invention, a particularly preferred coupler is represented by the following general formula (II-A).

[0030]

[Chemical 7]

(In the formula, R ₂ , R ₃ and X have the same meanings as in formula (II). R ₅ represents a substituent on the indolinyl ring, and a represents an integer of 0 to 4.) Examples of the substituent of R ₅ include the substituents listed above as R ₄ . Preferred substituents are halogen atom, cyano group, sulfonyl group, acylamino group, carbamoyl group,
An alkyl group, a sulfonamide group or a nitro group may be mentioned. As a, 0, 1 or 2 is preferable, and 0 or 1 is more preferable.

A preferred example of the coupler of the present invention is a diffusion resistant coupler. The diffusion resistant coupler is a coupler having a diffusion resistant group so as to be immobilized in the layer to which the coupler is added. The anti-diffusion group is usually a group that sufficiently increases the molecular weight, and an alkyl group having 8 to 30 carbon atoms, preferably 10 to 20 carbon atoms, or an aryl group having a substituent group having 4 to 20 carbon atoms is used. .. These diffusion resistant groups may be substituted in any of the molecules, or may have a plurality of groups. The coupler of the present invention has R ₁ ,
R ₂ , R ₃ , R ₄ , Y and X are divalent or 2
You may form the dimer or more multimer linked with each other through the group more than the valence. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range. Specific examples of the coupler of the present invention are shown below, but the present invention is not limited thereto.

[0033]

[Chemical 8]

[0034]

[Chemical 9]

[0035]

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical formula 12]

[0038]

[Chemical 13]

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

[0042]

[Chemical 17]

[0043]

[Chemical 18]

[0044]

[Chemical 19]

[0045]

[Chemical 20]

[0046]

[Chemical 21]

[0047]

[Chemical formula 22]

[0048]

[Chemical formula 23]

The compound of the present invention can be synthesized by a known method generally known in the art or a method similar thereto. For example, it can be synthesized by the following synthesis route. Synthesis route of coupler represented by general formula (I)

[0050]

[Chemical formula 24]

Synthesis route of coupler represented by formula (II)

[0052]

[Chemical 25]

In the formula, R ₁ , R ₂ , R ₃ , X and Y have the same meanings as described in the general formulas (I) and (II). R ₄ and R ₅ are a halogen atom (e.g. crawling atoms), - represents OH, alkoxy groups (e.g. methoxy, ethoxy), or a phenoxy group (e.g., phenoxy, 4-nitrophenoxy) a. HAL represents halogen. Under the reaction conditions of (a), when R ₄ and R ₅ are OH, a dehydration condensing agent (for example, N, N-dicyclohexylcarbodiimide, N, N-diisopropylcarbodiimide) is used. When R ₄ and R ₅ are halogen atoms, the reaction is carried out in the presence of a dehydrohalogenating agent. As the dehydrohalogenating agent, an organic base (eg, triethylamine, diisopropylethylamine, pyridine, guanidine, butoxy potassium), an inorganic base (eg, sodium hydroxide, potassium hydroxide, sodium hydride, potassium carbonate) and the like are used. 3a →
In the reaction of 4a and 3b → 4b, a halogenating agent is used as (b). For example, bromine, chlorine, sulfuryl chloride,
Examples thereof include N-bromosuccinimide and N-chlorosuccinimide. In the reaction of 4a → final product and 4b → final product, a dehydrohalogenating agent is generally used as (c). Examples include the above-mentioned organic bases or inorganic bases. A reaction solvent is generally used in each reaction. For example, chlorine-based solvent (for example, dichloromethylene), aromatic solvent (for example, benzene, chlorobenzene, toluene), amide-based solvent (for example, N, N-dimethylformamide, N, N-dimethylacetamide,
N-methylpyrrolidone), a nitrile solvent (eg acetonitrile, propionitrile), an ether solvent (eg tetrahydrofuran, ethylene glycol diethyl ether), a sulfone solvent (eg dimethyl sulfone, sulfolane) or a hydrocarbon solvent (eg cyclohexane). , Normal hexane).

It can be synthesized by a method other than the above-mentioned synthesis route. For example, J. Org. Chem., 2
It can also be synthesized by the method described in 9, 2932 (1964). In addition, the functional group may be further converted from 5a and 5b to induce the final target product. The change of the synthetic route or the additional reaction can be appropriately selected. The specific synthesis method is described below. Other exemplified compounds can be similarly synthesized. Synthesis example 1. Synthesis of Exemplified Compound (61) The compound was synthesized by the following synthesis method.

[0055]

[Chemical formula 26]

8.3 g of compound 6a and 2 of 7a
2.0 g was mixed, and the reaction was carried out at 130 ° C. for 4 hours while distilling off ethanol sometimes generated under reduced pressure. After the reaction, excess 6a was distilled off under reduced pressure, and hexane was added to the residue for crystallization. 20.8 g of 8a was obtained. 17.5 g of 8a were mixed with 150 ml of dichloromethane. A solution of 2.8 g of sulfuryl chloride in 10 ml of dichloromethane was added dropwise under ice cooling (5 ° C to 10 ° C). After reacting for 30 minutes, the solvent was distilled off under reduced pressure, and the residue 9a was directly used in the next step. 1-benzyl-5-ethoxyimidazolidine-
9.7 g of 2,4-dione and 5.6 ml of triethylamine were added to 150 ml of N, N-dimethylformamide. Into this solution, 9a obtained above was dissolved in 50 ml of N, N-dimethylformamide and added dropwise at room temperature. After reacting for 1 hour, 500 ml of ethyl acetate was added, and the mixture was transferred to a separating funnel and washed with water. After neutralization with diluted hydrochloric acid, the mixture was washed with water again, and the oil layer was separated. The solvent was distilled off under reduced pressure, and the residue was separated and purified by column chromatography. Silica gel was used as the packing material, and ethyl acetate / hexane (1/2) was used as the eluent. Fractions containing the target exemplified compound (61) were collected and the solvent was distilled off under reduced pressure to obtain 16.1 g of wax-like exemplified compound (61).

Synthesis Example 2. Synthesis of Exemplified Compound (62) Said Synthesis Example 1. Was synthesized in the same manner as. However, instead of 7a, an equimolar amount of the following 11a was used. The final product was purified by column chromatography to obtain 16.7 g of waxy (62).

[0058]

[Chemical 27]

Synthesis Example 3. Synthesis of Exemplified Compound (1) The compound was synthesized by the following synthesis method.

[0060]

[Chemical 28]

6.2 g of compound 6b, and 1 of 7b
9.9 g was dissolved in 150 ml N, N-dimethylformamide. To this solution, 40 ml of an N, N-dimethylformamide solution in which 6.8 g of N, N'-dicyclohexylcarbodiimide was dissolved was added dropwise at room temperature. After reacting for 2 hours, the precipitated N, N'-dicyclohexylurea was filtered off. The filtrate was added to 500 ml of water and extracted with 500 ml of ethyl acetate. The oil layer was collected using a separating funnel and washed with water, and then the oil layer was dried with Glauber's salt. The solvent was distilled off under reduced pressure, and hexane was added to the residue for crystallization. 21.2 g of 8b was obtained. 17.0 g of 8b was mixed with 150 ml of dichloromethane. Dichloromethane 1 containing 3.0 g of sulfuryl chloride
0 ml of the solution was added dropwise under ice cooling (5 ° C to 10 ° C). After reacting for 30 minutes, the solvent was evaporated under reduced pressure, and the residue 9b was used in the next step. 5,5-Dimethyl-2,4-dioxo-1,3-oxazolidine (5.2 g) and triethylamine (5.6 ml) were added to N, N-dimethylformamide (150 ml).
Added to. To this solution, add 9b obtained above to 50 ml of N,
It was dissolved in N-dimethylformamide and added dropwise at room temperature. After reacting for 1 hour, 500 ml of ethyl acetate was added, and the mixture was transferred to a separating funnel and washed with water. After neutralization with diluted hydrochloric acid, the mixture was washed with water again, and the oil layer was separated. The solvent was distilled off under reduced pressure, and the residue was separated and purified by column chromatography. Silica gel was used as the packing material, and ethyl acetate / hexane (1/2) was used as the eluent. Fractions containing the target exemplified compound (1) were collected, the solvent was distilled off under reduced pressure, and the residue was recrystallized with a hexane-isopropanol mixed solution to obtain 14.1 g of the exemplified compound (1).

Synthesis Example 4. Synthesis of Exemplified Compound (2) Synthesis Example 3. Was synthesized in the same manner as. However, an equimolar amount of 10b below was used instead of 6b, and an equimolar amount of 11b below was used instead of 7b. The final product was purified by column chromatography and recrystallized with a hexane-isopropanol mixed liquid to obtain 17.9 g of Exemplified compound (2).

[0063]

[Chemical 29]

Synthesis Example 5. Synthesis of Exemplified Compound (3) Synthesis Example 3. Was synthesized in the same manner as. However, instead of 7b, an equimolar amount of 12b below was used. The final product was purified by column chromatography and recrystallized with a hexane-isopropanol mixed solution to obtain 15.2 g of Exemplified compound (3).

[0065]

[Chemical 30]

The yellow coupler of the present invention is preferably added to the light-sensitive silver halide emulsion layer or its adjacent layer in the light-sensitive material, and is added to the light-sensitive silver halide emulsion layer, particularly to the blue-sensitive silver halide emulsion layer. Is particularly preferable. When the leaving group X contains a development inhibitor component, the total amount added to the light-sensitive material is 0.001 to 0.80 g / m ²
, And the preferably more preferably 0.005~0.50g / m ^2, a 0.02~0.30g / m ^2. Further, when the leaving group X does not contain a development inhibitor component, the addition amount thereof is from 0.001 to 1.20 g / m ² , preferably from 0.01 to 1.00 g / m ² . 0.10-
It is 0.80 g / m ² .

The yellow coupler of the present invention can be incorporated into a light-sensitive material by a known dispersion method. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid ester (Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-
Ethylhexyl phenylphosphonate, etc.), Benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecanoamide, N, N-diethyllaurylamide, N) -Tetradecylpyrrolidone etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol Tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.),
Hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like can be mentioned. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably about 50 ° C or higher.
An organic solvent at 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat.
LS) No. 2,541,274 and No. 2,541,230.

The light-sensitive material of the present invention may have a hydrophilic colloid layer containing the coupler of the present invention on a support, and as the hydrophilic colloid layer, a yellow color-forming silver halide emulsion layer or a silver halide emulsion layer thereof can be used. Adjacent layers are preferred. The light-sensitive material preferably has yellow-color-forming, magenta-coloring, and cyan-coloring silver halide emulsion layers, and each is preferably blue-sensitive, green-sensitive and red-sensitive. The light-sensitive material of the present invention can be formed by coating in this order, but the order may be different from this. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned photosensitive emulsion layers. As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochloride, silver iodochlorobromide, silver iodobromide and the like can be used, but the effects of the present invention are particularly preferable. From the viewpoint of effectively exhibiting the above-mentioned properties and the purpose of rapid processing, the silver chlorobromide or silver chloride emulsion having a silver chloride content substantially free of silver iodide of 90 mol% or more, further 95% or more, and particularly 98% or more. Is preferably used. In the light-sensitive material according to the present invention, for the purpose of improving the sharpness of an image, a hydrophilic colloid layer is provided with a dye which can be decolorized by the treatment described in European Patent EP 0,337,490A2, pages 27 to 76. However, an oxonol-based dye) is added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.70 or more, and 2 to 4 alcohols (eg trimethylolethane) are added to the water-resistant resin layer of the support. Titanium oxide surface-treated with etc. 1
It is preferable to contain 2% by weight or more (more preferably 14% by weight or more).

In the light-sensitive material of the present invention, it is preferable to use a color image storability-improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler. That is, the compound (F) that chemically bonds with the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the aroma remaining after the color development processing. The use of the compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine color developing agent, simultaneously or solely, for example, in storage after processing. It is preferable in order to prevent stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or its oxidant.

Further, the light-sensitive material of the present invention contains a mildew-proofing agent as described in JP-A-63-271247 in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image. Is preferably added. As the support used in the light-sensitive material of the present invention, a support provided on a support on the side having a silver halide emulsion layer with a white polyester support or a layer containing a white pigment for a display is used. May be. Further, in order to improve the sharpness, it is preferable to coat an antihalation layer on the side of the support coated with the silver halide emulsion layer or on the back surface. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.

The light-sensitive material of the present invention may be exposed to visible light or infrared light. The exposure method may be low illuminance exposure or high illuminance short time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, upon exposure, it is preferable to use the band stop filter described in U.S. Pat. No. 4,880,726. As a result, the light color mixture is removed, and the color reproducibility is significantly improved. Silver halide emulsions and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied to the light-sensitive material of the present invention, and processing methods and processing additions applied to process the light-sensitive material. Examples of the agent include the following patent publications, particularly European Patent EP 0,35.
Those described in 5,660A2 (JP-A-2-139544) are preferably used.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

[Table 4]

[0076]

[Table 5]

A method for processing a silver halide color light-sensitive material using a high silver chloride emulsion having a silver chloride content of 90 mol% or more is disclosed in JP-A-2-207250, page 27, upper left column to page 34, upper right. The method described in the section is preferably applied.

[0078]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constitutional layers were further applied to form a layer constitution shown below. A multilayer color photographic paper (Sample 001) was prepared. The coating liquid was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (ExY-1) 110.0 g, color image stabilizer (Cpd-1) 32.0 g, color image stabilizer (Cpd-
2) 8.0 g, color image stabilizer (Cpd-3) 16.0 g
50 g of the solvent (Solv-1) and the solvent (Solv-
2) Dissolve in 50 g and 180 cc of ethyl acetate, and add 60 cc of this solution to 10% sodium dodecylbenzene sulfonate.
100% 10% gelatin aqueous solution containing 10 g of citric acid
Emulsified and dispersed in 0 g to prepare an emulsified dispersion A. on the other hand,
Silver chlorobromide emulsion A (cubic, average grain size 0.88 μm
3: 7 mixture of large size Emulsion A of 0.70 μm and small size Emulsion A of 0.70 μm (silver molar ratio). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and silver bromide of 0.3 mol% was locally contained in a part of the grain surface in each size emulsion). This emulsion contains blue-sensitive sensitizing dyes A and B shown below.
Is 2.0 × 10 ⁻⁴ mol for each large-sized emulsion A per mol of silver, and for each small-sized emulsion A,
2.5 × 10 ⁻⁴ mol of each is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the composition described below. The emulsion coating amount indicates the silver coating amount.

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 gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Cpd-14 and Cp are added to each layer.
the total amount d-15 respectively is 25.0 mg / m ² and 50 mg / m ²
Was added. The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer. [Blue sensitive emulsion layer]

[0081]

[Chemical 31]

(2.0 × 10 ⁻⁴ mol for large size emulsion and 2.5 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) [Green-sensitive emulsion] layer〕

[0083]

[Chemical 32]

(Per mol of silver halide, 4.0 × 10 ^-4 mol for large-sized emulsion, 5.6 × 10 ^-4 mol for small-sized emulsion)

[0085]

[Chemical 33]

(1 mol of silver halide: 7.0 × 10 ^-5 mol for a large-sized emulsion and 1.0 × 10 ^-4 mol for a small-sized emulsion) [Red-sensitive emulsion layer ]

[0087]

[Chemical 34]

(0.9 × 10 ⁻⁴ mol for large size emulsion and 1.1 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) Further, red-sensitive emulsion The following compound F is used in the layer in an amount of 2.6 × per mol of silver halide.
10 ⁻³ mol was added.

[0089]

[Chemical 35]

1- (5-methylureidophenyl) is added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
-5-Mercaptotetrazole was added in an amount of 8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol and 2.5 x 10 ^-4 mol per mol of silver halide, respectively. Further, 4-hydroxy-6-methyl- was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
1,3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. To prevent irradiation, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer.

[0091]

[Chemical 36]

(Layer Structure) The composition of each layer is shown below. Numbers represent coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)]

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.20 Gelatin 1.36 Yellow coupler (ExY-1) 0.55 Color image stabilizer (Cpd-1) 0.16 colors Image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.25 Solvent (Solv-2) 0.25 Second layer (color mixing prevention layer) Gelatin 1.00 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-7) 0.03 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B having a grain size of 0.39 μm (Ag mol) The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface of each size emulsion.) 0.13 Gelatin 1.45 Magenta coupler (ExM) 0.16 Color image stabilizer (Cpd-5) 0.15 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd) -7) 0.01 Color image stabilizer (Cpd-8) 0.08 Solvent (Solv-3) 0.50 Solvent (Solv-4) 0.15 Solvent (Solv-5) 0.15 Fourth layer (color mixture) Preventing layer) Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.04 Solvent (Solv-7) 0.02 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18

Fifth Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C of 0.41 μm (Ag mol The coefficient of variation of the grain size distribution is 0.09 and 0.11, and in each size emulsion 0.8 mol% of AgBr was locally contained in a part of the grain surface.) 0.20 Gelatin 0.85 Cyan Coupler (ExC) 0.33 Ultraviolet absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.30 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) ) 0.01 color image stabilizer (Cpd-11) 0.01 solvent (Solv-6) 0.22 color image stabilizer (Cpd-8) 0.01 color image stabilizer (Cpd-6) 0.01 solvent (Solv-1) 0.01

Sixth Layer (Ultraviolet Absorbing Layer) Gelatin 0.55 Ultraviolet Absorber (UV-1) 0.38 Color Image Stabilizer (Cpd-12) 0.15 Color Image Stabilizer (Cpd-5) 0.02 Seventh layer (protective layer) Gelatin 1.13 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.05 Liquid paraffin 0.02 Color image stabilizer (Cpd-13) 0.01

[0097]

[Chemical 37]

[0098]

[Chemical 38]

[0099]

[Chemical Formula 39]

[0100]

[Chemical 40]

[0101]

[Chemical 41]

[0102]

[Chemical 42]

[0103]

[Chemical 43]

Next, the same samples 002 to 016 were prepared except that the yellow coupler ExY-1 in the first layer was replaced with the comparative yellow coupler or the coupler of the present invention in an equimolar amount with respect to the sample 001. .. The coupler species for each sample are shown in Table A. First, samples 001 to 003
A sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) was used for the exposure to give a gray exposure such that about 30% of the coated silver amount was developed. The exposed sample is continuously processed using a paper processor using a solution having the following processing step and processing solution composition until the replenishment amount is twice as much as the tank solution. A developing solution was prepared.

Treatment process Temperature Time Replenisher ^* Tank capacity Color development 35 ℃ 45 seconds 161ml 17 liters Bleach fixing 30-35 ℃ 45 seconds 215ml 17 liters Linse 30 ℃ 90 seconds 350ml 10 liters Dry 70〜80 ℃ 60 Second * Replenishment amount is as follows for each processing solution composition per 1 m ² of light-sensitive material.

(Color developer) Tank solution Replenisher Water 800 ml 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g-Triethanolamine 8.0 g 12.0 g Sodium chloride 1.4 g-potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine / 1Na 4.0g 5.0g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0g 2.0g Water is added 1000ml 1000ml pH (25 ° C) 10.05 10.45

(Bleach-fixing solution) The tank solution and the replenishing solution are the same water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Water is added. 1000 ml pH (25 ° C) 6.0 (rinse solution) The tank solution and the replenisher solution are the same. Ion-exchanged water (calcium and magnesium are below 3 ppm each)

Next, samples 001 to 016 were subjected to imagewise exposure using an optical wedge for three-color separation, and processed using the above-mentioned processing liquid. For the processed sample, the yellow color density was measured using a blue filter, and a sensitometric curve was created. From this, the maximum yellow color density (Dmax) was determined. However, the maximum color density is shown as the difference density with the density of the fogged portion as a reference (0.00). Another sample that was treated and measured in the same manner as above was used at 80 ° C
After storing at 70% relative humidity for 30 days, the yellow color image density was measured again to evaluate the dark fastness of the color image. This evaluation was performed by comparing the residual ratio of color images at an initial density of 1.5. Another sample was stored under 100,000 lux of xenon light (3 hours light / 1 hour dark irradiation) to evaluate the light fastness. In this evaluation as well, the residual ratio of the color image at the initial density of 1.5 was compared as in the above. The above results are shown in Table A. In Table A, it is shown that the higher the maximum color density is, the more excellent the color developability of the coupler is, and the higher the residual ratio of the color image is, the more excellent the color image fastness is.

[0109]

[Table 6]

[0110]

[Chemical 44]

[0111]

[Chemical 45]

From Table A, it can be seen that the couplers of the present invention are clearly higher in color developability than the comparative couplers ExY-1, 2 and have excellent color image fastness to heat and light.
Also, a comparative coupler ExY-3 having improved color development
It can be seen that the color developability is even higher than that of ~ 5.

Next, with respect to Sample 001, the kind and coating amount (mol%) of the yellow coupler of the first layer were changed as shown in Table B, and the molar ratio of silver halide and coupler was the same. Samples 021 to 031 were prepared in exactly the same manner except that the coating amount of the silver halide emulsion was changed so that These samples were exposed and processed in exactly the same manner as the above-mentioned samples. Next, the yellow color density and the magenta component density of the yellow color part of these samples were respectively adjusted with a blue filter (center wavelength 440 nm),
It measured using the green filter (central wavelength 550 nm). From this, the magenta component density at the exposure amount that gives a yellow color density of 1.5 was obtained and used as an index for hue evaluation. At this time, both the yellow density and the magenta density are shown as the difference density with the density of the fog portion as a reference (0.00). The smaller this value is, the less the magenta color turbidity component at the time of yellow color development is, and the more excellent the hue is. Further, the color image fastness to light and heat was evaluated in the same manner as the above-mentioned sample. The above results are shown in Table B.

[0114]

[Table 7]

From Table B, it can be seen that the couplers of the present invention have a high color-forming property, so that even if the coating amount is reduced, a color-developing density equivalent to that of the comparative coupler can be obtained. Further, the coupler of the present invention is improved in hue, and is further improved in hue as compared with the comparative couplers ExY-2 and ExY-2, 5 in which the magenta component in the yellow color image is small, and the light fastness is improved. ing. As described above, it can be said that the coupler of the present invention is an excellent coupler which is greatly improved in terms of color developability, hue, and color image fastness to light and heat.

Example 2 Sample 101 described in Example 1 of JP-A-4-73748
Sample 201 was prepared by making the following changes. 1. The addition amount of EX-4 in the fifth layer was 0.080 g / m ^{2 and} was 0.050 g / m ² . 2. Addition amount of compound A shown below in the fifth layer is 0.020
Added at g / m ² . 3. Addition amount of compound B shown below in the fifth layer is 0.025
Added at g / m ² . 4. Compound C shown below except for EX-8 in the 11th layer
Was added at 0.085 g / m ² .

[0117]

[Chemical 46]

Next, for sample 201, the coupler EX-9 in the 11th to 13th layers was replaced by the equimolar amounts of the comparative coupler used in Example 1 and the coupler of the present invention as shown in Table C. Samples 202 to 211 were prepared. The obtained samples 201 to 211 were subjected to wedge exposure with white light and developed by the method described in Example 1 of the above-mentioned JP-A-4-73748. The density of each sample after the treatment was measured, and in the obtained characteristic curve, the yellow density from the fog of each sample was determined from the fog of Sample 201 at the exposure amount at which the yellow density was 1.5, and the color of the blue sensitive layer was developed. The sex was evaluated.
In addition, each processed sample is a fluorescent lamp (20,000 lux)
Irradiation was carried out for 7 days with an irradiator, and a forced test of color image storability against light was conducted. In the evaluation, the density after the test was measured at the point where the yellow density from the fog before the test was 1.5, and the residual dye amount was expressed as a percentage and evaluated. The results are shown in Table C.
It was shown to.

[0119]

[Table 8]

From Table C, it can be seen that the yellow coupler of the present invention has high yellow color-forming property and excellent color image fastness.

Example 3 In Example 2, each sample was treated in JP-A-4-737.
The same evaluation results were obtained when the same treatment was carried out except that the stabilizing solution of the method described in Example 1 of No. 48 was changed as follows. (Stabilizer) Common for tank liquid and replenisher (g) Sodium p-toluenesulfinate 0.03 p-Nonylphenyl-polyglycidol (Average degree of polymerization 7) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-Triazole 1.3 1 , 4-4 Bis (1,2,4-triazole-1-iminomethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

[0122]

When the yellow coupler of the present invention is used, the color developability of yellow is high, and the hue and color image fastness are also excellent.

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[Procedure amendment]

[Submission date] May 25, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

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[0006]

[Chemical 2]

[Procedure Amendment 2]

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When X represents a nitrogen-containing heterocyclic group, it is specifically a monocyclic or condensed ring substituted or unsubstituted heterocyclic group. Examples thereof include succinimide, maleimide, phthalimide, diglycolimide, pyrrino,
Pyrazolyl, imidazolyl, 1,2,4-triazol-1-yl (or 4-yl), 1-tetrazolyl, indolyl, benzopyrazolyl, benzimidazolyl, benzotriazolyl, imidazolidine-2,4-dione-
3-yl (or 1-yl), oxazolidine-2,4
-Dione-3-yl, thiazolidine-2,4-dione-
3-yl, imidazolin-2-one-1-yl, oxazolin-2-one-3-yl, thiazolin-2-one-
3-yl, benzoxazolin-2-one-3-yl,
1,2,4-triazolidine-3,5-dione-4-yl, 2-pyridon-1-yl, morpholin-3,5-dione-4-yl, 1,2,3-triazol-1-yl or 2-Imidazolin-5-one may be mentioned. When these heterocyclic groups have a substituent, examples of the substituent include the substituents listed as R ₄ above.

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[Chemical 7]

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(Wherein R ₂ , R ₃ , m and X are represented by the general formula (I
Synonymous with each of I). R ₅ represents a substituent on the indolinyl ring, and a represents an integer of 0-4. ) R ₅
Examples of the substituent of are the substituents enumerated above as R ₄ . Preferred substituents are halogen atoms,
Examples thereof include a cyano group, a sulfonyl group, an acylamino group, a carbamoyl group, an alkyl group, a sulfonamide group and a nitro group. As a, 0, 1 or 2 is preferable, and 0 or 1 is more preferable.

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[Chemical 15]

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 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hajime Nakagawa 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a coupler represented by the following general formula (I) or (II) in at least one hydrophilic colloid layer on a support. [Chemical 1] (In the formula, R ₁ represents an alkyl group or a cycloalkyl group, R ₂ represents an aryl group, R ₃ represents an aryl group or a heterocyclic group, R ₄ represents a substituent, and m represents 0 to 3). Represents an integer, Y represents an organic residue necessary for forming a nitrogen-containing heterocyclic ring together with a nitrogen atom, and X represents a group capable of leaving in the coupling reaction with an oxidized product of an aromatic primary amine color developing agent. Represents.)