CA1313791C - Silver halide photographic light sensitive material - Google Patents

Abstract

ABSTRACT
A silver halide photographic light sensitive material, which contains at least one magenta dye image forming coupler expressed by the following general formula [I], at least one piperazine or homopiperazine compound expressed by the follow-ing general formula [XIIIa], at least one compound selected from a coumarane or a chroman compounds expressed by general formula [XIIIa] and hydoxyindane compounds expressed by [XIIIb], below, is described as being stable to light and moisture, and featuring an excellent color reproducibility.
General formula [I]
General formula [XII]

General formula [XIIIa]

General formula [XIIIb]

Description

13~3791 SPECIFICATION

SILVER HALIDE PHOTOGRAPHIC LIGHT SENSITIVE MATERIAL
FIELD OF THE INVENTION

The present invention relates to a silver halide light sensitive material, which features a dye image stable to light and heat, and, in which generation of a stain is prevented.

BACKGROUND OF THE INVENTION

It is conventionally whell known in the art that an oxi-dan~ derived from a color-forming developing agent and con-taining an aromatic primary amine couples with a color coupler when a silver halide color light sensitive material is treated in an image-wise exposure as well as color development, form-ing dyes, such as an indophenol, indoaniline, indamine, azomethine, phenoxyazine, phenazine and dyes similar to them, thus forming a dye image.
Whet is required for the dye image obtained in such a manner is that it does not show discoloration or color fading even if it is stored under high temperature and/or high humidity. Additionally, what is required for the non-colored portion in a silver halide light sensitive material (herein-after referred to as color photographic material) is that it does not show yellow-stain (hereinafter referred to as Y-stain) due to light, heat or moisture.
However, in the case of a magenta coupler, the Y-stain in the non-colored portion due to light, heat or moisture as well as the color fading of the dye image portion due to light are extremely great, when compared to a yellow coupler or a cyan coupler, often causing troubles.
5-pyrazolones are widely used as couplers to form magenta dyes. It is a great disadvantage that dyes formed from 5-pyrazolo-5-ones have a secondary absorption in the range around 430 nm in addition to a primary absorption around 550 nm. Various researches were conducted in order to solve this disadvantage. A magenta coupler having anilino group in the third position of a 5-pyrazolone has a limited secondary ab-sorption, mentioned above, and is advantageous in obtaining a printed color image. Such a method was disclosed, for example in US Patent No. 2343703 and UK Patent No. 1059994.
However, with the magenta coupler, mentioned above, a shelf stability is limited, and especially, a light resistance of a dye image was significantly poor, resulting in a disad-vantageously great Y-stain in a non-colored portion.
In order to reduce the secondary absorption around 430 nm of the above-mentioned magenta couplers, the magenta colors shown in the following were proposed so as to provide a new mesure:
pyrazobenzimidazoles mentioned in U.K. Patent No. 1047612;
indazolones mentioned in U.S. Patent No. 3770447;
lH-pyrazolo[5,1-c]-1,2,4-triazole couplers disclosed in US
Patent No. 3725067, UK Patents No. 1252418 and No. 1334515;
lH-pyrazolo[1,5,-b]-1,2,4-triazole couplers disclosed in Japanese Patent Publication Open to Public Inspection (herein-after referred to as Japanese Patent O.P.I. Publication) No.
171956/1974 and Research Disclosure No. 24531; lH-pyrazolo[l, 5,-c]-1,2,3-triazole couplers disclosed in Research Disclosure No. 24626; 1-H-imidazo~1,2,b-] pyrazole couplers disclosed in Japanese Patent O.P.I. Publication No. 162548/1984 and Re-search Disclosure No. 24531;
lH-imidazo[1,5,-b]pyrazole couplers disclosed in Japanese Patent O.P.I. Publication No. 43659/1985 and Research Dis-closure No. 24230; lH-pyrazolo[1,5,-d]tetrazole couplers dis-closed in Japanese Patent O.P.I. Publication No. 33552/1985 and Research Disclosure No. 24220.
Among these examples, dyes formed from lH-pyrazolo[5,1,-c]-1, 2,4-triazole couplers, lH-pyrazolo[1,5,-b]-1,2,4-triazole couplers, lH-pyrazolo[1,5,-c]-1,2,3-triazole couplers, lH-imidazo[l,2,-b]pyrazole couplers, lH-pyrazolo[1,5,-b]pyrazole couplers of lH-pyrazolo[1,5,-d]tetrasole couplers have a ~ 4 ~ 1313791 signiiEicantly smaller secondary absorption around 430 nm of wavelength, when compared to the previously mentioned dyes formed from 5-1,2-pyrazolo-ones having an anilino group in the 3-position. This feature is very advantageous in regard to the color reproduction. Additionally, it is an advantage of such dyes that they show the significantly decreased Y-stain in the non-colored portion due to light, heat or moisture.
However, azomethine dyes formed from the couplers, above, are extremely vulnerable to light. And worse, the above-mentioned dyes are easily discolored by light, significantly geopardiz-ing the performance of color photographic materials, especial-ly color photographic materials for print. Consequently, such dyes have not been employed for a practical use.
In order to improve the light-resistance of magenta dye images formed from lH-pyrazolo[5,2,-c]-1,2,4-triazole magenta couplers, a method was proposed in Japanese Patent O.P.I.
Publication No. 125732/1974, where phenol compounds or phenyl ether compounds were added to lH-pyrazolo[5,1,-c]-1,2,4-triazole magenta couplers.
However, it was revealed that such an art is not fully effective in preventing the magenta dye image, mentioned above, from fading, and that the prevention of the discolora-tion due to light was near-impossible.
In view of the disadvantages, above, the present inven-tion has been developed. Therefore it is the first object of ~ 5 ~ ~313791 the in.vention to provide a color photographic mater-al which features an excellent color reproducibility as well as a significantly improved light-resistance of a magenta dye image.
It is the second object of the invention to provide a color photographic material which features a magenta dye image where the discoloration due to light is minimized.
It is the third object of the invention to provide a color photographic material in which the generation of a Y-stain in a non-colored portion due to light, heat or moisture is prevented.
DISCLOSURE OF THE INVENTION
The objects of the present invention are attained with a silver halide photographic light sensitive material comprising at least one magenta dye image-forming coupler expressed by the following general formula [1], at least one compound ex-pressed by the following general formula [XII] and at least one compound selected from those expressed by the following general formulas [XIIIa] and [XIIIb]:
General formula [1]

X
R~" "

N N",~' [In the formula, above, Z represents a plurality of nonmetal atoms necessary to complete a heterocyclic ring containing a nitrogen atom; X represents a hydrogen atom or a substituent capab:Le of being split off upon reaction with an oxidation product of a color developing agent, and, R represents a hy-drogen atom or a substituent.], and;
General formula [XII]

R'--N~ Yl [In the formula, Rl represents an aliphatic group, a cycloalkyl group, an aryl group or a heterocyclic group. Yl represents a group of nonmetal atoms, necessary to complete a piperazine ring or a homopiperazine ring together with a nitrogen atom], and;
General formula [XIIIa]

R2 ~o ~
R30~ Y2 R~ Rs ~In the formula, R2 and Rs independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group; R3 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a ~ 7 ~ 1313791 cycloalkyl group or a heterocyclic group; R4 represents a hy-drogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acylamine group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group; provided that R3 and R4 may be combined with each other to form a 5- or 6-membered ring, and that R3 and R4 may form a methylenedioxy ring;
Y2 represents a group of atoms necessary to complete a chroman ring or a coumarane ring.], and;

General formula [XIIIb~

R'~
[In the formula, Rl2 and R14 independently represent a hydro-gen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group; Rl3 repxesents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamino group, an acyloxy group, a sulfo-namie group, a cycloalkyl group or an alkoxycarbonyl group provided that Rl3 and Rl4 may be combined with each other to form a 5- or a 6-membered hydrocarbon ring; and Y3 represents a group of atoms necessary to complete an inaane ring.].
The present invention is specifically described, below.
In a magenta coupler expressed by the before-mentioned general formula [1], according to the present invention, Z re-presents a group of nonmental atoms necessary complete a heterocyclic ring containing a nitrogen atom, and, the ring formed from the Z may have a substituent.
Additionally, R represents a hydrogen atom or a substi-tuent other than a hydrogen atom.
The substituents expressed by R, mentioned above, other than a hydrogen atom, include a halogen atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkinyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sul-famoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoy-loxy group, amino group, acylamino group, sulfonamide group imide group, ureide group, sulfamoylamino group, alkoxycarbo-nylamino group, aryloxylcarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group and heterocyclicthio group.
As the halogen atom, a chlorine atom or a bromine atom is available, however, a chlorine atom is preferred.
As the alkyl group expressed by R, one having 1 ~ 32 car-bon atoms is preferred. Also, as the alkenyl group or alkinyl group expressed by R, one having 1 ~ 32 carbon atoms is pre-ferred. Additionally, as the cycloalkyl group or cycloalkenyl group, expressed likewise, one having 2 ~ 32 carbon atoms, and, more specifically, 5 ~ 7 carbon atoms is preferred, and, the alkyl group, alkenyl group and alkinyl group may be which-ever straight-chained or branched.
At the same time, the alkyl group, alkenyl group, alkinyl group, cycloalkyl group and cycloalkenyl group, mentioned above, may possess the following substituents:
an aryl group, cyano group, halogen atom, heterocycle, cyclo-alkyl, cycloalkenyl, spiro compound residue, bridged hydrocar-bon compound residue, and; substituents so combined via a car-bonyl group, such as an acyl group, carboxy group, carbamoyl group, alkoxycarbonyl group or aryloxycarbonyl group. Addi-tionally, as the substituents so combined via a hetero atom, the following are available:
ones so combined via an oxygen atom, such as a hydroxy group, alkoxy group, aryloxy group, heterocyclicoxy group, siloxy group, acyloxy group, carbamoyloxy group, and;
ones so combined via a nitrogen atom, such as a nitro group, amino groups including dialkylamino and others, a sulfamoy-lamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, acylamino group, sulfonamide group, imide group or ure~de group, and;

- lo - 1313791 ones so combined via a sulfur atom, such as an alkylthio group, arylthio group, heterocyclicthio group, sulfonyl group, sulfinyl group, sulfamoyl group, and;
ones so combined via a phosphor atom, such as a phosphonyl group and others.
More specifically, there are the examples such as the following: a methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, l-hexylnonyl group, 1,1'-dipentylnonyl group, 2-chlor-t-butyl group, tri-fluoromethyl group, 1-ethoxytridecyl group, l-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group, 3-4'-{~-[4 " (p-hydroxybenzenesulfonyl)phenoxy]dodecaneuro-amino}phenylpropyl group, 3-{4'-~-(2'',4''-di-t-amylphenoxy)butaneamide]phenyl}propyl group, 4-[~-(o-chlorphenoxy)tetradecanaminophenoxy]propyl group, allyl group, cyclopentyl group and cyclohexyl group.
As the aryl group expressed by R, a phenyl group is pre-ferable and may have a substituent, such as an alkyl group, alkoxy group, acylamino group and others.
More specifically, as the aryl group, a phenyl group, 4-t-butylphenol group, 2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyroxyphenyl group, 131379~

4'-[~-(4''-t-butylphenoxy)tetradecanamide]phenyl group and others should be noted.
As the heterocyclic group expressed by R, a 5 ~ 7-mem-bered group is preferable, and, it may have a substituent or it may have been condensed. More specifically, a 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group and others should be noted. As the acyl group expressed by R, the examples including the following are available:
an alkylcarbonyl group such as an acetyl group, phenylacetyl group, dodecanoil group, ~-2,4-di-t-amylphenoxy-butanoil group and others, and; an arylcarbonyl group such as a benzoyl group, 3-pentadecyloxybenzoyl group, p-chlorobenzoyl and others.
As the sulfonyl group expressed by R, the examples in-cluding the following are available:
an alkylsulfonyl group such as a methylsulfonyl group and dodecylsulfonyl group; an arylsulfonyl group such as a ben-zenesulfonyl group and p-toluenesulfonyl group.
As the sulfinyl group expressed by R, the examples in-cluding the following are available:
an alkylsulfinyl group such as an ethylsulfinyl group, octyl-sulfinyl group and 3-phenoxybutylsulfinyl group; an arylsul-finyl group such as a phenylsulfinyl group and m-pentadecyl-phenylsulfinyl group.
As the phosphonyl group expressed by R, the examples in-cluding the following are available:
an al~ylphosphonyl group such as a butyloctylphosphonyl group;
an alkoxyphosphonyl group such as an octyloxyphosphonyl group;
an aryloxyphosphonyl group such as a phenoxyphosphonyl group;
an arylphosphonyl group such as a phenylphosphonyl group.
The carbamoyl group expressed by R may possess a substi-tuent such as an alkyl group, aryl group (preferably, a phenyl group~ and others. As the carbamoyl group, the examples in-cluding the following are available: an N-methylcarbamoyl group, N,N-dibutylcarbaboyl group, N-(2-pentadecyloctylethyl) carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-[3-(2,4-di-t-amylphenoxy)propyl]carbamoyl group.
The sulfamoyl group expressed by R may possess a substi-tuent such as an alkyl group, aryl group (preferably, a phenyl group). As the sulfamoyl group, the examples including the following are available: an N-propylsulfamoyl group, N,N-diethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group and N-phenylsulfamoyl group.
As the examples for the spiro compound residue expressed by R, a spiro [3,3]heptane-1-yl and others are available.
As the bridged hydrocarbon compound residue expressed by R, the examples including the following are available:
a bicyclo[2.2.1lheptane-1-yl, tricyclo[3.3.1.1 3'7]
decane-1-yl, 7,7-dimethyl-bicyclol2.2.1]heptane-1-yl and others.
The alkoxy group expressed by R may further possess one of the substituents exemplified for the alkyl group, mentioned before. For subh an example the following are available:
a methoxy group, propoxy group, 2-ethoxyethoxy group, penta-decyloxy group, 2-dodecyloxyethoxy group, phenethyloxyethoxy group and others.
As the aryloxy group expressed by R, a phenyloxy is pre-ferred. The aryl nucleus may further possess one of the sub-stituents or atoms exemplified for the aryl group, mentioned before. As the examples the following are included: a pheno-xy group, p-t-butylphenoxy group and m-pentadecylphenoxy and others.
As the heterocyclicoxy group expressed by R, one having 5 ~ 7-membered heterocycle is preferred, and additionally, the heterocycle may have a substituent. The examples include a 3,4,5,6-tetrahydropyranyl group 1-phenyltetrazole-5-oxy group.
The siloxy group expressed by R may further posses a sub-stituent such as an alkyl group or another group. The exam-ples include a trimethylcyloxy group, triethylcyloxy group, dimethylcyloxy group and others.
As the acyloxy group expressed by R, the examples such as an alkylcarbonyloxy group and an arylcarbonyloxy group are available. Further, such an acyloxy group may possess a sub-stituent. More specifically, an acetyloxy group, a-chloro-acetyloxy, benzoyloxy and others should be noted as the exam-ples for such an acyloxy group.
The carbamoyloxy group expressed by R may have a substi-tuent such as an alkyl group or aryl group. For such a car-bamoyloxyl group, an N,N-diethylcarbamoyloxy group, N-phenyl-carbamoyloxy group and others are available.
The amino group experssed by R may have a substituent such as an alkyl group or aryl group tpreferably, a phenyl group). For such an amino group, an ethylamino group, anilino group, m-chloranilino group, 3-pentadecyloxycarbonylanilino group, 2-chloro-5-hexadecanamidanilino and other groups are available.
As an acylamino group expressed by R, an alkylacarbonyl-amino group, arylcarbonylamino group (preferably, a phenylcar-bonylamino group) and others are available. Further, such an acylamino group may possess a substituent, and, more specifi-cally, the examples such as an acetamide group, ~-ethylpro-panamide group, N-phenylacetamide group, dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, ~-3-t-butyl-4-hydroxyphenoxybutanamide group and others are available.
As a sulfonamide group expressed by R, an alkylsulfonyl-amino group, arylsulfonylamino group and others are available.
Further, such sulfonamide groups may possess a substituent, and, more specifically, the examples including a methylsul-fonylamino group, pentadecylsulfonylamino group, benzenesul-fonamide group, p-toluenesulfonamide group, p-toluenesulfon-amide group, 2-methoxy-5-t-amylbenzenesulfonamide group and others are available.
An imide group expressed by R may be whichever an open-chained group or a cyclic group, and, may possess a substi-tuent. For such an imide group, the examples including an imide succinate group, 3-heptadecylimide succinate group, phthalimide group, glutarimide group and others are available.
An ureide group expressed by R may have such a substi-tuent as an alkyl group or aryl group (preferably, a phenyl group). The examples of such an ureide group include an N-ethylureide group, N-methyl-N-decylureide group, N-phenyl-ureide group, N-p-tolylureide and other groups.
An sulfamoylamino group expressed by R may have such a substituent as an alkyl group or aryl group (preferably, a phenyl group). The examples of such a sulfamoylamino group include an N,N-dibutylsulfamoylamino group, N-methylsulfamoy-lamino group, N-phenylsulfamoylamino group and others.
An alkoxycarbonylamino group expressed by R may possess a substituent. As the examples of such a group, a methoxycar-bonylamino group, methoxyethoxycarbonylamino group, octadecyl-oxycarbonylamino group and others are available.
An aryloxycarbonylamino group expressed by R may possess a substituent. As the examples of such a group, a phenoxy-carbonylamino group, 4-methylphenoxycarbonylamino group and others are available.
An alkoxycarbonyl group expressed by R may possess a sub-stituent. As the examples of such a group, a methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, ethoxymethoxycarbonyl group, benzyloxycarbonyl group and others are available.
An aryloxycarbonyl group expressed by R may possess a substituent. As the examples of such a group, a phenoxycar-bonyl group, p-chlorophenoxycarbonyl group, m-pentadecyloxy-carbonyl group and others are available.
An alkylthio group expresesd by R may possess a substi-tuent. As the examples of such a group, an ethylthio group, dodecylthio group, octadecylthio group, phenethylthio group and 3-phenoxypropylthio group are available.
As an arylthio group expressed by R, a phenylthio group is preferred. Additionally, the arylthio group may possess a substituent. For such a group, the following examples are available: a phenylthio group, p-methoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenyithio group, p-acetaminophenylthio group and others.
As a heterocyclic thio group, a 5 ~ 7 membered group is preferred. At the same time, such a group may possess a con-densed ring and/or a substituent. For such a group, the fol-lowing examples are available: a 2-pyridylthio group, 2-benzothiazorylthio group and 2,4-diphenoxy-1,3,5-1,3,5-triazole-6-thio group.
As a substituent, expressed by X, which may split off due to a reaction with an oxidant derived from a color developing agent, the similar substituents which are so coupled through one of halogen atoms (a chlorine atom, bromine atom, fluorine atom and others) or a carbon atom, oxygen atom, sulfur atom or nitrogen atom contained thereof are available.
Other than a carboxy group, for the substituents so com-bined through a carbon atom, a group expressed by the follow-ing general formula as well as a hydroxymethyl group and a triphenylmethyl group are available. (R1' has the same mean-ing as R, mentioned previously, Z' has the same meaning as Z, mentioned previously. R2' and R3' respectively represent any one of a hydrogen atom, aryl group, alkyl group and hetero-cyclic group.) R2 '--C--R3 ' Rl ~" "i N--N ,:

The substituents so combined through an oxygen atom thereof include an alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, sulfonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyloxalyloxy group and alkoxyoxalyloxy group.
The alkoxy groups may further possess a substituent, and, the examples for such a substituent include an ethoxy, 2-phenoxyethoxy group, 2-cyanoethoxy group, phenethyloxy group, p-chlorobenzyloxy group and others.
As the aryloxy group, phenoxy groups are preferable, and, the aryl group may further possess a substituent. More speci-fically, the examples for the substituent include a phenoxy group, 3-methylphenoxy group, dodecylphenoxy group, 4-methane-sulfonamidephenoxy group, 4-[~-(3'-pentadecylphenoxy)butan-amide]phenoxy group, hexadecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-naphthy-loxy group, p-methoxyphenoxy group and others.
As the heterocyclic oxy group, a 5 ~ 7-membered hetero-cyclic oxy group is preferred, and, the group may be of a con-densed ring or may have a substituent. More specifically, the heterocyclic oxy groups include a l-phenyltetrazolyloxy group, 2-benzothiazolyloxy group and others.
As the acyloxy groups, the following examples are avail-able: alkylcarbonyloxy groups including an acetoxy group and butanoyloxy group; alkenylcarbonyloxy groups including a cynnamoyloxy group; arylcarbonyloxy groups including a benzoy-loxy group.
As the sulfonyloxy groups, a butanesulfonyloxy group and methanesulfonyloxy groups, for example, are available.
As the alkoxycarbonyloxy groups, an ethoxycarbonyloxy group and benzyloxycarbonyloxy group, for example, are avail-able.
As the aryloxycarbonyl groups, a phenoxycarbonyloxy group and others are available.
As the alkyloxalyloxy groups, a methyloxalyloxy group, for example, is available.
As the alkoxyoxalyloxy groups, an ethoxyoxalyloxy group and others are available.
The substituents so coupled through a sulfur atom thereof include, for example, an alkylthio group, arylthio group, heterocyclic thio group alkyloxythiocarbonylthio group.
The alkylthio groups include a buthylthio group, 2-eyanoethylthio group, phenethylthio group, benzylthio group and others.
The arylthio groups include a phenylthio group, 4-methanesulfonamidophenylthio group, 4-dedecylphenethylthio group, 4-nonafluoropentanamidophenethyl group, 4-carboxyphenyl-thio group, 2-ethoxy-5-t-buthylphenylthio group and others.
The heterocyclic thio groups include, for example, 1-phenyl-1,2,3,4-tetrazolyl-5-thio group, 2-benzothiazolyl group and others~
The alkyloxythiocarbonylthio groups include a dodecyloxy-thiocarbonylthio group and others.

., ' , .
.
, . ' .

- 20 - ~313791 The substituents, mentioned above, which are so coupled through a nitrogen atom include, for example, ones expressed by a general formula - N R4'- In this case, R4' and Rsl re-spectively represent any one of a hydrogen atom, alkyl group, aryl group, heterocyclic group, sulfamoyl group, carbamoyl group, acyl group, sulfonyl grouparyloxycarbonyl group and alkoxycarbonyl group. R4' and R5' may combine with each other to form a heterocycle. However, R4' and R5' are not simul-taneously hydrogen atoms.
The alkyl group may be whichever straight-chained or branched, and, preferably, should have 1 ~ 22 carbon atoms.
Additionally, such an alkyl group may contain a substituent.
As the substituent the following are available:
an aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylamino group, arylamino group, acylamino group, sulfonamide group, imino group, acyl group, alkylsul-fonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxy-carbonylamino group, aryloxycarbonylamino group, hydroxyl group, carboxyl group, cyano group and halogen atom. As the specified examples for the alky group, an ethyl group, octyl group, 2-ethylhexyl group and 2-chlorethyl group are available.
The aryl group expressed by R4' or R5', one having 6 ~ 32 carbon atoms, in particular, a phenyl group or naphthyl group is preferred. The aryl group may have a substituent. For such a substituent, those substituents expressed by R4' or Rsl~ and described, above, as contained in the alkyl group as well as the alkyl group itself are available. More specifi-cally, the aryl groups include, for example, a phenyl group, l-naphthyl group and 4-methylsulfonylphenyl group.
As the heterocycle group expressed by R4' or R5', a 5 ~

6-membered group is preferred, and, the group may be of a con-densed ring or may have a substituent. More specifically, the heterocycle groups include a 2-furyl group, 2-pyrimidyl group, 2-benzothiazolyl group, 2-pyridyl group and others.
As the sulfamoyl group expressed by R4' or R5', an N-alkylsulfamoyl group, N,N-dialkylsulfamoy group, N-arylsul-famoyl group, N,N-diarylsulfamoyl group and others are avail-able. The alkyl group or aryl group contained in the sul-famoyl group may have the substituent contained within the alkyl group or aryl group mentioned before. As the specific examples for the sulfamoyl group, an N,N-diethylsulfamoyl group, N-methylsulfamoyl group, N-dodecylsulfamoyl group and N-p-tolysulfamoyl group, for example, are available.
As the carbamoyl group expressed by R4' or Rs', an N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcar-bamoyl group, N,N-diarylcarbamoyl group and others are avail-able. The alkyl group or aryl group contained in the cabamoyl group may have the substituent contained within the alkyl group or aryl group mentioned previously. As the specific examples for the carbamoyl group, N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-p-cyanophenylcarbamoyl group and N-p-tricarbamoyl group are available.
As the acyl group expressed by R4' or R5', an alkylcarbo-nyl group, arylcarbonyl group and heterocyclic carbonyl group, for example, are available. The alkyl group, aryl group and heterocyclic group may possess a substituent. As the specific examples of the acyl group, a hexafluorobutanoyl group, 2,3,4, 5,6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthoyl group, 2-furylcarbonyl group and others are avail-able.
As the sulfonyl group expressed by R4' or R5', an alkyl-sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group aer available. Such sulfonyl groups may have a substi-tuent, and, more specifically, include an ethanesulfonyl group, benzenesulfonyl group, octanesulfonyl group, naphtha-lenesulfonyl group, p-chlorobenzenesulfonyl group and others.
The aryloxycarbonyl group expressed by R4' or R5' may contain a substituent contained in the previously mentioned aryl group. More specifically, for such an aryloxycarbonyl group, a phenoxycarbonyl group and others are available.
The alkoxycarbonyl group expressed by R4' or Rs' may con-tain a substituent contained in the previously mentioned alkyl group. More specifically, for such an alkoxycarbonyl group, a , methoxycarbonyl group, dodecyloxycarbonyl group, benzyloxycar-bonyl group and others are available.
The heterocycle formed by mutual bonding of R4' and R5', a 5 ~ 6-membered one is preferred, and, may be saturated or unsaturated, and, may be whichever aromatic or unaromatic, and may be of a condensed ring. The examples of the heterocycle, mentioned above, include an N-phthalimide group, N-succinimide group, 4-N-urazolyl group, l-N-hydantoinyl group, 3-N-2,4-dioxooxazolidinyl group, 2-N-l,l-dioxo-3-(2H)-oxo-1,2-benzothiazolyl group, l-pyrrolyl group, l-pyrrolidinyl group, l-pyrazolinyl group, l-pyrazolisinyl group, l-piperidinyl group, l-pyrrolinyl group, l-imidazolyl group, l-imidazolynyl group, l-indolyl group, l-isoindolynyl group, 2-isoindolyl group, 2-isoindolynyl group, l-benzotriazolyl group, 1-benzoimidazolyl group, l-(1,2,4-triazolyl) group, 1-(1,2,3-triazolyl) group, l-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, l,2,3,4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2-lH-pyridone group, phthaladinone group, 2-oxo-1-pyperidinyl group and others. These heterocyclic groups may have any one of the substituents such as an alkyl group, aryl group, alkyloxy group, aryloxy group, acyl group, sulfonyl group, alkylamino group, arylamino group, acylamino group, sulfonamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureide group, alkoxycarbonyl group, arylkoxycarbonyl group, imide group, nitro group, cyano group, carboxyl group, halogen atom and others.
As the heterocycle containing nitrogen atoms and formed from Z or Z', a pyrazole ring, imidazole ring, triazole ring, tetrazole ring and others are available. As the substituent each of the heterocycle may have any one of the substituents described for R, mentioned previously.
Additionally, if the substituent (for example R, Rl ~ R8) in the heterocycle expressed by general formula [I] or one of general formulas ~ ~ [III], which are described later, has the portion, below, the so-called bis-type coupler is formed;

R ' ' ~

N--N~ ";

(R'', X and Z'' are, respectively, the same as R, X and Z in general formula [I].) Naturally, such a type of a coupler is included within the scope of the invention. Additionally, the ring formed from Z, Z', Z'' or Zl, which is mentioned later, may further contain another condensed ring (for example, a 5 7-membered cycloalkene ring). For exmaple, R5 and R6 in gen-eral formul [V], or, R7 and R~ in general formula [VI] may mutually combine to form a ring (for example, a 5 ~ 7-membered cycloalkene or benzene ring).
The groups which are expressed by general formula [I] are more specifically expressed by the general formulas, such as, - 25 - i313791 [II] ~ [III], below.
General formula ~II]
X H

Rl~N~N

General formula [III]
X H

Rl~N~l~R3 N--N N

General formula [IV]

R~ N

N--N NH

General formula [V]

R~ R~

General formula [VI]

R~ R8 N--N--NH

- 26 - 131~791 General formula [VII]
X H

Rl~lh~N`N
N--N--N
In the above-mentioned general formulas [II] ~ [VII], R
~ Ra and X respectively have the same meanings as Rs and X, mentioned previously.
Additionally, among those expressed by general formula [I], the preferable ones are expressed by general formula [VIII], below.
General formula [VIII]

X H

R~ N ~
N--N :

Rl, X and Zl are the same as the R, X and Z in the gen-eral formula lI].
Among the magenta couplers expressed by the above-mentioned general formulas [II] ~ [VII], the similar coupler expressed by general formula [II] is especially preferred.
Additionally, in regard to a substituent contained within a heterocycle in general formulas [I] ~ [VIII], R in general formula [I] is preferred. In general formulas [II] ~ [VIII], Rl is preferred if it satisfies the following criterion 1, and is more preferred if it satisfies the criteria 1 and 2, and, is much more preferred if it simultaneously satisfies the criteria 1, 2 and 3.
Criterion 1: A root atom directly coupled to a hetero-cycle is a carbon atom.
Criterion 2: Only one hydrogen atom, if any, is coupled to the carbon atom, mentioned above.
Criterion 3: The coupling between the carbon atom, men-tioned above, and ad~acent atoms are exclusively of single coupling.
As a substituent R or Rl within the above-mentioned he-terocycle, the similar substituent expressed by the general formula [IX], below, is most highly favored.
General formula [IX]

Rs Rlo - f -Rll In the formula, Rg, Rlo and Rll respectively represent any of the following:
a hydrogen atom, halogen atom, alkyl ~roup, cycloalkyl group, alkenyl group, cycloalkenyl group, alkinyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, residue of spiro compound, residue of bridged hydrocar-bon compound, alcoxy group, aryloxy group, heterocyclic oxy - 28 - ` 1~13~91 group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureide group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycar-bonyl group, alkylthio group, arylthio group, heterocyclic thio group. However, only one of Rg, R1o and Rl1 is, at maxi-mum, a hydrogen atom.
Additionally, two of Rg, R1o and R11, mentioned above, Rg and Rl~, for example may mutually combine to form a ring, whichever saturated or unsaturated (for example, a cycloalkane, cycloalkene and heterocycle), wherein R11 may combine with the ring, above, to form a residue of a bridged-hydrocarbon com-pound.
Any of the groups expressed by Rg ~ R1l may have a sub-stituent. As the examples of groups expressed by Rg ~ Rll as well as the exmaples of a substituent which the above-mentioned groups may contain, the groups, expressed by R in general for-mula [I], mentioned before, and the substituents thereof are available.
Additionally, as the rings formed by bonding of Rg and Rlo, for example, and, as the examples of residues of bridged hydrocarbon compounds formed from two of Rg ~ Rlo~ and, as the substituents which such residues may contain, the examples of a cycloaklyl, cycloalkenyl, and heterocyclic bridged-hydrocar-bon compound residue expressed by R in general formula [I], - 29 - ~313~1 mentioned previously, and, the substituents which the examples may contain, are available.
The following cases are preferable among those expressed by generai formula [IX].
(i) Two of Rg ~ Rll are alkyl groups.
(ii) One of Rg ~ Rll, Rll, for example, is a hydrogen atom, and, other two, that is, Rg and Rlo mutually combine to form a cycloalkyl group in combination with a root hydrogen atom.
More specifically, in (i), the example, where two of R
Rll are alkyl groups, and, the remaining one is a hydrogen atom or an alkyl group, is preferable.
In this case, the alkyl groups and the cycloalkyl group may further possess a substituent. As th~ examples for the alkyl groups, cycloaklyl group and the substituent, the exam-ples for the alkyl groups and cycloalkyl groups expressed by R
in the previously mentioned general formula [I] and for the substituents possessed by the groups are available expressed.
Additionally, as the examples for the substituents whose ring is formed from Z in general formula [I] or Zl in general formula [VIII], and, as R2 ~ R8 in general formulas [II~ ~
[VI], those expressed by the general formula [X], below, are preferable.

General formula [X]
- Rl - SO2 - R2 In the formula, above, Rl represents an alkylene, R2 de-- 30 - 13137~1 notes an alkyl, cycloalkyl or aryl.
The alkylene expressed by Rl should have more than two, and, more preferably, three to six carbon atoms in the straight chain portion. The alkylene may be whiche~er straight-chained or branched, and, further, may possess a sub-stituent.
As the examples for the above-mentioned substituent, the substituents which was so described that the alkyl group re-presented by R in the previously mentioned general formula [I]
may possess, are available.
As the preferable substituent, a phenyl should be noted.
The following are the preferable examples ~or the alky-lene expressed by Rl.

-CH2CII 2CI12 ~~ -CllCli2CII 2 ~ t ~ ICIICH2CH 2 ~
CH3 C211s -Cl12CI12CH- -Cl12CH2CH- ~ -Cl12ClJ2CI12CI12-t C7H~ s C211s -CH2CH2CH2CH-~ -CIICI12CI12-~ CH3 ,~ ~C ~CII 2 Cll 2 ~
C61l~3 ~ Cl13 The alkyl group expressed by R2 may be whichever straight-chained or branched.
More specifically, the examples for such an alkyl group include a methyl, ethyl, propyl, isopropyl, butyl, 2-ethyl-- 31 - 13~3791 hexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 2-hexyldecyl and others are available.
As the cycloalkyl group expressed by R2, 5 ~ 6-membered groups are preferable, and, a cyclohexyl, for example, is available.
The alkyl or cycloalkyl expressed by R2 may have a sub-stituent.
As the examples for such a substituent, those described for the substituents which the previously-mentioned Rl may have are available.
As the aryl expressed by R2, the examples include a phenyl and naphthyl. The aryl group may have a substituent.
As examples of such a substituent, a straight-chained or branched alkyl group as well as those described as substi-tuents the previously mentioned R1 may possess.
If the aryl group have more that two substituents, these substituents may be whichever identical or different.
The compounds expressed by general formula [I] and most highly favored are those expressed by general-formula [XI], below.
General formula [XI]

X H

~N/ N R~-so2-R2 Xn the formula, R and X have the same meaning as R and X
in general formula [I], and, Rl and R2 are identical to Rl and R2 in general formula [X].
The following illustrate the examples of the compounds employed in the present invention.

_ ~ _ _ _ __ _ __ _ _ _ _ L~ ~D _ C~ CD 1~ 1` 2- _ _ CD _ _ ~ _ _ _ __ _ ~ _ _ _ _ ~.
~ _. _. _, _. _, _, _, _. _. _, _ _, _, _ ~ _ _ _ _ ___ _ _ _ _ e~ e~ e~ ~r cY~ e~ c~ t- e~ a~ c~ e~ ct~
X ~ _ CO _ __ C~ ct~ _ ~0 O ~ ~ O~ O ~ ~ ~ ~ In CD 2--~ a~
C~ c~ c~ _ _~ cr~ ~ c.~ _ _ ~ _ c~
_ ~o ~ _ _ a~ o o e~ _ _ __ oo ~D
~ oo o ~ ~n ~ o~ c~ CD ~_ ~ ~ O~ C~
P~ _ _ _ _ . _ _ _ _ _ _ _~ _I e~ ~r ~ c~ c~ ~n ~n ~ ~ u~
~/Z= P~ _. _- _~ ._ _. C~ C~ ~ _ _~ _, ~ _~
X~; 7~ X _ C`~ _ ~ C`~ C~ C`~ ~ _ _ _ _ C~
Z ~ _ _ _ _ _ _ _ _ ~ , O ~ In CD r- oo a~ o _. c~ c~ ~r ~n CD
~ _ _~ _ _l _, _~ C" C`~ _ C`~ _ _ C`-c~ _I I_ ~ c~ co ~ ~r _, ~n e~ e~ c~
r- e~ CD CD ~ _~ C~ _I _l _ Ct~ ~r _ _ _l _ _ ~ ~_ _~ _~ _ _ _ _ _~
P~ _~ _~ _ _~ _~ _l _l ~ _ _ _ _ _~
e~ c~ e~ c~ c~ ~ e~ ~ e~ c~ ~ c~ c~
X oo _ _ _ oo _ _ o _ N _ _ _ _ _ _ _ o _ _ ~ _ _ _ ___ _ _ _ _ - 34 - 1313~91 _ ~ _ _ _ _ __ _ _ _ _ _ __ e~ o _, _, _. o ~ ~ _~ o oo ~ ~
~ _. _, _. _. _, _, _~ _, ~ _, 4 _, ~
_ _ _ _ __ _ _ _ _ _ _ _, _, _, _. ~ _, ~ _~ _, _. ~ _.
e~ _, c~ c~ ~ ~ c~ ~r c~ c~ e~ c~ c~
X C~ oo Co~
~ ~ _ _ _ o _ _ _ _ _ _ _ _ 0~ CD C9 CD e~ r~ ~ 1- -- 1- - - 1- -o _ , _ o _ _ o _ _ ~ _ N C~:l ~ C~ e~ ~ ~r C~ e~ ~1 _ I O C`~ _ I
N P~ _I _ _I _I _ _ _ _~ _ _1 _ _I _ _ ~O Ir~ ~) ~n ~ 1~ tf~ In U~ ~ U-~ ~n u~
/Z= P:~ ~ _'~ ~ _~ ~ ~_ _~ _~ _l _~ _~ _~ _l ~::Z _ _ _ _ _ _ _ _ _ _ . _ ~ ;r C~ C~ ~ C~ C~ e~ C~ C~ C~ C~ C~ C~ ~r X~/I X 0 ~Z; ~ _ _ _ _ _ _ _ _ _ _ __ O e~ ~ ~n ~D r- oo ~n o _. c~ ~ ~ u~
~ IL-~ LC~ U') ~n I~') ~ 1~ CD __ eD tCI U~ _ _ C`~ _ e~ _ _----e~--1---I~--N e~ O O cr~ C~ e~ Ct~ C ~ C~ e~ e~ Ct~ C~
P~ _~ _~ _~ _~ _~ ~_ _~ _l ~ ~ _l _~
_ ~ _ u~ u~ _ _ _ u~ _ ~n _ u7 _ _ _. _ _1 ,_4 _1 _1 _. _1 _~ _ ~ _1 X ~ _ C~ ~ _ _ _ C~l _ _ _ e~ _ ~:: _ _ _ _ _ __ _ _ _ _ O O ~ C`~ CY~ ~ It> tD r- ~ o~ o _~ ~
~ ~r _ _~ _ _ _ _ _ _ _ _~

r ~ . , . .

_ 35 _ 1313791 _ _ _ __ _ _ _~ _ _ _ _ _ N eD ~ C~ e~ )~ eD O~ CO ~ O O C~ ~_ _l _~
_ _ _ __ tD _ _ e~ _ __ _ _ 0 _ _ _ _~ _~ _ _1 _1 _~ _ _ _ ~
_ _ _ _ _ _ _ _ _ _ _ _ ~ ct~ c~ c~ ~r c~ r~ c~ o c~ c~ c~ e~-X ~ O~ C~l C`~ 00 ~ _ _ _ _ _ _ _ _ _ _ _ O n CD 1- ~ a~ o _ c~ c~ ~r ~ CD t-~ O O O O O _ _~ _ _~ _~ _~ ~ _~
~ _l _~ _ ~ _~ _~ _l _ _~ _~ _ _~ _l _ _ _ _l _ U~ _ ~_ _ C~ _ _ __ ~ u~ oo ~r o e~ o~ ~ t~- ).t~ .~) )~ c-~ eD
P _ _~ _ _l _ _ _ _ _ _ _ _ cr~ _ C~ _ C~ _ _ CD _ __ ~ e~ CD
~_ _ ~ 1~ U~ In ~ 1~ ~n ~_ _ _~ _I ._ _ P~ _1 _~ _1 _~ _1 _~ _ _ _ _ ~; ~ X e~ _ e~ ~r e~ _ _ e~ _ _ _ e~ e~
x~/ l c`~ c`~
~ ~ - - -- - - - - - - - - -O ~ et~ ~ U~ C~ 1- ~ 0 --C`~ e~ ~
~ o~ ~ ~ cn a~ ~ cn ~ o o o o o o -- - - - ~- - -~ - -- oo - c~ - ~ - - eo o - - - -N e ~ )1~ ~ ~ ~ ~ ~r -- -- If ~ CY~ t-- ~--_ _ _ __ _ _ _ _ _ _ _ _ ~ u~ ~ u~ a~ _ _ _ ~r ~ ~ c.~ c-~
~ _ _ _ _l _ C~ ~ e~ C~ e~ e~ ~ U~
_ _ _ __ __ _ _ _ _ _ _ _ ~ _ ~ ~ C`~ e~ e~ e~ C~ C`~ C`~ ~
X C~ e~ ~ ~.
~ _ _ _ _ _ _ __ _ _ _ _ O ~ o _l c~ c~ ~r ~ e~ ~ oc~ ~ o _l ~ 1- ~ ~ 00 ~ 00 00 CO C~ 01~ a~ o>
U _ _ __ _ _ _ _ _ _ - 36 - ~313791 _ ~ _ _ . _ _ __ o _ _ ~ U~ ~D ~ U~ _l e~ ~ ~ _ _ ~ _ _ _ _ _ __ _ _ _ ~ _~ _~ ~D eD 1- ~ C~
~ _~ _~ _ _ _~ _~ _ ~ C~ _ _ X co ~ C~ _ ~ ~ C~ C~ ~ _ _ O . ~ c~ et~ ~r u~ CD 1-~ ~r ~ ~ ~ ~ ~r ~r ~r ~ _, . _, ~ _, _~ _, ~ _ .
~n c~ c~ ~ e~ ~r c~ e~ e~
C`~ _. C~ C`~ C~ ~ ~ U~ ~ e~
~ P~ ~ ._ _~ _~ ._ e~ _ _ _ _ CO _ _ CD CL~ eD CD CD cn oo ~n ZC _, _, 4 _, _, C~ _, _. C~
/
:;CZ _ _ _ _ _ _ _ _ _ ~; r X c~ C~ c~ :r CO c~ ~ a~ e~ c~
I
_ _ _ _ _ _ _ _ O o ~ c~ c~ ~ ~ ~ r- ~ o>
Q. Cl~ C~ e~ C~ Cl~ Cl~ Cl~ ~ tn e~
~0' _~ _~ _1 _1 _ _~ _~ _ _~ _ C~ __ _ _ _' _ _ _ CD ~ _ ~D C~ ~
N ~ t-- 1-- C~ Cl~ _ _ _ CY~ ~r _ _ _ _ _ _ _ _ ._ ~D CD CD U~ eD eD CD ~D C~ e~
~ _ _l _ _l _ _ _~ _~ _ _~
_ _ _ _ _ _ __ _ _ X e~ C~ C~ C~ cr~ e~ c~ c~ e~ c~
_ _ _ _ _ _ _ _ _ _ ~0 ~ o _~ c~ ~ ~r ~n CD t-. _l _~ e~ c~- e~ ~ c~ ~ e~ c~ c~
. ~ _ _ _l _ _~ _~ _ _ _~ ~_ _~
'O
~ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~ o _ _ _ ~ _ oo ~ , _l _. U. ~ ~ eD ~
_ _ _ o _ _ _ _ _ _ _ ~ CD ~_ C~ ~ a~ _~ _l _l _l _l eD
_ _ _ _ _ _ o o _ _ _ _ .... o c ~ cY~ cn c~ c~ cn c~
~ C~ e~ e~ C`~ e~ . e~
~:5 _ _ _ _ _ _ _ _ _ _ ~ _. ~ C~ ~ Ln C~ ~ ~ C~ o _, O ~ r--~ ~_ r~ ~ ~ 1--t- ~
~ _~ _, _. _, _, _, ~ ~ _. _l , _ _ _ _ _ _ _ _ _ . _ _ ~ ~ o~ oo _. c~ ~ ~ _, ._ ~r c~
~ _l In ~ _. cs~ ~n ~ _, oo oo a~

C~ _, ~ , C~ ~ ~ ~_ _, ~
_ C~ _~ ~ CD _l ~ ~ ~ _l _~ _~
~1 _ ~ _ _ _ _ _ c~ ~n _ _ ~
~Z X ~ 00 C`~
X~/ ~ ~ _ _ _ _ _ _ _ __ _ _ ~ o _, c~ e~ ~r u~ eD ~ oo ~ o O C~ e~ CD ~D ~D ~D CD ~D CD a~ ~_ ~ _~, _ _ _ _ _ _l _l _ _ ~

e~ c~ ~ _I _t _~ _1 ~ ~r ~ _, c~ ~r CD ~n _~ _~ _l _~ _. e~ ._ ._ .' _ _ _ _ _ _ _ _ _ _ _ _ C~ ~ e~ C~ CD a~ ~ e~ _~ CD a~
_~ ~ _l CD ~ OD e~ a~, _l u~

X e~ c~ c~ e~ c~ e~ oo c~ ~ c~ e~
~ _ _ _ _ _ _ _l __ _ _l ~ cn o _l c~ c~ ~ u-) CD ~ 0~ a) O ~r ~ u~ ~ If ~ U~ ~n ~ ~ ~ ~
~ _ _ _ _ _ _ _ __ _ _ - i _ 38 - 131379 _ _ _ _ . ~ C~ _~
P~ _~ oo _.
_ _ _ _ _ _ _ _ _ _ _ 0~ a~ ._ ~ P~ ~ o~ :~ _~ : ~
_ _ _ _ _ _ _ _ _ _ _ ~, C~ 00 vl ~D _~ r- ~ ~
c~ _, :~ P~ ~ :r: _, ~ _.
_ _ _ _ _ _ _ _ _ _ ~ e~ ~ ~ ~ ct~ e.
; ~ oo ~ o _ _~ _~ C~ e~ e~ e~
~ ~ c~ a~ ~ _ _ ~ _ _ _ _ _ _ ~ C~ ~ e _~ __ _ X oo ~ X
P~ _~ r~ oo ~ _ _ _ _ _ _ _ eD _ In ~ ~ ~ r- a~ o~ o o e~
:r . cn c~ _~ ~ ~ _~ _~ ~_ c~ c~
~-Z ~ _ ~ ~ _ _ _ _ _ _ --~¦ _ 00 a~ ~ ~--, r _ _ _ _ _ _ X~ I X ~`~ ~ ~ X~ P~ ~ ~ ~ ::C . 1-r _ ~ _ O ~ O _ CO ~ ~
O _ _ _ _ _ _ U CD ~ ~
_ _ _ _ ---I --~ `--1--`--~ e~ , , P~ _ _ _ _ .
C~ C" C~ C~ ~ C~
_ _ _ _ OC~
_ CD e~ C~
~ , ~ C~ ~ _ _ _ _ _ _ _ _ _ ~ ~ e~ c1~ ~ U~ ~D
. e~ c~ ~ O cs~ a~ a~ ~ a~ ~
X U~ _ _ . _ : ~ ~ _ ~ C~ e~ ~
~ ~ 0 Q Q Q

, . .

- ~ e~ ~P ~ cr~ O
~ ~- _ _ _~ _ ~ ~
P~ ~ X :r: ~: :r :~ X e~ ~ c~
_l CD CD ~ C~ C~ _ _ _ _ , _, . _, C~l e~ ~ . ~ _ _ ~ _ _ _ _ _ ~ ~ ~ ~
X ~--~ o~ _ ~ ~ ~D a~ o~

o o _~ c~ c~ ~r _ c~ e~ c~ c~ c~ c~ _ ~ a~ c~
O _ _ _ /~=~ X e~ a~
h I ~ _ o~ ~ _ ~ ~ I _ _ _ ~ I ~ ~ C~ O ~O CD a~ \~--Z; ~ _ _ _ x~ ¦ ~--. x~l ~ oo a~ o _~Z ~ ~ ~ ~ ~: ~ _~ ~ O O- ~ CD `.
_ _l _l C~ ~ _~ C~ ~ C~ _ C~

x 1~ - ~ ~ '~ x oo ~ ~- C`~ C`~ _ C`~ ~ U~ ~o ~-~ c~ ~r ~ ~ r- ~ ~ c~ ~ ~
~ ~L~ C~ _ C`~ ~ L_ _ . ~: ' . ., ~313791 The figures in tables correspondingly represent`the fol-lowing groups.

CQ --Br -CH3 -CF3 -C2Hs -CaH7 -(i)CaH7 -(t)C~Hs /C2Hs CIH3 -CsHIl -CH\ -Cl-C3H7 C2Hs CH3 /C~H.
-C7H~s -CH\ -C~sHa C2Hs & ~H~s ClsH~
-Cl7Has -CH\ -C-CsH~
C~H~s CsH

CH3 /OC2Hs ICH3,~

CH3 C~zH2s CHa --CH2~3NHCOCIaH27 Cl2Hs~CsH~I(t) --CH2~ CsH~I(t) 3 1 C~H3(t) --C H 2~ C ~ H . C~Hs(t) CsHll(t) --CH2~NHCOCHO~CsHI~(t) [~

- 42 - 13i3791 --CH2~3NHcocl HO~SO2~0H
C~oH

--C H 2~N H C O C H O~S O 2 4~o H
C I o H 2 1 --(CHz)z~NHCOCHO~
C2Hs --\C
I s H

C s H I I (t) --(CH2)2~NHCOCHO~CsHIl(t) ~C~

C ~ H 9 (t) --(CH2)2~NHCOCHO~C~H~(t) C~Hs ~ 43 ~ 1313791 C~s H I I (t) --(CH2)2~NHCOCHO~3CsHIl(t) C4Hs --(CH2)2~NHCOCI HO~NH SO2N\
C~2H2s H3 --Cl HCH2~NHSO2~0H
O(CH2)20CI~H2s OC~Hs --( C H ~) 2~N H S 0 2 ~
C 8 H ~ 7 (t) --(CH2)2~NHSO2~0CI2H2s .. . .

~ 44 ~ 1313791 --Cl H C H 2 ~N H S 0 2 ~0 C 1 2 H 2 5 --(CH 2) 24~

NH SO2~0CI2H2s --( C H 2) 3 --( C H 2 ) a4 >~ ~ .
NHCOCHO~>
C I o H 2 1 --(CH2)3~ C.~Hs(t) NHCO I HO~OH
C 1 2 ~1 2 5 ~ 45 ~ 1313791 --(CH,),~3 ~OC~H~s NHCOCI HO
C2Hs --(CH2)3~ CsH~(t) NHCOCHO ~CsHlt(t) C2Hs Cl2H2s CQ
NHCOCHO ~3 S O 2 ~ OCH

--(CH2)3~ CQ

51 C H,l(t) --(CHz)a~3 NHCOCH20 ~ CsHll(t) C Hll(t) --(CH2)a~NHCOCHO~CsHIl(t) C2Hs - 46 - :~L313791 5 3 C H~(t) --( C H 2 ) a~ N H C O C H O ~ C s H I I ( t ) ~C~I

C 4 H 9 ( t) (CH2)3~NHCOCHO~C~Hs(t) C~Hs C~s H

--(C H 2) 3~ C ~ H ~ C s H

5 6 CsHIl(t) --(CH2)3~NHCOCI HO~CsHIl(t) C~Hs C~H~
--(CH2)3~N HCOCHO~SO2~0H

.

C 5 H " (t) --(CH2)3~3NHCOCHO~CsHIl(t) --(CH2)3~3NHCocHo~csHll(t) C I oH2~

--(C}-12)3~NHCOCHO~CsH~(t) C s H I I (t) --(CH2)a~NHCOCI HO~
C~o 21 CHa --(CH2)a~NHCOCHO~SO2~0H
C ~oH2~

63 C~

--(CH2)3~NHCOCI Ho~3 --(CH2)3~NHCO I HO~
C,2 25 --(CH2)3 ~ NHCoCHo~ 3 CN
C~2H2s 6 6 C ~ H ~ (t) --(CH2)3~NHCOCHO~OH

C~H,(t) --( C H ) ~ N H C O C~ H 0 ~ 49 ~ 131379~

--(CH2)a~NHCO I HO~NHSO2C~HD
C ~2H2s --(CH2)3~NHCOCI HO~SO2~0H

7 CQ C~

--(CH2)a~NHCOCHO~3S02~0H
C~2H2s C 5 H I I (t) --(CH2)a~ 3 NHCO(CH2)aO ~ CsHll(t) --(H2)a~NHCOCHCH2SO2~0CI2H2s I

C H

13~791 --(CH2)3~NHCOCHCH2SCI2H2s --( C H 2 ) 3--Ç3 NH SO2C~6H33 --(C H2)34~
N~S O 2~ C 1 2 H 2 6 --(CH2)3~NH SO2CI2H2s --(CH2)3~NH SO2C~6H33 7 8 .

--I HCH2CH2~NHSO2~C12H2s --(CH2)3~NHSO2~0CI2H2s --( C H z ) 3~3 N H S 0 2 N

OCsHI7 --( C H 2) 2 N H S 0 2~
CsH~7(t) --(CH2)2NHCOCI HO~ O~H~
C~2H2s // \\
NHS02~
C~H~(t) C s H I I (t) --(CH2)aNHCO(CHz)30~CsHIl(t) OCsH~7 --( C H 2) 3 N H S O z~
C 8 H " ( t) --(CHz)aOCI2H2s CsHIl(t~

--Cl HO~NHCOCI HO~CsHIl(t) C~Hs C2Hs --( C H 2) 2 ~
C 1 sH

C\s H I I (t) --(CH2)30~CsHI~(t) --( C H z ) a 04 C 1 sHa _ 53 - 1313~91 g o CQ CQ
--(CH2)20~NHCOCI HO~S02~0H

--(CH2)~o~3NHCoCHo~ CsHIl(t) C s H I I (t) --( C H 2 ) 3 ~ Cl 2 H s~
C I s H 3 1 --(CH2)30~3NHCocl Ho~NHS02~30H
C I o H 2 1 C~Q C Q
--(CH2)304~NHcocl Ho~3So2~>H
C ~oH

C~sH~(t) --(CH2)30~NHCoCI HO~CsH~
C ~2H2s CQ
--(CH2)aO~3NHCOCI H0 C,2H~--S02~0 H

--(CH2)30~ CQ

CsHll(t) --I(cH2)3o~3NHcocl H0~3CsHIl(t) CH3 C4Hs --(CH2)30~S 02~0 H

C4Hs(t) --(CH2)~0~S02~0H
C4Hs(t) - 55 - ~ 9 Cl H3 --CHCH2SClaH37 -- lC--CH2SCII,H37 CH3 CH~

C5H"(t) --CH2So2(CH2)20~3C5H"(t) 1 04 ~C8HI7 --CH2CH2CH2S02CH2CH~
C.H,3 --CH2CH2lCHS02C12H25 C 7 H~s --CH2CH2CH2SO2CH2CHzS02C12H2s --CH2CH2CH2l HS02CRH,.
C B H,3 --~ HCH2S02CI~H3 1 o 9 --CHCH2CH2S02CH2~NHCOOC~HI7 --CHCH2CH2SO2C2Hs C2Hs C s H I I (t) --CHCH2CH2SO~CH2CH20~CsHIl(t) 1 1 2 C\sHll(t) --Cl HCH2CH2SO2CH2CH2(~ NHCOCH20~C s H I I ( t) OC~Hs --CHCH2CH2SO2CH2CH2S~
CH3 CsHI7(t) 1 1 4 0 C s H 1 7 C2Hs OCgH~

_ 57 - 131379~

1 1 5 C~H
--CHCH2CH2SO2CH2CH~
CH3 CcHI3 --I HCH2CH2SO2C,2H26 C2Hs --C~ HCH2CH2SO2CI~H2 --Cl HCH2CH2SO2C,6H33 C~Hg --ICHCH2CH2SO2C,6H33 --CHCH2CH2SO2C,8H37 - 58 - 1313~91 ].2 2 ~ H3 /CsHI7 --C--CH2CH2S02CH2CH\
C H3 C 6 Hla -- I--CH2CH2S02CI2H2s -- I CH2CH2SO2CIsHa3 --~--CH2CH2S02CI~H37 1 26 ~
--Cl HCH2CH2S02~,>
C2Hs --(CH2)3S02~C~2H2s 1 28 OC~Hs --(CH2)3S02~
CsH~7(t) OCBH,7 --CH2CH2CI HSO2~
C2Hs OC~HI7 --CH2CH2 ICHSO2~0Cl2H2s C O N H C 1 2 H 2 s --(CH2)3SO

N~H C O C 4 H g (t) --CH2CH2(j~H SO
C7Hls --~C H 2) 3 S 02~ \ ~~
CO

--(CH2)~SO2~NH SO2~0CI2H2s . 3 5 --(C H2)4 S O2~
C8HI7(t) 1 ~6 --ICHCH2CH2SO2 ~ 0Cl2H2s C H a --ICHCH2CH2SO2~0C~2H2s C2Hs --RH C H2C H2 S 02~0C ~2H2s 1 3 9 OC~Hs --ICHCH2CH2SO2~
CH9 C~H~7(t) 14 0 OC~2H2s --I HCH2CH2S02~
CHa CH9 - 61 - ~31379 14 1 C~sHIl(t) -- ICHCH2CH2SO2~NHCO(CH2)30~CsHtt(t) C2Hs --I --CH2CH2S 02~0C,2H.5 OC tH~

CH3 C~HI7(t) O C 8 H t 7 CHa ~~
-- I--CH2CH2SO2~
CH3 CsHIl(~) C~ I ~ ~

l 6 l 1 62 C ~2Has ~ ~NHCOCHO~

~NHCOCI HO~C~Hs(t) C ~Hs(t) ~NHCO I HO~OH

C~ C~2H2s ~CH3 C~sHIl(t) C~NHCOCI HO~CsHIl(t) C2Hs .

.

i313791 C~,(t) NHCO(CH2)30~C5H"(t) ~ C,5H3, ,_ NHCO ~CHO~
C ~oH

4~ C,5 H " (t) C z H s C 5 H " (t) ~ CN --COCH~

C~5 H I , (t) --CONH(CH2)~0~C5H"(t) IC 2 H s --N~
--N(CH2CHC~H~)2 FN ,N=
_ N¦ ~ N~=

~Nq )=N
--N --N
\=--NHSO2C~H~7 ~)=N

/N~ C~
--N~ N H~

N H C O C I ~ H 2 7 NHCOC7H~s CQ
.
--NH--~ ~ \~
NH SO2~0C~2H2s --NHCOCF3 --NHCOC3F7 --NHCO(CF2).H

C\sHll(t) -NHCOCHO ~ CsHI~(t) I

C~Hs C\sH~(t) -NHCO(CH2)3-O ~ CsHI~(t) -NHCO(CH2)3 ~ NHCOCHO ~ OH
C~oH21 C~H~(t) -NHCO ~ -N

-N ~ ~ OC~Hs 200 20 l F

S O 2~3 S O 2~F

--NHSO2C6H,3 --NHSO2 --NH SO2~CH3 --NH SO2N~

2 1 3 2 1 ~

--OCH2C.H2SO2CH, --o~3 --O~C,H"(t) --O~
C, 5H3, --O~COOH --O~COOC2Hs --O~C N

C~Hs(t) --O~NHCOCI HO~OH
C IzH2s --O~NOz ~O~OCHa --0~ S 0 2 C H a ~ ~ S 0 2--(~0 H

C~Q C Q
--O~S 02~0H

--OCOC~4H29 --OSO2CH3 C~5 H " (t) --SCH2CH2~NHCOCI HO~C5H,l(t) --SC8H,. --SC,~H37 OC4}19 -s~3) -s~
C~H,7(t) 236 . 237 ~=/
COOH

--S 0 2 C , ~ H 3 7 - 69 - 13137~

These couplers employed in the present invention can be synthesized by referring to the descriptions in, for instance, Journal of the Chemical Society, Perkin I (1977), 2047 ~ 2052, U.S. Patent No. 3725067, Japanese Patent O.P.I. Publications No. 99437/1984, No. 42045/1983, No. 162548/1984, No. 171956/
1984, No. 33552/1985, No. 43659/1985, No. 172982/1985 and No.
190779/1985.
The couplers employed in the present invention may be principally employed at the rate of 1 x 10-3 ~ 1, or, prefer-ably, 1 x 10-2 ~ 18 x 10~1 mol per mol silver halide.
Additionally, the couplers according to the present in-vention may be employed in combination with other types of magenta couplers, as far as such an employment does not jeopardize the objects of the present invention.
In the present invention, a compound, employed in combi-nation with a magenta coupler expressed by the previously men-tioned general formula [I] and having a piperazine or homo-piperazine ring, and, a coumarane ring expressed by the pre-viously mentioned general formula [XIIIa] as well as a hydro-xyindane compound expressed by general formula [XIIIb] are compounds independently known in the art.
For example, Japanese Patent O.P.I. Publication No.
31297/1985 and Japanese Patent Examined Publication No. 85194/
1985 disclosed that the compounds comprising piperazine or homopiperazine, according to the invention, expressed by the previously mentioned general formula [XII] is effective in stabilizing a magenta dye image derived from a magenta coupler employed in the invention.
Also, Japanese Patent Application No.
280486/1984 published November 18, 1986 and Japanese Patent O.P.I. Publication No. 85195/1985 disclosed that coumaran or chroman compounds expressed by the previously mentioned general formula [XIIIa], according to the invention, are effective in stabilizing a magenta dye image derived from a magenta coupler employed in the invention.
Additionally, Japanese Patent Application No.
25793/1985 published May 28, 1986 disclosed that hydroxyindane compounds expressed by the general formula [XIIIb], according to the invention, are effective in stabilizing a magenta dye image derived from a magenta coupler employed in the invention.
However, the previously mentioned specifications totally failed to state the effect, - obtainable from the combined employment of at least one compound selected from the compounds expressed by the general formula [XII] of the invention and the general formula [XIIIa] of the invention, upon the stabilization of a magenta dye image derived from a magenta coupler employed in the invention.
The inventors have found, after the concentrated study, that the light fastness of a magenta dye image derived from a magenta coupler of the invention, may be remarkably improved when a magenta coupler expressed by general formula [I] of the '~:
~.

invent:ion, is simultaneously employed with not only a compound expressed by general formula [XII] of the invention, but at least one compound selected from compounds expressed by gen-eral formulas [XIIIa] and [XIIIb] of the invention.
The compounds expressed by general formulas [XII], [XIIIa] and [XIIIb], mentioned above, are, unless otherwise specified, referred to as magenta dye stabilizers employed in the present invention.
Every magenta dye image stabilizer employed in the inven-tion in combination with a magenta coupler, according to the invention, features preventive effects against fading and dis-coloration of a magenta dye image due to light. One type of such a stabilizer is a compound, comprizing a piperazine or homopiperazine, and expressed by general formula [XII], below.
General formula [XII]

- R '--N Y, [In the formula, above, R1 represents an aliphatic group, cycloalkyl group, aryl group or heterocyclic group. y1 repre-sents a plurality of nonmetal atoms necessary for forming a piperazine or homopiperazine ring, in combination with an nitrogen atom.]
In the above-mentioned general formula [XII], R1 repre-sents an aliphatic group, cycloalkyl group, aryl group or heterocyclic group. As an aliphatic group expressed by Rl, saturated alkyl groups or unsaturated alkyl groups, for exam-ple, are available, and, such groups may have a substituent.
The saturated alkyl groups include a methyl group, ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group and others. The unsaturated alkyl groups include an ethynyl group, propenyl group and others.
As a cycloalkyl group expressed by Rl, 5 ~ 7-membered groups, more specifically, a cyclopenthyl group, cyclohexyl group and others are available, and, such groups include those having a substituent.
As an aryl group expressed by Rl, a phenyl group, naph-thyl group and others are available, and, such groups include those having a substituent.
As a heterocyclic group, a 2-pyridyl group, 4-piperidyl group, 2-furyl group, 2-thienyl group, 2-pyrimidyl group and others are available, and, such groups include those having a substituent.
As a substituent which an aliphatic group, cycloalkyl group, aryl group or heterocyclic group, expressed by Rl, may have, an alkyl grouparyl group, alkoxy group, carbonyl group, carbamoyl group, acylamino group, sulfamoyl group, sulfonamide group, carbonyloxy group, alkylsulfonyl group, arylsufonyl group, hydroxy group, heterocyclic group, alkylthio group, arylthio group and others are available, and, such groups may 1~13791 further possess a substituent.
In the above-mentioned general formula [XII], Yl repre-sents a plurality of nonmetal atoms necessary for forming a piperazine or homopiperazine ring, in combination with a nitrogen atom, and, additionally, such a piperazine or homo-piperazine ring may possess a substituent. The examples for such a substituent include an alkyl group, cycloalkyl group, aryl group, heterocyclic group and others.
As piperazine compounds among the compounds employed in the invention and expressed by the above-mentioned general formula [XII], piperazine compounds expressed by general for-mula [XII'], below, are especially preferable.
General formula [XII']

R " ~ R ' ~

In the formula, above, Rl represents an alkyl group, cycloalkyl group or aryl group. Rl'' represents a hydrogen atom, alkyl group, cycloalkyl group or aryl group.
At the same time, as homopiperazine compounds among the compounds expressed by the above-mentioned general formula [XII], homopiperazine class compounds expressed by general formula [XII''], below, are especially preferable.

General formula [XII'']

R " ~ R ' ~

In the formula, above, Rl' and ~1ll respectively repre-sent the same atom or group as Rl' and Rl'' in the above-mentioned general formula [XII`].
Additionally, the total number of carbon atoms contained in Rl' or Rl'', in general formula [XII'] or [XII''], includ-ing a substituent which Rl' or Rl'' have, should be preferably 6 ~ 40.
The following are the typical examples for a compound expressed by the above-mentioned general formula [XII]. ~ow-ever, the scope of the present invention is not limited only to these examples.

13~3791 C~21125--N N--Cl21125 Cl4112 9--N\ N--Cs41J2 9 C~4112g--N NH

Cl 4112 9--N N--COC113 \

Cl61133--N~--C~61133 p -- 6 \
Cl 4H2 9 ~ N N--CH3 ~CIk--N N--Cl1 \

~ 3 P- ~

A A
Cl 4H2 9--N N--Cll 2 Cll 2--N N--C ~ 4112 9 A A
t--C8lll7--N N--(C112)6--N N--C8l1l7(t) CS~ (t) CH3--N3--CH20 ~CsHll(t) P - lZ

A A
CI4H~9--N N--CH2--N N--Cl41l29 A
Cl 41l2 9--N N--CONHC ~ l19 t--C8lll7--N3--Cl12 _ 77 _ 1~13791 P - 1~

C,41129--N N--COCF3 \

Cl4ll29--N3-CooC2H5 C51~ll(t~
CH3 --N3--COCH0 ~3C5Hll (t) Cl41129--N N--C,.,1129 Cl 4112 9--yN--C 1 4112 9 Cl~3 C~3 C~3 C~13 ~L~c~3 Cl 4112 9--N N--Cl 4112 9 C~3 >~C~3 C~13 C~3 C~511l~(t) C113 - N 3 - Cl12CI12 ~ NHCOCHO ~ CsH~(t) C4~9 Cl13 > ~
Cl2H2s~ N N- CH3 Cl~3 Cl21125--N N--C~21125 y ~ CH3 Cl6H33 - N N- Cl6H33 >~
~ Cll= Cll- Cl12 - N\___/ - Cl21ks - 79 - 131379~

P ~ 26 ~N~lL N3--C, 2H2s [~LN3--Cll 2 P ~ 28 o N N--C~ ffH3:1 ~L N3--Cl .~1121 [~3LN3--C, 2H2s .

Cl61l33--N~--C16H33 P ~ 32 ~ .
Cl4H2s--N~ --Cs4112s Cl21125--N N--C~2112S

C ~ 4112 9--N N--COCH~

~ C~t) C2115 --NJ--COCI~2CO ~=~Csllsl(t) P --3~1 Cl4112 9--N~--COOC2115 Cl 4112 9--N N--CONIICI13 C~41129--N N--SO2N(C11~)2 Cl2H2s--N N--CH2--N N--Cl21125 \ \J

[~LN3--C~2H2 5 N~

~ 3LN3--C, ~H29 p - 45 ~ o~N N--C, 8H~:, ~LN3--CH 2 ~3 i313791 `

~ ~ N N-CH2-The previously mentioned magenta dye image stabilizer, expressed by the before-mentioned general formula [XII] and employed in the invention, can be synthesized by employing a synthesis method disclosed, for example, in Japanese Patent Applications No. 31297/1985 and No. 85194/1985, respectfully published April 23, 1986 and October 28, 1986.
Next, the compounds expressed by the previously mentioned general formula [XIIIa] are further described in detail.
`~ach group expressed by R2 ~ Rs in general formula [XIIIa] may possess another substituent, and, the examples of such a substituent include, for example, an alkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, acylamino group, carbamoyl group, sulfonamide group, sulfamoyl group and others.
A chroman or coumarane ring formed by containing Y2 may possess a substituent such as a halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkenyl group, alkenyloxy group or heterocyclic group, and, further, may form a spiro ring.
Among the compounds expressed by general formula [XIIIa], the compounds most useful for the invention include those ex-~'` 7 : -pressed by general formulas [XIVa], [XVa], [XVIa], [XVIIa] and [XVIIIa].
General formula [XIVa]

~.

General formula [XVa]

R2 R"
R' ~R' Rs R~ R7 General formula [XVIa]
R2 R; ~,R4 R30 ~~ ~O/~\OR3 R4 / Rs~R~ R9 R2 - 84 - ~313791 General formula [XVIIa]
R ' I
R2R l o R'O

General formula [XIIIa]

R"R2 R"

R ' ~R' R2, R3, R4 and R5 in general formulas [XIVa], [XVa], ~XVIa], [XVIIa] and [XVIIIa] respectively have the same mean-ing as those in the previously mentioned general formula [XIIIa]. R6, R7, R8, R9, Rl and Rll respectively represent any one of a hydrogen atom, halogen atom, alkyl group, cycloalkyl groupalkoxy group, hydroxy group, alkenyl group, alkenyloxy group, aryl group, aryloxy group and heterocyclic group.
Additionally, R6 and R7, or R7 and R8, or R8 and R9, or R9 and Rl, or Rl and Rll may mutually cyclize to form a hydrocarbon ring, and, further, an alkyl group may, as a sub-stituent, take a position in the carbocycle.

With the previously mentioned general formulas [XIVa], [XVa], [XVIa], [XVIIa] and [XVIIIa], the compounds which have a hydrogen atom, alkyl group, alkoxy group, hydroxy group or cycloalkyl group in the positions R2 and Rs, and, a hydrogen atom, alkyl groupor cycloalkyl group in the positions R3 and R4, and, a hydrogen atom, alkyl group or cycloalkyl group in the positions R6, R7, R8, R9, Rl and Rll are especially use-ful.
The following are the typical examples for the compounds, above. However, such examples do not limit the compounds em-ployed in the present invention.

C ~

C1~3 110 ~_Cl13 Cl13 Cll- 2 ) Cl~3 HO ~CH3 C~13 Cll-- 3 ) Cl13 Clzll2~CI13 C~13 Cll-- 4 ) Cl13 ~CI13 Cll-- 5 ) C~13 Cl13Q~cll3 Cl13 Cl~- 6 ) 110 ~3 Cll-- 7 ) Cll~
IIO~CI13 (i)C3 Cll- 8 ) Cl13 ~/ \~CH~
CQ

Cll-- 9 ) 110 ~3 Cll-- 10) Cl13 Cl13COO ~CII

C113 \ CH3 - 88 - 13~3791 C ll ~
c,l3 C3 11 70 ~Ccll33 Cl13 Cll- 1~) ~r C113 ~CIi3 Cll- 13) Cl~3 ~ 0\o~/o\
~>< \C11201 Cl13 Cl13 Cll- 14) ~ ~3 \~ Cl13 Cl13 C~13 Cll- 15) Cl13 0 Cl12=CllCI12COO ~011 Cl13 CH3 Cll-- 16) CI13 OC}13 \~\OCH3 Cl13 Cl13 Cl13 S02 Nll Cll-- 17) C~3~CQ
CQ
Cll--18) Cl13 Ç~13 ~CI12-O~CI13 CII~CONII

Cll-- 19) liO ~,~O\~CH3 < ~J~CU3 Cll-- 20) CH2=CHCI120 ~ =CH3 Cll--21) C31170 ~yO~N~

(n)C3H7/ ~ CH3 Cll- 22) 110~

Cll- 23) Cl13 C~13 '10 ~~CII
~b~C''3 C~l- 24) 1~0,~, H3C CH3 o 011 - Cll--25) Cll- 26) ~ ( t ) C4H g C~l- 2~) C1130 ~ ,~

Cl~- 28) Cl13~CI13 Cll--29) IIO~CI120lCIC21~5 C2ll5cOOc1l2 ~3 ~3 o oll Cll- 30) ~CN2 ~ ~OCI12 Cll- 31) Cll- 32) `1~ ~'' 3 Cl13 CONH '~ ~1, OH

Cll--33) ( t)C81ll7 (t)C811~

Cl13 Cll--34) ~C112~113C c/~(cll2~

Cll- 3~) 110~ ~oll Cl13 113 Cll- 36) C3~ c3ll7 Cll- 37) ~C113 C1130~ 0/l~\0C~13 Cl13 Cl13 Cl~--38) ~\~C4119(t) HO ~o\~ ~OH

(t)C4119/~<
CH3 Cl13 - 94 - i31379~

Cll--39) ~ C~ 3C~13 110~1~~ ~011 C113~3 Cll--40) ~,~NRSO2 Cl{3 ~`,I~o /~ OH
Cl13 SO2 Nl CH--41) ~ ~ i ¢~

Cll--42) (t)C41190 ~OC4119(~) - 95- ~313791 Cll- 43) ~CII~ NIICOCI13 Cl2ll25~\l~ ~l~oC~2~l25 Cl13 CONII /~
Cl13 Cl13 Cll--44) C~113 yy~(t)c8~1~7 HO ~ O~ ~o/~OH

(t)C8H~
Cl~3 C~13 Cll- 4~) ~3 ~\o~Oil Cll--46) 113C ~/O O C113 113C /~)<CI13 Cll--47) 113C \~O~ O~C~13 ~13C~ I~C~13 Cll--'~8) ll3 C ~ C~13 C211g ~,~C2115 Cll--49) ~1 Cll--50) 113C ~`~ CH3 113C ~CH3 Cl13 CH3 Cll--51) C3H7 X)~ C3117 Cll- ~2) C~13~ C~13 OH
Cll--~3) CH3 ~0~ ~0~ CM3 C~13~ CI13 OC3~17 ~ 97 ~ 1313791 CIJ - 54) OCli3 Cl~30 ~ C113 Cll~ 55) < )~Cll~

The magenta dye image stabilizers expressed by the pre-viously mentioned general formula lXIIIa] include the com-pounds disclosed in the following literature Q and can be syn-thesized by employing a method disclosed in the literatures:
Tetrahedron, 1970, vol. 26, pp 4743 ~ 4751; Journal of Chemi-cal Society of Japan, 1972, No. 10, pp 1987 ~ lggo; Chemical Letter, 1972 (4~, pp 315 ~ 316; Japanese Patent O.P.I. Publi-cation No. 139383/1980.
The compounds expressed by the previously mentioned gen-eral formula [XIIIb] are further described, below, in detail.
As specific examples for a halogen atom, alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group and alkoxycarbonyl group expressed by either Rl2 or Rl4, the groups described in detail for R in general - 98 - 131379~

formula [I] are available.
As specific examples for a halogen atom, alkyl group, alkenyl group, aryl group, acyl group, acylamino group, acy-loxy group, sulfonamide group, cycloalkyl group and alkoxy-carbonyl group expressed by Rl3, the groups described in de-tail for R in general formula [I] are available.
Each group, mentioned above, may possess another substi-tuent. The examples Eor such a substituent include an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, acylamino group, carbamoyl group, sulfonamide group, sulfamoyl group and others.
Additionally, a 5- or 6-membered hydrocarbon ring formed by mutual closure of Rl3 and Rl" may possess a substituent such as a halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkenyl group, hydroxy group, aryl group, aryloxy group or heterocyclic group.
Y3 represents a plurality of atoms necessary for the forming of an indane ring. Such an indane ring may possess a substituent such as a halogen atom, alkyl group, alkenyl group, alkoxy group, cycloalkyl group, hydroxy group, aryl group, aryloxy group or heterocyclic group, and may further form a spiro ring.
Among the compounds expressed by general formula [XIIIb], the especially useful compounds for the invention include the - 99 - 13i3791 compo~mds expressed by general formulas [XIVb] ~ [XVIb].
General formula [XIVb]

R' 3~R ' General formula [XVb]

R' 2 R20RI g ~ R ~ 3 R' R20RI2 General formula [XVIb]

RIsRlsR'4 HO~R' ~R' 3 l~\OH
R~ 3/~\R' 7 R~ 2 R'~ R'sR'6 Rl2, Rl3 and Rl4 in general formulas [XIVb] ~ [XVIb] have the same meanings as in general formula [XIIIb]~ Rls, Rl6, Rl7, Rl9, Rl9 and R20 respectively represent any one of a hy-drogen atom, halogen atom, alkyl group, alkoxy group, alkenyl group, hydroxy group, aryl group, aryloxy group or heterocyc-lic group. Rl5 and Rl6, or, Rl6 and Rl7 or Rl7 d l9 Rl3 and Rl9, or, Rl9 and R20 may mutually cyclize to form a loo- i313791 carbocycle, and, further, an alkyl group may, as a substituent, take a position in the carbocycle.
~ ith the previously mentioned general formulas [XIVb]
lXVIb], the compounds where a hydrogen atom, alkyl group, alkoxy group, hydroxy group or cycloalkyl group takes the positions Rl2 and Rl4, and a hydrogen atom, alkyl group, hy-droxy group or cycloalkyl group takes the position Rl3, and a hydrogen atom, alkyl group or cycloalkyl group takes the posi-tions Rls Rl6 Rl7 Rl8, Rl9 and R20 are especially useful.
The typical examples for these compounds are shown below.
However, these examples do not limit the scope of the com-pounds employed in the present invention.

HO~

Hû ~CH3 lol- 1313791 CH3 C~ 6H3 3 110~

C113 c~ 6113 3 1~0~
HO
H I -- ~

~lo~
Cl13 I~~$cll3C113 CQ
~CH3 CQ~c~3c~3 Cl~3 Cl~3 \~ll3 C~13 l~o~3 110~

Cl13 Cl13 C31~7 )~$C~13C113 Cl13 Cl13 t--C~ ~ ~ CH3 Cl13 CH3 CI~3 C~13 CIJ3 CH3 Cl13 .

~$C~13 Cl~3 l~o,~3 Cl13 CH3 Cl13SO2NU~13c113 Cl~3 C1~3 Cl13CO)~c113c113 ~CI~3 C~13 Cll3 Cl13 ~ Cl 2 ~ CH3 1~0~
a C~1~3 CIJ3 W~ CH3 C~13 Cl~3 Cl13 ~CIJ3 Cl13 ¦ Cl13 CN3 C~ C~13 Cl13 C~3 Ç113 CIIB ~OH
Cl13 Cl13 Cl~3 Cl13 C~ ~ ~ ~C
C~13 3 Cl13 Cll 110~ ~ C

~` ~` C3l17 CH3 Cl13 ~011 Cl13 C~13 C

Cl13 3 110 ~

Cl13 Cll~

~C113 ~' 110~o.

H I ~ 37 CH3 Cl13 0~1 CH3)~3 Cl18 ~) ~ 01' ~ C~CI~3 ''~

Cl~3 C113 o J~ C3 ~I C2~s ~,2n5 1~0~
~C~13 01 log- 1313791 UO~ ;

Ho~C4Hg(t) t-C4Hg X

HO ~ C8Hl7(t) ~ OH
t-C8Hl7 The method for synthesizing the magenta dye image stabi-lizers employed in the present invention and expressed by the - llo - 1313791 previously mentioned general formulas [XIIIb], [XIVb] ~
[XVIb], is known in the art, and, such stabilizers can be synthesized by referring to the descriptions in such litera-tures as:
Journal of Chemical Society, 1962, pp 415 ~ 417; Japanese Patent Examined Publication No. 32785/1984; Bulletin of Chemical Society of Japan, 1980, 53~ pp 555 - 556.
The magenta dye image stabilizer expressed by general formula [XIIIb] and employed in the invention was disclosed in Japanese Patent Examined Publication No. 32785/1984 and was used as a stabilizer for a magenta dye image derived from a magenta coupler involving a pyrazolone, indazolone or cyano-acetyl. The Publication further states that the stabilizer, mentioned above, is especially useful as a stabilizer for a magenta dye image derived from a magenta coupler involving a 5-pyrazolone. However, the Publication totally fails to sug-gest that the stabilizer, mentioned above, is useful as a stabilizer for a magenta dye image derived from a magenta coupler of the invention, which has a constitution completely different from that of the previously mentioned magenta coup-ler. Furthermore, it is unexpected from the above-mentioned Publication that, if the stabilizer, expressed by the formula [XIIIb], and a magenta dye image stabilizer expressed by the previously mentioned magenta dye image stabilizer expressed by general formula [XII], mentioned above, are combinedly em-ployed, the preservability of a magenta dye image derived from a magenta coupler of the invention, is uniquely and effective-ly improved to the unpredictable degree.
The amount employed of magenta dye image stabilizers ex-pressed by the previously mentioned general formula [XII], [XIIIa] or [XIIIb], is 5 ~ 400 mol %, or, more preferably, 10 ~ 250 mol % per 100 mol % magenta coupler expressed by the previously mentioned general formula [Il and employed in the invention.
When a compound expressed by the previously mentioned general formula [XII], according to the invention, and a com-pound expressed by the previously mentioned general formula [XIIIa] are combinedly employed, or, when a compound expressed by the previously mentioned general formula [XII], according to the invention, and a compound expressed by the previously mentioned general formula [XIIIb] are combinedly employed, the total amount employed of magenta dye image stabilizers is 10 500 mol ~, or, more preferably, 20 ~ 400 mol ~ per 100 mol magenta coupler of the invention.
Additionally, the proportion of amounts employed, in terms of molar ratio between a compound expressed by the pre-viously mentioned general formula [XII], according to the in-vention, and a compound expressed by the previously mentioned general formula [XIIIa~ or general formula [XIIIb], according to the invention, is within the range of 0.1 ~ 10, or, more - 112 - ~313791 preferably, 0.25 ~ 4Ø
When three compounds respectively expressed by the pre-viously mentioned general formula [XII], according to the in-vention, the previously mentioned general formula [XIIIa] and the previously mentioned general formula, the total amount employed of a magenta dye image stabilizer is 15 ~ 500 mol %, or, more preferably, 30 ~ 400 mol % per 100 mol % magenta coupler, according to the invention.
Additionally, when three magenta dye image stabilizers are combinedly employed, the amount employed of each dye image stabilizer is 5 ~ 90 mol %, or, more preferably, 10 ~ 70 mol %
of the total amount employed of all the dye image stabilizers.
According to one of the most favorable embodiment of the present invention, the object of the invention is best attain-ed under the coexistance of at least one metallic complex hav-ing a singlet oxygen of which optical quenching rate is more than 3 x 107M~l sec~1.
Next, the description on a metallic complex, utilized in the invention and having a singlet oxgen of which optical quenching rate constant is more than 3 x 107M~l-sec~1, is given below.
The optical quenching rate constant of the above-mention-ed singlet oxygen is determined with a measuring method for the light-fading of rubrene disclosed in Journal of Physical Chemistry, 83, 591 (1979) and others.

~ ccording to the method, aboev, the chloroform solution eonta:ining rubrene as well as the ehloroform solution contain-ing the mixture of rubrene and a compound to be measured are respectively exposed to lights having an equal energy.
In this method, when assuming that the initial concentra-tion of rubrene is [R], and that the concentration of the com-pound to be measured is [Q], and that the post-test rubrene eoneentration of the solution singly containing rubrene is [R]FO, and that the post-test rubrene concentration of the solution simultaneously eontaining rubrene and the compound to be measured is [~]FQ, the optical quenching rate constant of singlet oxygen (kq) is determined with the following expres-sion.

5.3X 107([R]~--[R]0)+ 1,7X lO~n([R]Q/[R]0) [ Q ~n([ R ]/ [ R ]~) The metallic eompounds employed in the invention are the eompounds having the optieal quenehing rate eonstant of singlet oxygen, determined with the expression, above, more than 3 x 107M~1-see~l, or, more preferably, 1 x 108M~1 see~1.
Furthermore, the prineipal metal within a metallie eomplex is preferably a transitional metal, or, more preferably a metal-lie atom sueh as Fe, Co, Ni, Pd, Pt, and, most favorably, a Ni metallic atom.
As the metallie eomplexes, employed in the invention and having an optical quenching rate constant of singlet oxygen more t:han 3 x 107M-l sec~l, those expressed by the following general formulas [L - I] ~ [L - IV] are preferable.
General formula [L - I]

X' M X2 b~ Y~ c R~ R5 General formula [L - II]

zo x ~I x 2 /~\~c\
R~ R5 General formula [L - III]
R3 ~R6 R ~--C~ \ ~l' ~C--R s ~Y-- ~M< Y
Rs--C ~\ ~C--R~
~C--X3 X'--C~

[In general formulas [L - I], [L - II] and [L - III], M
represents a metallic atom.]
Xl and x2 respectively represent an oxygen atom, sulfur atom or -NR7- (R7 represents a hydrogen atom, alkyl group, aryl group or hydroxy group). X3 represents a hydroxy group or mercapto group. Y represents an oxygen atom or sulfur atom. R3, R4, R5 and R6 respectively represent any one of a hydrogen atom, halogen atom, cyano group, or, an alkyl group, aryl group, cycloalkyl group or heterocyclic group which directly or via a bivalent bonding group cGnnects with a car-bon atom. Additionally, at least one combination, that is, R3 and R4, and, R5 and R6, may form a 5- or 6-membered ring by mutually combining and bonding a carbon atom Z represents a compound which may be coordinated at the position M or a residue derived from such a compound.
General formula [L - IV]

R22 R2~ ~

R ~ N ~ M
R25 ¦ 2 [In the formula, above, R2l, R22, R23 and R24 respective-ly represent any one of a hydrogen atom, halogen atom, hydroxy group, cyano group, or, an alkyl group, aryl group, cycloalkyl group or heterocyclic group which may directly or indirectly via a bivalent bonding group combine to a carbon atom on a benzene ring. Additionally, R21 and R22, or, R22 and R23, or, R23 and R24 may mutually combine to form a 6-membered ring.
R2s represents a hydrogen atom, alkyl group, or aryl - 116 - 13137~1 group. A represents a hydrogen atom, alkyl group, aryl group or hydroxy group. M represents a metallic atom.]
In the above-mentioned general formulas [L - I], [L - II]
and [L - III], X1 and x2 may be whichever identical or differ-ent, in addition, they respectively represents any one of an oxygen atom, sulfur atom or -NR7- (R7 represents any one of a hydrogen atom, alkyl groups including, for example, a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, i-butyl group, benzyl group and others), or, aryl groups (such as a phenyl group, tolyl group, naphthyl group and others) or hydroxy group. Among these examples, an oxygen atom of sulfur atom is favorable, and, more specifical-ly, an oxygen atom is more favorable.
X3 in general formula [L - III] represents a hydoxy group or mercapto group, and, a hydroxy group is more preferred.
Y in general formulas [L - I], lL - II] and [L - III] re-presents an oxygen atom or sulfur atom, and, a sulfur atom is favorable. Additionally, two Ys in general formula lL - III]
may be whichever identical or different.
R3, R4, R5 and R5 in general formulas [L - I], lL - II]
and [L - III] may be whichever identical or different, and, may be respectively one of the following:
a hydrogen atom; a halogen atom such as a fluorine, chlorine, bromine or iodine; a cyano group; an alkyl group (such as a methyl group, ethyl group, propyl group, butyl group, hexyl ~ 117 - 13~3791 group, octyl group, dodecyl group, hexadecyl group and others, and, a.dditionally, these alkyl groups may be whichever straight-chained or branched ones) which directly or via a bivalent bonding group (such as -O-, -S-, -NR7'- [where R7' represents one of such monovalent groups including a hydrogen atom, hydroxy group, or, an alkyl group (such as a methyl group, ethyl group, n-propyl group,~i-propyl group, n-butyl group, t-butyl group, i-butyl group and others), aryl group (such as a phenyl group, tolyl group, naphthyl group and others)], -OCO-, -CO-, -NHCO-, -CONH-, -COO-, -S02NH-, -NHS02-, -SO2- and others) connects with a carbon atom; an aryl group such as a phenyl group, naphthyl group and others; a cycloalkyl group such as a cyclopentyl group, cyclohexyl group and others;
a heterocyclic group such as a pyridyl group, imidazolyl group, furyl group, thienyl group, pyrrolyl group, pyrrodinyl group, quinolyl group morpholinyl group and others. Among these examples, as a group formed from an alkyl group, aryl group, cycloalkyl group in combination with a bivalent bonding group, above, and connecting with a carbon atom via the biva-lent bonding group, above, the following examples are avail-able:
an alkoxy group (a straight-chained or branched alkyloxy group, such as a methoxy group, ethoxy group, n-butyloxy group, octyloxy group and others); an alkoxycarbonyl group ~a straint-chained or branched alkyloxycarbonyl group such as a - 118 - 1 3 137 ~1 methoxycarbonyl group, ethoxycarbonyl group, n-hexadecyloxy-carbonyl group and others); an alkylcarbonyl group (a straight-chained or branched alkylcarbonyl group such as an acetyl group, valeryl group, stearoyl group and others); an arylca-bonyl group such as a benzoyl group and others; an alkylamino group (a straight-chained or branched alkylamino group, such as an N-n-butylamino group, N,N-di-n-butylamino group, N,N-di-n-octylamino group and others); an alkylcarbamoyl group (a straight-chained or branched alkylcarbamoyl group such as an n-butylcarbamoyl group, n-dodecylcarbamoyl group and others);
an alkylsulfamoyl group (a straight-chained or branched alkyl-sulfamoyl group such as an n-butylsulfamoyl group, n-dodecyl-sulfamoyl group and others); an alkylacylamino group (a straight-chained or branched alkylcarbonylamino group such as an acetylamino group, palmitoylamino group and others); an aryloxy group such as a phenoxy group, naphthoxy group and others; an aryloxycarbonyl group such as a phenoxycarbonyl group, naphtoxycarbonyl group and others; an arylamino group such as an N-phenylamino group, N-phenyl-N-methylamino group and others; an arylcarbamoyl group such as a phenylcarbamoyl group and others; an arylsulfamoyl group such as a phenylsul-famoyl group and others; an arylacylamino group such as a benzoylamino group and others.
Additionally, any of R3, R4, R5 and R6 in general formu-las [L - I], [L - II] and [L - III] may form a 5 or 6-membered ring, together with a carbon atom to which at least one of the combinations, R3 and R4, and, R5 and R6, couples by mutual closure of the two compoennts. In this case, the 5 or 6-membered rings formed from mutual bonding, involving a carbon atom, within at least one combination of components expressed by R3 and R4, and, Rs and R6, include a hydrocarbon ring and a heterocycle (for example, a 5 or 6-membered heterocycle con-taining a nitrogen atom), which, having at least one unsatu-rated bond, are exemplified by, for example, a cyclopentene ring, cyclohexene ring, benzene ring (the benzene ring, how-ever, contains a condensed benzene ring, that is, for example, a naphthalin ring, anthracene ring and others). If such a 5 or 6-membered ring has a substituent, the examples for the substituent include the following:
a halogen atom (fluorine, chlorine, bromine and iodine), a cyano group, an alkyl group (for exmaple, a straight-chained or branched alkyl group containing 1 ~ 20 carbon atoms, such as a methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, t-octyl group, n-hexadecyl group and others), an aryl group (for example, a phenyl group, naphthyl group and others), an alkoxy group (for example, a straight-chained or branched alkyloxy group, such as a methoxy group, n-butoxy group, t-butoxy group and others), an aryloxy group such as a phenoxy group and others, an alkoxycarbonyl group (for exam-ple, a straight-chained or branched alkyloxycarbonyl group, - 120 - i31~91 such aLs an n-pentyloxycarbonyl group, t-pentyloxycarbonyl group, n-octyloxycarbonyl group, t-octyloxycarbonyl group and others), an aryloxycarbonyl group (for example, a phenoxycar-bonyl group and others), an acyl group (for example, a straight-chained or branched alkylcarbonyl group such as an acetyl group, stearoyl group and others), an acylamino group (for example, a straight-chained or branched alkylcarbony-lamino group such as`an acetamide group and others, and, an arylcarbonylamino group such as a benzoylamino group and others), an arylamino group (for example, an N-phenylamino group and others), an alkylamino group (for example, a straight-chained or branched alkylamino group such as an N-n-butylamino group, N,N-diethylamino group and others), a car-bamoyl group (for example, a straight-chained or branched alkylcarbamoyl group such as an n-butylcarbamoyl group), a sulfamoyl group (for example, a straight-chained or branched alkylsulfamoyl group such as an N,N-di-n-butylsulfamoyl group, N-n-dodecylsulfamoyl group and others), a sulfonamide group (for example, a straight-chained or branched alkylsulfony-lamino group such as a methylsulfonylamino group and others, and, an arylsulfonylamino group such as a phenylsulfonylamino group and others), a sulfonyl group tfor example, a straight-chained or branched alkylsulfonyl group such as a mecyl group and others, and, an arylsulfonyl group such as a tocyl group and others), a cycloalkyl group (for example, a cyclohexyl 1~1379~

group and others).
General formulas [L - I], [L - II] and [L - III] are pre-ferred when an alkyl group or aryl group expressed by R3, R4, R5 and R6 forms a 5 or 6-membered ring combinedly with a car-bon atom wherein at least one pair among R3 and R4, and, R5 and R6 mutually combine and connect with the atom. Further, the case where the pairs R3 and R4, and, R5 and R6 respective-ly form a 6-membered ring, or, preferably, a benzen ring by mutually bonding and connecting with a carbon atom.
Additionally, in general formulas [L - I], [L - II] and [L -III], M represents a metal atom, which is preferably a transition-metal atom, or, more preferably, a nickel atom, copper atom, cobalt atom, palladium atom or platinum atom, or, most favorably, a nickel atom.
A compound which may coordinate with M represented by Z
in general formula [L - II] is preferably an alkylamine having a straight-chained or branched alkyl group, and, more prefer-ably, dialkylamine or trialkylamine having 2 ~ 36 carbon atoms within an alkyl group. The specific examples of such an alkylamine include the following: monoalkylamines including a butylamine, octylamine (for example, a t-octylamine), dodecy-lamin ~for example, n-dodecylamine), hexadecylamin, octano-lamine and others; dialkylamines including a diethylamine, dibutylamine, dioctylamine, didodecylamine, diethanolamine, dibutanolamine and others; trialkylamines including a triethy-amine, tributylamine, trioctylamine, triethanolamine, tributa-nolamine, trioctanolamine and others.
The more favorable metallic complexes of the invention among those expressed by general formulas [L - I], [L - II]
and [L - III] are the metallic complexes expressed by the fol-lowing general formulas [L - Ia], [L - IIa] and [L - IIIa].
General formula [L - Ia]

X ~--M x2 ~,~
(R")~ (R'2)n General formula [L - IIa]

~o X'--~ X2 ~Y~

(R~ ~ )m (Rl 2)n General formula [L - IIIa]

~X ~ l~X3~

(R~ 2)n (R' 3)n In general formulas [L - Ia], [L - IIa] and [L - IIIa], M, X1, X2, X3, Y and Z have the same meanings as were pre-i313791 viously mentioned.
In general formulas [L - Ia], [L - IIa] and [L - IIIa], Rll, Rl2, Rl3 and Rl4 respectively represent any one of the following: an alkyl group (a straight-chained or branched alkyl group having 1 ~ 20 carbon atoms, such as a methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, t-octyl group, n-hexadecyl group and others); an aryl group, such as a phenyl group, naphthyl group and othres; an alkoxy group (a straight-chained or branched alkyloxy group, such as a methoxy group, n-butoxy group, t-butoxy group and others); an aryloxy group, such as a phenoxy group and others;
an alkoxycarbonyl group la straight-chained or branched alky-loxycarbonyl group, such as an n-pentyloxycarbonyl group, t-pentyloxycarbonyl group, n-octyloxycarbonyl group, t-octyloxy-carbonyl group and others); an aryloxycarbonyl group, such as a phenoxycarbonyl group and others; an acyl group (a straight-chained or branched alkylcarbonyl group, such as an acetyl group, stearoyl group and others); an acylamino group (a straight-chained or branched alkylcarbonylamino group, such as an acetamide group and others, and, an arylcarbonylamino group, such as a benzoylamino group); an arylamino group such as an N-phenylamino group and others; an alkylamino group (a straight-chained or branched alkylamino group, such as an N-n-butylamino group, N,N-diethylamino group and others); a car-bamoyl group (a straight-chained or branched alkylcarbamoyl ~ 124 - 1313791 group, such as an n-butylcarbamoyl group and others); a sul-famoyl group (a straight-chained or branched alkylsulfamoyl group, such as an N,N-di-n-butylsulfamoyl group, N-n-dodecyl-sulfamoyl group and others); a sulfonamide group (a straight-chained or branched alkylsulfonylamino group such as a methyl-sulfonylamino group and others, and, an arylsulfonylamino group, such as a phenylsulfonylamono group and others); a sul-fonyl group (a straight-chained or branched alkylsulfonyl group, such as a mesyl group, and, an arylsulfonyl group, such as a tosyl group); a cycloalkyl group, such as a cyclohexyl group and others). m and n respectively represent any one of the integers, O ~ 4. Among the compounds expressed by general formulas [L - I], [L - IIa] and [L - IIIa], those more favored are the compounds expressed by general formula [L - IIa].
Among the compounds expressed by general formula [L - IIa], the most favorable ones are expressed by general formula [L - IIb].
General formula [L - IIb]

R~ 6 R ~ R ~ 7 X'--~ X2 ~Y~

(R" )m (Rl 2)n In general formula [L - IIb], M, Xl, X2, Y, R1l, Rl2, m - 125 - i313791 and n respectively have the same meaning as mentioned before.
Rl5, Rl6 and R17 respectively represent any one of a hydrogen atom, alkyl group (such as a butyl group, octyl group, stearyl group and others), or an aryl group (such as phenyl group, naphthyl group and others). Additionally, at least two or Rl5, R16 and R17 represent an alkyl group or aryl group.
In general formula [L - IV], mentioned previously as a halogen atom expressed by R21, R22, R23-and R24, a fluorine atom, chlorine atom, bromine atom and iodine atom are avail-able.
An alkyl group expressed by any one of R21, R22, R23 and R24 should be preferably one having 1 ~ 19 carbon atoms, and may be whichever a straight-chained or branched alkyl group, and may possess a substituent.
An aryl group expressed by any one of R21, R22, R23 and R24 should be preferably one having 6 ~ 14 carbon atoms, and may possess a substituent.
A heterocyclic group expressed any one of R2l, R22, R23 and R24 should be preferably a 5 or 6-membered ring, and may possess a substituent.
A cycloalkyl group expressed any one of R21, R22, R23 and R24 should be preferably of a 5 or 6-membered ring, and may possess a substituent.
As a 6-membered ring formed from mutual bonding between R2l and R22, the following are available.

or ¢~3 O .0 As a 6-membered ring formed from mutual bonding between R22 and R23, or, R23 and R24, a benzene ring is preferred, and, such a benzene ring may have a substituent, and may have been condensed.
As an alkyl group expressed any one of R2l, R22, R23 and R24, the examples such as a methyl group, ethyl group, propyl group, butyl group, t-butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and others are available.
As an aryl group expressed by any one of R2l, R2z, R23 and R24, a phenyl group and naphthyl group, for example, are available.
A heterocyclic group, expressed by any one of R2l, R22, R23 and R24, is a 5 or 6-membered similar group having within a ring thereof at least one nitrogen atom, oxygen atom or sul-fur atom serving as a hetero atom. The examples for such a heterocyclic group include a furyl group, hydrofuryl group, thienyl group, pyrrolyl group, pyrrolidyl group, pyridyl group, imidazolyl group, pyrazolyl group, quinolyl group, indolyl group, oxazolyl group, thiazolyl group and others.
As a cycloalkyl group, expressed by any one of R2l, R22, ' ' .

R23 and R24, a cyclopentyl group, cyclohexyl group, cyclo-hexenyl group, cyclohexadienyl group and others are available.
~ s a 6-membered ring formed from mutual bonding between any two of R2l, R22, R23 and R24, a benzene ring, naphthalene ring, isobenzothiophene ring, isobenzofuran ring, isoindone ring and others are available.
An alkyl group, cycloalkyl group, aryl group or hetero-cyclic group, expressed by any one of R2l, R22, R23 and R24, mentioned above, may combine with a carbon atom on a benzene ring via a bivalent bonding group, such as an oxy group (-o-), thio group (-s-), amino group, oxycarbonyl group, carbonyl group, carbamoyl group, sulfamoyl group, carbonylamino group, sulfonylamino group, sulfonyl group, carbonyloxy group and others. Some of such cases may provide a favorable group.
The examples wherein an alkyl group expressed by R2l, R22, R23 or R24 combines with a carbon atom on a benzene ring via vibalent group, mentioned above, include an alkoxy group (for example, a methoxy group, ethoxy group, butoxy group, propoxy group, 2-ethylhexyloxyl group, n-decyloxy group, n-dodecyloxy group, n-hexadecyloxy group and others), an alkoxy-carbonyl group (for example, a methoxycarbonyl group, ethoxy-carbonyl group, butoxycarbonyl group, n-decyloxycarbonyl group, n-hexadecyloxycarbonyl group and others), an acyl group (for example, an acetyl group, valeryl group, stearoyl group, benzoyl group, toluoyl group and others), an acyloxy group (for example, an acetoxy group, hexadecylcarbonyloxy group and others), an alkylamino group (for example, an n-butylamino group, N,N-diethylamino group, N,N-didecylamino group and others), an amylcarbamoyl group (for example, a butylcarbamoyl group, N,N-diethylcarbamoyl group, n-dodecylcarbamoyl group and others), an alkylsulfamoyl group (for example, a butylsul-famoyl group, N,N-diethylsulfamoyl group, n-dodecylsulfamoyl group and others), a sulfonylamino group (fo~ example, a methylsulfonylamino group, butylsulfonylamino group and others), a sulfonyl group (for example, a mesyl group, ethane-sulfonyl group and others), an acylamino group (for exmaple, an acetylamino group, valerylamino group, palmitoyl group, benzoylamino group, toluolylamino group and others).
The examples wherein an cycloalkyl group expressed by R2l, R22, R23 or R24 combines with a carbon atom on a benzene r.ing via bivalent group, mentioned above, include a cyclohexy-loxy group, cyclohexylcarbonyl group, cyclohexyloxycarbonyl group, cyclohexylamino group, cyclohexenylcarbonyl group, cyclohexenyloxy group and others.
~ he examples wherein an aryl group expressed by R2l, R22, R23 or R24 combines with a carbon atom on a benzene ring via bivalent group, mentioned above, include an aryloxy group (for example, a phenoxy group, naphthoxy group and others), an aryloxycarbonyl group (for example, a phenoxycarbonyl group, naphthoxycarbonyl group and others), an acyl group (for exam-ple, a benzoyl group, a naphthoyl group and others), an anilino group (for example, a phenylamino group, N-methylanilino group, N-acetylanilino group and others), an acyloxy group (for example, a benzoyloxy group, toluoyloxy group and others), an arylcarbamoyl group (for example, a phenylcarba-moyl group and others), an arylsulfamoyl group (for example, a phenylsulfamoyl group and others), an arylsulfonylamino group (for example, a phenylsulfonylamino group, p~tolylsulfonyla-mino group and others), an arylsulfonyl group (for example, a benzenesulfonyl group, tosyl group and others), an acylamino group (for example, a benzoylamino group and others).
An alkyl group, aryl group, heterocyclic group and cyclo-alkyl group expressed by any of R21, R22, R23 and R24, men-tioned above, as well as a 6-membered ring formed from mutual bonding between R21 and R22, or, R22 and R23, or, R23 and R24, may have a substituent such as the following:
a halogen atom (for example, a chlorine atom, bromine atom, fluorine atom and othres), a cyano group, an alkyl group (for example, a methyl group, ethyl group, i-propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, heptadecyl group, octadecyl group, methoxyethoxyethyl group and others), an aryl group (for example, a phenyl group, tolyl group, naphthyl group, chlorophenyl group, methoxyphenyl group, acetylphenyl group and others), an alkoxy group (for example, a methoxy group, ethoxy group, butoxy group, propoxy group, methoxyethoxy group and others), an aryloxy group (for example, a phenoxy group, tolyloxy group, naphthoxy group, methoxyphenoxy group and others), an alkoxycarbonyl group (for example, a methoxycarbo-nyl group, butoxycarbonyl group, phenoxymethoxycarbonyl group and others), an aryloxycarbonyl group (for example, a phenoxy-carbonyl group, tolyloxycarbonyl group, methoxyphenoxycarbonyl group and others), an acyl group (for example, a formyl group, acetyl group, valeryl group, stearoyl group, benzoyl group, toloyl group, naphthoyl group, p-methoxybenzoyl group and others), an acyloxy group (for example, an acetoxy group, and acyloxy group and others), an acylamino group (for example, acetamide group, benzamide group, methoxyacetamide group and others), an anilino group (for example, a phenylamino group, N-methylanilino group, N-phenylanilino group, N-acetylanilino group and others), an alkylamino group (for example, an n-butylamino group, N,N-diethylamino group, 4-methoxy-n-butyla-mino group and others), a carbamoyl group (for example, an n-butylcarbamoyl group, N,N-diethylcarbamoyl group, n-butylsul-famoyl group, N,N-diethylsulfamoyl group, n-dodecylsulfamoyl group, N-(4-methoxy-n-butyl) sulfamoyl group and others), a sulfonylamino group (for example, a methylsulfonylamino group, phenylsulfonylamino group, methoxymethylsulfonylamino group and others), a sulfonyl group (for example, a mecyl group, tocyl group, methoxymethanesulfonyl group and others).

- 131 - 1313~9~

Alkyl groups expressed by R25 and A include those having a substituent, and may be whichever straight-chained or branched. Such alkyl groups, preferably, have 1 ~ 20 carbon atoms other than the similar atoms in a substituent, and in-clude a methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetra-decyl group, hexadecyl group, heptadecyl group, octadecyl group and the like. I
Aryl groups expressed by R2s and A include those having a substituent, and, are preferably the similar groups having 6 14 carbon atoms other than the similar atoms in a substituent.
Such aryl groups include a phenyl group, tolyl group, naphthyl group and the like. Further, two ligands may combine with such an aryl group via A.
In the formula, M represents a metallic atom, which is preferably a transitional metallic atom, and, more preferably Cu, Co, Ni, Pd, Fe or Pt. The most favorable one is Ni. As a group expressed by A, a hydroxy group is preferred.
Additionally, among complexes expressed by the above-mentioned general formula [L - IV], those preferably employed have the following features: the place, R2l, is occupied by an oxy group, thio group, an alkyl group which is combined via a carbonyl group, or, a cycloalkyl group, aryl group, hetero-cyclic group, hydroxy group or a fluorine atom, and; at least one group expressed by R22, R23 or R24is a hydrogen atom, - 132 - ~313~91 hydroxy group, alkyl group or alkoxy group. Among such com-plexes, the similar complex havong a hydrogen atom in R2s, and having more than four carbon atoms in total within the groups expressed by R22, R23 and R24.
The example metallic complexes of the invention are given below, however, the scope of the present invention is not limited only to these compounds.

. - 133 - 1313791 Exemplified metallic complexes ( 1 ) O--Ni--O

~C~ ~C~
Il H

(2) : , O--N;--O
1`
( )C H ~C~ ~S~ ~C~C H ( ) I CB~ (n) CBII I 7 (n) ( 3 ) O N i O

C8R, 7(t) CaHI 7(t) ( 4 ) N112C~ 7 ( t) O Ni O

HC~C~S~C~
11 ~I

( S )Nll2CBII I 7 ( t) O N i-- O

C~l, 7(t) C~l~, 7(t) ( 6 ) Nl12C~H 1 7 (n) O N i O

Cl~ r(t) C811l 7(t) ( 7 )NH2C~ 2ll2S(n) O N; O

CRHI 7(t) CBIII 7(t) ( 8 ) Nll2C"~II37(n) O Ni--O

C811~ 7(t) C8111 7(t) i31~79~ `

( ~ ) NH2C~II 17 ( t) S--Ni S

C811 1 7 ( t ) C B1l ~ 7 ( t ) (10) Nll2CB}I, 7(t) O --N i O

(t)Csll~ IOOC COOCsHI I (t) (11) NH2C"II, 7( t) O Ni --O
CQ~ C~

:

( 12) NH2C311, 7(t) O Ni O
~' (t)C4Dg~No S SO N~C4119(t) (t)C4Hg ~ \CillD(t) (13) NH~C411~011)2 O Ni O
~S~

C8H, 7(t) C8H, 7(t) ( 1~) N(C411BOII) O --Ni O

C~ 7(t) C8~1~ 7(t) (1~) N}12C,21125(n) O Ni--O
(t)C~lls~ C4119(t) (n)C~IIgO OC4119 ( 1 G ) (t)C811, 7 ~0 IIO~CBIII 7(t) S ~ Ni ' S
( t)C811~ 7 ~011 ~CBIII 7( ~ ) ( 1 7 ) Nll(C4119)2 O--Ni--O

(18) Nll(C4119)2 O Ni--O

C81~l7(t) C811l7~t) ( 1 9 ) N(C2115)3 O Ni--C8~1l7(t) CB1117(t) (20) Nll(c8lll 7)2 O Ni--0 C811l7( t) C911l7( t) ( 2 1 ) C2~15 Il-- N--c8Hl7(n) O Ni--O

(t)ll,TC~ 5 ~ Cull~7(~) C811 1 7( t ) C811 1 7( t ) (22) Cl2H2s(n) Il-- N--Cl2112s(n) O Ni--O

(n)llllCsOOC COOC5'1ll(~) .

.

(23) (C~2)4--O--C2115 H-- N--( CH2~ 0--C2 lls O Ni--O

Cgll~7( t) Csll~7( t) (24) HsC2--N--C211s S Ni--S
~3/ \~3 C811l7(t) C811l7(t) (2~) Nll(C811l7)2 O Ni--O

(D)IIITC~ ~C~ 17(D~

Cglll7(n) Csll~7(n) 1~1379~

(26) Nll(C4119)2 0--Ni--0 ~$~
( t)HgC4\ ~C4119( t) ( t)llgC4/ \C4119( t) (2~) C4119( t) C4119( t) (t)11~7C~S 1~0~3C811l7(t) ( t ) 111 7C8~S ~ S ~3 C8H ~ 7( t ) C4119( t) C4Hg( t) (28) (t)D~7Cf~o ~ ~0 ~C8~l7(t) ,S_Ni~ N~N )Ni ~S ~
(t)1117C~O/ --/ \0 ~C81~l7(t) :"

i`31379~

(29) Nll(C8Hl7)2 O Fe--O
~t~

Cglll7( t) Cg~1l7( t) (30) Nll(Cl21125)2 O AQ--O
~t~

CgNl7(t) Cslll7(t) (31) , 1l ,011 `

)--N~--N i OCI12CII(C211s ~C~H9 (32) )--N l ~: N i OC112C~1 ( Cclll 3 ~ C811, 7 (~3) ' 1l /0~1 ~
)= N

~0~ _Ni O( i~o)C, ~,~137 (34) 8 I~
, ~ _ _ ,--N i OC, 61~33 _ 143 ~

(35) ~1~ /O~

OCI12CI12CII(CI13)(CI12)3CII(C113)2 (36) ~ OII
~--N
(t)C~H~ ~O~--Ni OCH2CH(C211s )C~lls ~37) C,U, (C~Us )CIICII,O ~~

(38) H ~OH
~--N~

11,~,0 OC,II, (39) , 1l 011 ` I
~--N ~
p~O _Ni ~ 2 112sCI 20 OCI 2~125 (40) --N ~
N i C~ 119 (C2H s )CIICII 20 OCH2CII (C211s )C~Hs (41) OH
)=N
_Ni Cclll ~OCH2CH20OCII2CII20CBII~ 3 (42) ~N

C~lls(C211s)CllCH~OOCI12Cll(C211s)C~H~

(43) ~ 1l 0~1 `

~N --N i SCI12CII~C2}1~)C~III, (44) 1~ 011 [ ~0 llsCzO
O( iso)CI ~lla7 (45) ~ H ~011 ~ ( i 90 ) ~ ~ N i ( iso)C41190 OC~12Cll(C211s C,139 (46) ' 11 011 `
--N~
--N i C4}19(C211s)CllCI120 OCII~

(4-1) ~ 11 0~1 ~
C~H~(C2Hs)CllCI120~N --Ni OCD2ClltC2Hs)C~H3 (48) ~ H OH
>i=N~
~O~--N i CN3 Ocll2cH(c2Hs)c~Hs (49) ~ 11 Oll ~

--Ni O( i~o)CI ~137 (50) ~t)ll~ vC~ ~--N~

OCI12Cll(C211s )C~lls - 147 _ 1313791 (51) C4H~ (C2Hs)CHCHzO ~N --N i C411~(C211s)CllCI120 ~=o C211s (52) ~11 011 H l 3C60 ~N --N i ~l.3c6o C~=O
C~l 3 (53) 1~ 01~ ~

(t)H~ 7Ca ~O----Ni (54) H~N~~
~o - ~N i C~lls tC21is )CIIC1120 0}1 ( ) ~ ,0 Il O ~511, ~ (t) (5~ Ni C4H9(C2H5)CHCllzO OCH2CH(C2115)C4119 Il"C5 Oll ,--Ni OCI~2CII(C2115 )C411, (58), 1l ,OII `

~--N
l ~CU
C4119(C211s)CllCI120 OCH2CII(C2115)C4119 (59) , ~ oll ~ I
~--N
~ Co C~lls(C211s)CllCI120 OCI12Cll(C21~s)C~lls ( 60 ) ~ H ~0~

C~lls(C2Hs)CHCI120 OCN2Cll(C211s)C~Hs (61) --N'OII
~ Pt C411s(C2Hs)CNCI120 OCI12Cll(C211s)C~lls (~2) N OH
~11. (C,ll,)CIICII, ~0 o (63) Il ~11 1 C~lls(C2Hs)CllCH2 \ _~ ~Ni ~IN~(C2Hs)CHCI12 ~ 2 (64) 11~ ,011 , ¦ , .

(t)ll~ 7C8~--_Ni ~N--N
N~

(65) ' H~ ,OH `

(t)1l,7CB~O--~Ni N<C6H, 3 (66) ~ H ~0~

C~)N~ICBI{ I 7 ( i YO) . .

(6~) ~ ll 011 ~
)--N~--N i S02C811 1 7 ( i ~30) (68) ~ ~l 01~
C3~70 ~N --N

C31170 COOc-lll 7( ig ) (~9) ~ 11 ,0~

(~ 7C~ ~0~

(~0) , 0 0 --N ~
(t)ll, 7Cs ~0 _Ni .

- 152 - ~31379~

C5~

N i (72) ~ t"" ,H~

(73) ' C,H " J~

( t)C~Ng ~--(r?4) H ,H

(t)C~II, ~o - 153 - i31379~

C " 112 3 ,o~L

(t)C,H9 ~0~ =Ni ~ ~10)=~ ~ 2 (76) ~ Cl13 ,o~L

~ ~~e C, cH33 (77) ' Cgll,l ,011 `
IJO ~N ~ N i 1lO (t)C~lJ~

(78) N~

l ( t ) C~ 0 ;: 110 (-79) ~ C9ll 1 9 ~~

(t)C~119~0 HO

(t~C 11 ~ ?
UO

(81)Cl13 ,01l `

[

(82)C" 1~2 :1 0 ~O

(83) ~ H ( t~L

l ~ t)C~ ~O~e (84) ~ 11 C,~

l ( t )C"19 ~0--(8~) , C911, ~, 01 )--N~

(t)C~119 ~o~--Cu (8~) Cgll~g ~g~

l~t)C,II,~C

(87) ~ C511~ 1 ~0 ~0 (89) ~ C~H, g l(t)C.8.~0~Pt (90) ~N~
lo~C.~,.~o~i .

- 157 - 131379~

(91) [ Cll. =~

Cl 1112~ ~I

(92) , Cll:~ `

~ ~ N i C, 71~3s ~I

(93) ; (~)C,ll~ ~0 (94) ! CN3 `

i ~N
C511" H 2 - 158 - 131379~

(t)C~ ~0~

C7~1,5 1l (96) ¦' (t)C~ ~0 C ~ 2 a ~1 (97)Cl sHa b~ N
C11a H 2 (98)C~s~131 ~ l (99) c, 511 (100) ~ O ~' C,;115 1l (101) ~ Cll~

l C ~ 1l " C ,~

(lOZ) ~ C,511" ~

~ 1 N;
~ C~ 2 - 160 - 1313~9~

(103) ~ Cl sH3l =~

C, sH3- 1 2 (104) , C~13 ~ .

~ ~-- ,~

(~0 (t)C,U,. ~ 0 C"ll.. o (10~) CHa N
C"1123 H 2 (107) Cl13 ~

(108) (t C~ Ni 109) sH~ I (t) ~
(t)Csll~ I ~0 =~Ni ~ CH3 ~ 2 (110~ ~ C~l~l 7(t) l(t)~ 7 ~~

Cl 7H3s oll 2 (111) ~ Cl13 I

i I , _ Pd C~ ~1123 1 2 (112) C113 ' >~O'~Pt' N
~ C- IH2a 1l ~ 2 (113) ~

Cl IH2a 1~ 2 (114) ( t ) C~ ll, ~ ~ N i C~ 51~3 1 ~

~116) (11~) C~

( 118) OCII2CII(C2H5 )C~II9 CSII I, 1H 2 - 16~ - 131379~

(119) OCI12Cll(C2Hs)C~Hs ~ ~ _ N i C91~ 1 9 1~ 2 ( 120~ Clla ~ 0 ~;

(121) ( t )C~ H g ~0 --N i (122) (123) C, 2~25 C, z112 50 ~ ~:Ni (124) C "Il"

(125) OCI12Cll(C21J6)C~lly ~

,F:N;

C611, 3SC112 OH 2 (126)OCI12CII(C2N5)C~IID

C7H, 5 1N 2 :

- 166 - 1~13791 (IZ7) OCH~C~ lls)C~

C"112 3 1~1 2 (128) NIISO2C~II, 7 ~

Ni CsH~ I 3H

(129) 011 (t)C4119--~ ~Ni C9HI3 0ll J2 (130) ~l ( t)C,U " ~O

C ll OH 2 .

(131) 0~112CI~(C2II5)C~I~9 ~ ~N;
(C211s )CllCH20 ¦ J

(132) Nl ~OC,II . =

(133) ~ (t)C~H~

N
C3H, 9 1H 2 ~134) ~ (t)C8~17 `

~ 30 ~0 ~

c.u~ 1 2 .. ...

- 168 - 131~791 (135) ~ ~

C = N = _ Ni C 1~ / I 2 C C = N

( 137) ' C~ slla I

_ N i Clla C112 (138) ~
~ ~ ~ .
N S ~ N i (138) ~ ~
~S~ ~
N--C N i N S ~ 2 (139) ' C113 `
~-~S~ ~`'' '' , .
N--C Ni N S ~ 2 (140) ~ Qo o/ \\ N i ~ ~ ~ 2 (141) ~ ~

C~llsO \p/S ~?Ni (142) C~2112sO\ ~S ~ `Ni C12~1250/ ~S- ~ .

(143) (I.)C~ S ~
N--C~ ~N i (144) ' ~ l ~N--~ N i (14~) ~ I

CF ~¢S~j ~ "1 Ni ~\S 2 ( 14~) C~2 C112 Cl13-lCI~ N ~C-CI13 O ~ l O
Cll 2--Cll 2 ~ ~ .

~313791 (150) ~5 lle~ _~

(n)C, 2H23 2 The metallic complexes expressed by the general formulas [L - I] ~ [L - III], mentioned pxeviously, can be synthesized with a method described in U.K. Patent No. 858890, West German OLS Patent No. 2042652 and others.
The metallic complexes expressed by general formula [L -IV], mentioned previously, can be synthesized with a method described in E.G. Cox, F.W. Pinkard, W. Wardlaw and K.C.
Webs,ter, Journal of Chemical Society, 1935, 459.
Though varying according to the type of a metallic com-plex employed and the type of a coupler employed, the amount employed of a metallic complex o~ the present invention is within the range of 0.1 ~ 2 mol, or, more preferably, within the range of 0.5 ~ 1 mol per mol magenta coupler which is ex-pressed by the previously mentioned general formula [Il.
: The amounts employed of the compounds expressed by gen-::

eral formulas [XII], [XIIIa] and [XIIIb], mentioned previously, as well as the cases where a metallic complex, according to the invention, (hereinafter referred to as the metallic com-plex oE the invention), having an optical quenching rate con-stant of a singlet oxygen more than 3 x 107 M~l sec~l are des-cribed below.
In the case where the three contents, that is, a metallic complex of the invention, a compound expressèd by the previ-ously mentioned general formula [XII] and a compound expressed by the previously mentioned general formula [XIIIb], are com-binedly employed, each favorable amount employed is, respec-tively, 0.1 ~ 1 mol, 0.5 ~ 2 mol and 1 ~ 2 mol per mol magenta coupler, according to the invention.
When the four contents, that is, a metallic complex of the invention, compounds expressed by the previously mentioned general formulas [XII], [XIIIa] and [XIIIb], are simultaneous-ly employed, each favorable amount employed is, respectively, 0.1 ~ 1 mol, 0.5 ~ 2 mol, 1 ~ 2 mol and 1 ~ 2 mol per mol magenta coupler of the invention.
Additionally, these image stabilizers may be employed in combination with another type of image stabilizer. The stabi-lizers whose combined em~loyment is preferable are those ex-pressed by the following general formulas [A], [J] and [K].

- 174 - 13~3791 General formula [A]

\ /Rc R'$~OR, In the formula, above, Rl represents a hydrogen atom, alkyl group, alkenyl group, aryl group or heterocyclic group.
R2, R3, ~5 and R6 respectively represents any one of a hydro-gen atom, halogen atom, hydroxy group, alkyl group, alkenyl group, aryl group, alcoxy group, or acylamino group. R4 re-presents an alkyl group, hydroxy group, aryl group or alcoxy group.
Additionally, Rl and R2 may mutually close a ring of a counterpart, forming a 5 ~ 6-membered ring. In such a case, R4 represents a hydroxy group or alcoxy group. R3 and R4 may mutually close a ring of a counterpart, forming a 5-membered hydrocarbon ring. In such a case, Rl represents an alkyl group, aryl group or heterocyclic group. However, the latter is not applicable, if Rl is a hydrogen atom, and at the same time, R4 is a hydroxy group.
As a ring which R1 and R2 form, in combination with a benzene ring by mutualiy closing a ring of a counterpart, the examples such as a chroman ring, coumarane ring and methylene-dioxybenzene ring are available.
As a ring which R3 and R4 ~orm, in combination with a benzene ring, by mutually closing a ring of a counterpart, an indane ring, for example, is available. Such rings may have a substituent such as an alkyl group, alcoxy group and aryl group.
Additionally, the atom within a ring, which is formed by mutual closure of Rl and R2, or, R3 and R4, may be allowed to function as a spiro atom, forming a spiro compound, or, a bis compound may be formed by involving~R2 or R4 as a bonding group.
Among phenol compounds or phenylether compounds expressed by the above-mentioned general formula [A], those favorable are biindane compounds having four RO- groups (R represents an alkyl group, alkenyl group, aryl group or heterocyclic group), and, the most favorable compounds can be expressed by the following general formula [A - 1].
General formula [A - l]

Rs \ CH2R~ I

R~ ICH2 H 9 C a In the formula, above, R represents an alkyl group, alkenyl group, aryl group or a group represented by a hetero-cyclic group (for example, tetrahydropyranyl or pyrimidyl).
Either Rg or Rl~ represents a hydrogen atom, halogen atom, alkyl group, alkenyl group or alcoxy group. R11 represents a hydrogen atom, alkyl group or alkenyl group.
The compounds expressed by the general formula [A], des-cribed previously, include those disclosed in U.S. Patents No.
3935016, No. 3982944 and No. 4254216, Japanese Patent O.P.I.
Publications No. 21004/1980 and No. 145530/1979, U.K. Patent Laid-Open Publications No. 2077455 and No. 2062888, U.S.
Patents No. 3764337j No. 3432300, No. 357462i and No. 3573050, Japanese Patent O.P.I. Publications No. 152225/1977, No.
20327/1978, No. 17729/1978 and No. 6321/1980, U.K. Patent No.
1347556, U.K. Patent Laid-Open Publication No. 2066975, Japanese Patent Examined Publications No. 12337/1979 and No.
31625/1973, U.S. Patent No. 3700455 and others.
The amount employed of a compound expressed by the gen-eral formula [A], mentioned previously, is preferably 5 ~ 300 mol~, or, more preferably, 10 ~ 200 mol~ per 100 mol~ magenta coupler.
The typical examples for the compounds expressed by the general formula [A] are as follows.
Type (1) OR' R ~R

R~

Type ( 2 ) R ~R
R~ Ra , Type ( 3) R )~$'R3 R~

Type (4) <(I~(R' Type (S) R'~R2 ~31~791 Type ( 6 ) OR6 OR' RS~R7 _~/

R~ R3 Type (7) R" R' 2 ~, ~.

., . .

m X~
_ _ . .. ; R ~
m ~ m .__.

= m m s ~ C~ _ Z ~
C C

. C~ '` .
S- = ~
U- tD ~ S ~
P~ ~ ~
:C
o$~o P S S` S S Sl - ~ V 3 ~ C~ .
U CC~

Type (4) Compound R ' R 2 No.

A 9 C H, _ -CH,O~ .IIC . ~ .

Type ( 5 ) Compound R' R2 R3 R4 R5 NO.
A-5 CH3CH3 C2HsO (t)CtH~ 7 OH

Type (6) Compounc R' R2 R3 R~R5 R6 R7 No.
A-6 H(t)C~Hs CH3 CH3 (t)C~Hs H CH2 t~-15 CH3(t)C~Hs CH3 CH3 ~t)C~Hs CH3 CH2 _ -.
n ~ ~ n ~ n n n ~ ~ n n ~
~ n n O
n n nr~ ~ n n :~ n n C_~ n n ~ n ~
C~O O oO

o r o ~ ~n n vlm) C.~ r ~
n ~ ~ ~ 3~,> 1~ r o ~ ~
o O o o ~> O~~ ~o o _ n ~> n . = mx = = = = x x:~ x ~ x= =

. n n I` x x x m m m x x m x m x m x e~

~ x X X X X m m x X ~ ~ a x x Q. .
u n n n n n n n n n n n n n n n ~ :~ m :-~ a a:~ m x ~ :W m m ~, m m m n n n n u n n n n O X n n ~:: x :-~ m x~ ~ m C~ ~ = m ~ ~

ON-- O
n o o um ~ oo,, ~C: " n t = n X = nu 20 ~a x ~ 3 x u na:l N ~ __ 1I n~ ~
C.> cX~:C

O ^X -- O O
N~ O ~ u O u~ ~ O = O n a ~n a ~ = ~ x= ~ 1I n ~ ~ D n . C X 2 _ O

_ O
x x m ~-- x 2 m = x x 2 x = = x ~ o~ a~ o ~ ~ O
Z ~
~ e c c c c e c c c c c c c c c - 1~3 - 131~791 (t)C~Hg C~H9tt) HO ~ o ~ OH
(t)C,H9 C~Hs(t) General formula [J]

L
R '-- N~ ,Y

[In the formula, above, Rl represents an aliphatic group, cycloalkyl group or aryl group. Y represents a plurality of nonmetal atoms necessary for forming a 5 ~ 6-membered hetero-cycle, in combination with a nitrogen atom. However, among the nonmetal atoms including a nitrogen atom and forming the heterocycle, if there are more than two hetero atoms, at least two hetero atoms are those who do not neighbor with each other.]
The examples for an aliphatic acid expressed by Rl include a saturated alkyl group which may possess a substituent and an unsaturated alkyl group which may possess a substituent.
In the general formula [J], above, Y represents a plural-ity of nonmetal atoms necessary for forming a 5 ~ 7-membered heterocycle, in combination with a nitrogen atom, and, at least two atoms among the nonmetal atoms including a nitrogen atom must be hetero atoms, and, additionally, these at least two hetero atoms must not neighbor with each other. If all the hetero atoms in a heterocycle within a compound expressed by the general formula [J] are in adjacency with each other, a function expected for a magenta dye image stabilizer is not fulfilled, and, such a case is undesirable.
The above-mentioned 5 ~ 7-membered heterocycle within a compound expressed by general formula [J], mentioned previous-ly, may have a substituent.
At the same time, the 5 ~ 7-membered heterocycle may be whichever saturated or unsaturated, however, saturated hetero-cycle is preferred. Additionally, a benzene ring or another ring may have been condensed into the heterocycle, or, the heterocycle may form a spiro ring.
The amount employed of the compound expressed by the pre-viously mentioned general formula lJ], according to the inven-tion, is preferably 5 ~ 300 mol%, or, more preferably, 10 200 mol% per 100 mol% magenta coupler expressed by the pre-viously mentioned general formula [I], according to the inven-tion.
The typical examples expressed by the general formula [J]
are as follows.

R~ -O

X R, J-l o Cl2H25 J-2 O C,~H29 J-3 0 C6115CH =CH-J-4 O ÇH3CONH ~ .

J-5 O X-naphthyl J-6 0 ~ OCHCONH ~ (CH2)3-C,5H3, C2Hs J-7 O 110 ~ S02 ~ 0CHCONH ~ (C112) 3 -J-8 0 ~ S0zNH ~ CH 2 -J-9 0 t-C5HI~ ~ 0CHCONb-(CH2) 2 -J-lO o3 - CH2 ~ CH2 J-ll S CI~U2~

J-12 ~ C5HIl ~ CH2-J-13 S ~ SO2NH ~ CH2-J-14 S ~

J-15 S ~ -CH2 ~ H2-J - 1~

A~0 C~2H25--N~ ~o, Cl41129--N N

N
Cl4H2 9--N~l ~ V
Cll~ N \~3 C2Hs Cl13--N/~
>GN
C~7H3s /~
Cl2~125--N~_ I

~3 ' ~ 187 - 1313791 ~}~
OC1~3 C811 t 7--N~ CH3 ~5N

Cl2N25--N >=S

C~} N >c o :~ J --2~

~C----C--Cl~2--N C=S

0~ N >C~3 Cl2112~

~313~91 General formula [K]
R2 R~
H ~R5 R'--N Y
H >~R7 In the formula, R1 represents an aliphatic group, cyclo-alkyl group or aryl group. Y represents a mere bonding group or a bivalent hydrocarbon group necessary for forming a 5 ~ 7-membered heterocycle, in combination with a nitrogen atom.
R2, R3, R4, R5, R6 and R respectively represent any one of a hydrogen atom, aliphatic group, cycloalkyl group or aryl group. At the same time, R2 and R4, or, R3 and R6 may couple with each other, forming a mere bonding group, so as to form an unsaturated 5 ~ 7-membered heterocycle, in combination with a nitrogen atom as well as Y. Additionally, if Y is simply a bonding group, Rs and R7 may couple with each other to form an unsaturated 5-membered heterocycle, in combination with a nitrogen atom as well as Y. If Y is not simply a bonding group, R5 and Y, or, R7 and Y, or, Y itself may form an un-saturated bond, further forming an unsaturated 6 or 7-membered heterocycle, in combination with a nitrogen atom as well as Y.
As an aliphatic group represented by Rl, a saturated alkyl group which may possess a substituent and an unsaturated alkyl group which may possess a substituent are available.

- 189 - ~313791 In the general formula [K], above, Y represents a mere bonding group or a bivalent hydrocarbon group necessary for forming a 7 ~ 7-membered heterocycle, in combination with a nitrogen atom. At the same time, if Y is simply a bonding group, Rs and R7 may couple with each other to form a mere bonding group, further forming an unsaturated 5-membered heterocycle, and, if Y is a bivalent hydrocarbon group, that is, a methylene group, R5 and Y, or, R7 and ~ may form an un-saturated bond, so as to form an unsaturated 6-membered heterocycle. Additionally, if Y is an ethylene group, Rs and Y, or, R7 and Y, or, Y itself may form an unsaturated bond, so as to form an unsaturated 7-membered heterocycle. Further, A
bivalent hydrocarbon group expressed by R may possess a sub-stituent.
In general formula [K], mentioned previously, R2, R3, R4, Rs, Rs and R7 respectively represent any one of a hydrogen atom, aliphatic group, cycloalkyl group or aryl group. As an aliphatic group, expressed by any of R2 ~ R7, a saturated alkyl group which may possess a substituent and an unsaturated alkyl group which may possess a substituent are available.
As a compound expressed by the general formula [K], men-tioned previously, one having a saturated 5 ~ 7-membered ring is preferable to one having an unsaturated ring.
The amounts employed of the following compounds expressed by the general formula [K} are within the range of 5 ~ 300 ~313791 mol~, or, more preferably, 10 ~ 200 mol% per 100 mol~ magenta coupler, expressed by the previously mentioned general formula [I] and employed in the invention.
The typical compounds expressed by the previously men-tioned general formula [K] are later exemplified.
As the methods where a magenta coupler and a metallic complex, according to the invention, as well as image stabi-lizers, expressed by general formulas [XII], r [IIIa] and [XIIIb], are dded into a silver halide photographic light sensitive material, various methods are applicable, in addi-tion to a method where an ordinary hydrophobic compound is em-ployed. These methods include solid dispersion method, latex dispersion method, oil-in-water type emulsification distribu-tion method and others. A suitable method may be selected from the examples, above, in compliance with a chemical con-stitution, for example, of a hydrophobic compound such as a coupler. For the oil-in-water type emulsification distribu-tion method, various methods for distributing a hydrophobic compound such as a coupler may be applied, and, principally, a low-boiling point and/or soluble organic solvent is combiedly used, in compliance with a requirement, with a high-boiling point organic solvent having a boiling point higher than 150C, wherein the compound is solved, which is emulsified and dis-tributed within a hydrophilic binder such as a gelatin solu-tion, by means of a agitator, homogenizer, colloid mill, flow jet mixer, ultrasonic wave apparatus and the like, then, the emulsion is added into a hydrophilic colloid layer which needs the emulsion. Additionally, a fluid dispersion or a process, where a low-boiling point organic solvent is removed at the same time with dispersion the emulsion, may be also incorpo-rated.
As a high-boiling point organic solvent, those which do not react with an oxidant derived from a developing agent and have a boiling point higher than 150C, such as a phenol derivative, phthalic ester, phosphoric ester, citric ester, benzoic ester, alkylamide, aliphatic ester, trimesic ester and others are employed.
In the present invention, the high-boiling point organic solvents preferably employed when distributing a metallic com~
plex of the invention as well as the above-mentioned image stabilizer and others are compounds with a dielectric constant less than 6.0 and include, for example, esters such as a phthalic ester, phosphoric esters and others, organic amides, ketones, hydrocarbonic compounds and others, all of which have a dielectric constant less than 6Ø Preferably, such sol-vents are the high-boling point organic solvents having a di-electric constant within the range less than 6.0 and more than 1.9 and having a vapor pressure less than 0.5 mmHg at 100C.
More preferably, such compounds are a phthalic ester or phos-phoric ester contained in the high-boiling point organic sol-vent. Additionally, the high-boiling point organic solvent may b~ a mixture of moer than two solvents.
The dielectric constant in respect to the present inven-tion refers to the dielectric constant at 30C.
As the phthalic ester advantageously employed in the in-vention, the similar esters expressed by the following general formula [a] should be noted.
General formula [a]

COOR, ~ COOR2 In the formula, above, either R1 or R2 represents an alkyl group, alkenyl group or aryl group. However, the total of carbon atoms within groups expressed by both Rl and R2 is 8 ~ 32, and, more preferably, 16 ~ 24.
The alkyl groups employed in the invention and expressed either by R1 or R2 in general formula [a], above, may be which-ever straight-chained or branched type.
As the phosphoric esters advantageously employed in the invention, those expressed by the following general formula [b] are available.
General formula [b]

Il R s O -- P -- O R 3 O R ~

In the formula above, R3, R4 and R5 respectively repre-sent any one of an alkyl group, alkenyl group or aryl group.
However, the total of carbon atoms contained in those express-ed by R3, R4 and R5 is 24 ~ 54. The following are the typical examples for the organic solvents employed in the invention, however, the scope of the invention is not limited only to these examples.
Exemplified organic solvents S - 1 ~ COOC6H, 3 COOC6H,3 S ~ 2 C2Hs COOCI12CH(CIJ2)3CH3 COOCI12CIH(Cl12)3C113 C2Hs S ~ 3 ~COOC8~11 7 ~COOC 8 H, 7 ~COOCgllI 9(; ) ~ COOCsHIs(i) ~COOC9~
COOCsHI 3 COOCH2CH2CHCH2C(CH3)3 COOCH2CH2CHCH2C(CH3)3 ` Cl13 COOC~H2~(i) ~ COQCIoH21(i) S ~ 8 COOCloH
~ COOCIoH

S - g COOC" H2 3 ( i ) ~ COOCI~H23(i) ~COOCI 2H2s ~ COOCI2~2s COOC~2H2s(i) COOCI2H2s(i~

I'hese organic solvents are employed, pricipally, at the rate of 5 ~ 100 weight %, and, preferably, 30 ~ 80 weight ~
per the total amount representing at least one compound se-lected from the metallic complexes of the invention, the com-pounds expressed by the previously mentioned general formula [XII] as well as the compounds expressed by the previously mentioned general formulas lXIIIa] and [XIIIb]. Additionally, the magenta coupler of the invention should be preferably em-ployed in a silver halide photographic light sensitive mate-rial by using such organic solvents in addition to a metallic complex as well as the above-mentioned image stabilizer.
As an dispersion auxiliary used when solving a hydro-phobic compound such as a coupler and others into the solvent solely comprizing a high-boiling point solvent or containing both high-boiling point and low-boiling point solvents, and, then, dispersing the compound, above, into water mechanically or by means of ultrasonic, an anion surface active agent, nonionic surface active agent and cation surface active agent can be employed.
The silver halide photographic light sensitive materials can be, for example, those for color negative film, color positive film and color photographic paper, however, especial-ly in the case of a color photographic paper which is appre-ciated by human eyes, the effect of the method, according to the invention, is effectively attained.

The silver halide photographic light sensitive materials, including the color photographic paper, above, can be which-ever monochromatic or multi-colored. In principal, a multi-colored silver halide photographic light sensitive material has, in order to provide a subtractive color reproduction, a constitution wherein silver halide emulsion layers containing magenta, yellow and cyan couplers serving as photographic couplers as well as non-light sensitive laye~s are laminated on a support in an adequate number and order, however, the number and order may be arbitrarily modified in compliance with the important performance and utilization purposes.
For the silver halide emulsions employed in the silver photographic light sensitive materials of the invention, any of the silver halides, contained in ordinary silver halide emulsions and containing silver bromide, silver iodo-bromide, silver iodo-chloride, silver chloro-bromide, silver chloride and the like, may be arbitrarily employed.
The silver halide grains employed in the silver halide emulsions may be obtained through whichever an acid process, neutral process or ammonium process. The grains may be allowed to grow at once or may be allowed to develop after forming seed grains. The two methods to form seed grains and to grow grains may be whichever same or diferent.
In preparing a silver halide emulsion, both halide ions and silver ions may be simultaneously added into an emulsion, or, halide ions may be added into an emulsion containing only silver ions, or, vice versa. Additionally, considering the critical growth rate of a silver halide crystal, the halide ions and the silver ions may be added into a mixing kiln whichever consecutively or simultaneously while controlling the pH and pAg values within the siln, so as to generate the silver halide crystals. After the crystals have grown up, the silver halide constitution within the grains may be transform-ed by means of a conversion process.
During the course of the production of the silver halide of the invention, the size, configuration, size distribution and growth of silver halide grains may be controlled by, if so required, employing a silver halide solvent.
With the silver halide grains employed in the silver halide emulsion layer of the invention, while the grains are formed and/or developed, the interior and/or surface of the grains are allowed to contain metallic ions, by employing a cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt, iron salt or complex salt, and, the interior and/or surface of the grains may be endowed with reducing sensitization cores by placing the grains under an adequate reducing atmosphere.
Unnecessary soluble salts may be whichever removed from or remained in the silver halide emulsion of the invention after silver halide grains have satisfactorily grown. If the salts are removed, the removal can be exercised by following the method mentioned in Research Disclosure No. 17643.
The interior and the surface of a silver halide grain employed in a silver halide emulsion, according to the inven-tion, may be whichever of the identical layer or difference layers.
The silver halide grains employed in the silver halide emulsion of the invention may be the grains ~herein a latent image is principally formed whichever on the surface thereof or in the interior thereof.
The silver halide grains employed in the silver halide emulsion of the invention may be the grains having whichever regular crystals or irregular crystals such as circular or sheet-shaped. Among such grains, the proportion between [100]-faced and [101]-faced crystals may be arbitrarily se-lected. Additionally, such grains may have ccmposites between the crystal configurations, above, or contain grains of vari-ous crystal configurations.
More than two of separately prepared silver halide emul-sions may be mixed to prepare the silver halide emulsion, ac-cording to the invention.
A silver halide emulsion of the invention is chemically sensitized with a conventional method. More specifically, a sulfur sensitization method where a compound or activated gelatin containing sulfur and can react with silver ions, a selenium sensitization method involving a selenium compound, a reducing sensitization method involving a reducing substance, a noble metal sensitization method involving gold and other noble metals and other methods may be independently or com-binedly employed.
A silver halide emulsion of the invention can be optical-ly sensitized to the desirable wavelength range by employing a dye known as a sensitizing dye in the photdgraphic art. The sensitizing dyes may be whichever independently or combinedly employed. The emulsion may allowed to contain, in addition to a sensitizing dye, a supersensitizer which is a dye not having a light-sensitization capability or a compound not actually absorbing visible radiation and serving to enhance a sensiti-zation function of the sensitization dye.
Into a silver halide emulsion of the invention may be added a compound, known as an anti-fogging agent or a stabi-lizer in the photographic art, during and/or at the completion of the chemical ripening of a light sensitive material and/or after the chemical ripening before the coating of a silver halide emulsion, in order to prevent the fogging of the light sensitive material during the preparation, storage and photo-graphic treatment of the similar material.
It is advantageous to use gelatin as a binder ~or, a pro-tective colloid) of the silver halide emulsion, according to the invention. Other than this material, above, a gelatin - ;200 - 1313791 derivative, graft polymer between gelatin and another high polymer, protein, sugar derivative, cellulose derivative, or a hydrophilic colloid derived from synthesized high polymer com-pound such as a monomer or copolymer may be also employed.
The photographic emulsion layers containing silver halide emulsion of the invention as well as other hydrophilic colloid layers may be hardened by independently or combinedly employ-ing hardeners which bridge binder (or, a protective colloid) molecules so as to enhance the fastness of the layers. The amount of hardners should be so much as to harden the light sensitive material and to the extent that the addition of hardener into processing solutions is not required, however, the addition of the hardener into the processing solutions is also allowable.
In order to improve the plasticity of the silver halide emulsion layers containing light sensitive materials involving silver halide emulsion of the invention and/or other hydro-philic colloid layers, the similar layers may be allowed to have a plasticizer, and, the silver halide emulsion layers containing light sensitive materials involving silver halide emulsion of the invention and other hydrophilic colloid layers are allowed to contain a material (latex) wherein an unsoluble or slightly soluble synthesized polymer is dispersed so as to improve the dimension stability and other properties.
In the emulsion layers of a silver halide color photo-graphic material, a dye forming coupler is employed, and, this dye forming coupler couples, during hte color forming develop-ment process, with an oxidant derived from an aromatlc primary amine developer (for example, a p-phenylenediamine derivative or aminophenol derivative and the like). Normally, the dye forming coupler is selected so that a dye which absorbs a photosensitive spectrum of an emulsion layer can form in every corresponding emulsion layer, and, in a blue sensitive emul-sion layer a yellow dye forming coupler, in a green sensitive emulsion layer a magenta dye forming coupler, in a red-sensi-tive emulsion layer a cyan dye forming coupler are respective-ly employed. However, a combination other than those mention-ed above may be employed to prepare a silver halide photo-graphic ilght sensitive material, in compliance with a speci-fic purpose.
As a cyan dye forming coupler of the invention, a 4-equivalent or 2-equivalent type cyan dye forming couplers de-rived from phenols or naphthols are typically used, and, the specific examples of which were disclosed as follows:
U.S. Patents No. 2306410, No. 2356475, No. 2362598, No.
2367531, No. 2369929, No. 2423730, No. 2474293, No. 2476008, No. 2498466, No. 2545687, No. 2728660, No. 2772162, No.
2895826, No. 2976146, No. 3002836, No. 3419390, No. 3446622, No. 3476563, No. 3737316, No. 3758308 and No. 3839044; Speci-fications in U.K. Patents No. 478991, No. 945542, No. 1084480, No. 1377233, no. 1388024 and No. 1543040; Gazettes for Japanese Patent O.P.I. Publications No. 37425/1972, No. 10135/
1975, No. 25228/1975, No. 112038/1975, No. 117422/1975, No.
130441/1975, No. 6511/1976, No. 37647/1976, No. 52828/1976, No. 108841/1976, No. 109630/1978, No. 48237/1979, No. 66129/
1979, No. 131931/1979 and No. 32071/1980.
Additionally, as a cyan dye forming coupler employed in the silver halide emulsion of the invention, those expressed by the following general formulas [C - 1] and [C - 2] are pre-ferable.
General formula ~C - 1]

OH
Ra ~NIICOR2 R I CON~

In the formula, above, R1 represents either an alkyl group or aryl group. R2 represents any one of an alkyl group, cycloalkyl group, aryl group or heterocyclic group. R3 repre-sents any one of a hydrogen atom, halogen atom, alkyl group or alkoxy group. Additionally, R3 and Rl may combine with each other to form a ring. Z represents a hydrogen atom or a group which may split off by the reaction with an oxidant derived from an aromatic primary amine color forming developing agent.

General formula [C - 2]
OH
CQ ~NHCOR5 R~ /~
z In the formula, above, R4 represents a straight-chained or branched alkyl group containing 1 ~ 4, or, preferably, 2 4 carbon atoms. R5 represents a ballast groùp. Z has the same meanings as Z in general formula [C - 1]. R4 is, most favorably, a straight-chained or branched alkyl group contain-ing 2 ~ 4 carbon atoms.

R N~
RS R~
R2 R3 R~ RS

K 2 CH3CONII ~ 11 11 11 11 ' 011 K--3 CN CII2~ I; 11 11 H
K--4 Cl21125 11 H
K 5 Cl ~1129 H 11 K 6 C l 6113 3 11 11 K 7 C l ~112 9 ~
K 8 (~3 Cll 3 CH 3 11 11 K 9 C6115CII=CIICII2 11 11 11 11 C511 1 (t) K--10 ~t)CSIII ~OCII2CONII~CII=CII Cll2--R2 1~3 R N~,~- R 4 l~6/--R5 R2 R3 1~1 RS R6 K 11 (t)C 5H~ 7 H H H H
K 12 CH 3 CONII ~ 11 11 11 11 H

K 14 C ~H29 11 11 11 K--16 Cl ~H29 CH3 H H H 11 Cslll l(t) K 17 (t)Csll~ ~OCIICONII~(CH2)2--K 18 CH3 CIJ3 CIJ3 11 Cll3 Cll3 K--19>~N--(Cl12)6-- CH3 11 11 CH3 H
K 20 CH3 11 H Cl 2112sOCOCI12-- 11 11 K 22 Cl13 C~ 61133 11 11 11 11 K--23 C611s 11 11Cl 2112sOCO-- 11 H
K--24 Cll 3 C 6Hs H H H H
K 25 CN ~ 11 11 11 11 11 - 206 - ~313791 R N~

K--26C611, 7 ~I
K 27CH3CONII ~ 1 H
K 28CN CH 2 ~CH 2--K 29Cl ~1128 K--30O~--(C112)8-- 1~
K 31 Cl 6H33 Cll3 K--32 ~) . .

Cslll ,(t) K--33 ( t ) C 6 H 1 1~ OCIICONII ~ CH 2-- H
C~llg 13i3791 Cl ~112g--N~

]K--35 C~ ~1129--N~

C I ~1129--N~3 , Csll I I CONH ~ CH2--N3 Cl ~1129--N/--9 ~N--Cl12 ~C112--N3 K--40 ~ } 3 Cs~l I I ( t) t--Cslll ~OCI12CONII~ (Cllz)3--~3 - ~08 - 1313791 Among the cyan dye forming couplers expressed by general formula [C - 1], those preferred are the compounds expressed by the following general formula [C - 3].
General formula [C - 3]

0~1 R 9 ~ NHCOR 6 R 7~ X--R ~ t~ CONH /~ l~

In general formula [C - 3], above, R~ represents a phenyl group, which may either have a single or a plurality of sub-stituents.
Rs represents a straight-chained or branched alkylene group having 1 ~ 20, or, more preferably, 1 ~ 12 carbon atoms.
R9 represents eithre a hydrogen atom or halogen atom, or, more preferably a hydrogen atom.
nl represents 0 or a positive integer, or, more prefer-ably, either 0 or 1.
X represents one of the bivalent groups, -0-, -C0-, -C00-, -OC0-, -S02NR-, NR'S02NR"-, -S-, -S0- and -S2-. R' and R"
respectively represent an alkyl group and may have a substi-tuent. The preferable examples for X are -0-, -S-, -S0-,and Z has the same meanings as Z in general formula [C - 1].

R4 is, preferably, an alkyl group having 2 ~ 4 carbon ~3~379~

atoms.
A ballast group expressed by R5 is an organic group featuring such a size and configuration as to give a coupler molecule a bulk sufficient to prevent a coupler contained within the layers supposed to hold the coupler from diffusing into the other layers.
As a typical example for such an ballast group, either an alkyl group or aryl group having total 8 ~ 32 carbona toms should be noted.
Among the ballast groups, the favorable ones are those expressed by the following general formula [C - 4].
General formula [C - 4]

--Cll--O--Ar I

R~o In the formula, above, R1o represents a hydrogen atom or an alkyl group having 1 ~ 12 carbon atoms. Ar represents an aryl group, such as a phenyl group and the like, and, such an aryl group may have a substituent.
In general formulas [C - 1], [C - 2] and [C - 3], the examples for a group expressed by Z and is split off by the reaction with an oxidant derived from an aromatic primary amine color developing agent are well known to those experi-enced in the photographic art. The typical examples include halogen atoms exemplified by a chrorine atom and a fluorine - 21~ - 1313791 atom, and, an alkoxy group, aryloxy group, arylthio group, carbamoyloxy group, acyloxy group, sulfonyloxy group, sulfo-namide group, heteroylthio group and heteroyloxy group, all of which may whichever possess or do not possess a substituent.
The most favorable example for Z is whichever a hydrogen atom or chorine atom.
More precisely, these groups o~ atoms are described in Japanese Patent O.P.`I. Publications No. 10135/1975, No. 120334/
1975, No. 130441/1975, No. 48237/1979, No. 146828/1976, No.
14736/1979, No. 37425/1972, No. 123341/1975 and No. 95346/1973, Japanese Patent Examined Publication No. 36894/1973, U.S.
Patents No. 3476563, No. 3737316 and No. 3227551.
The typical examples for a cyan coupler expressed by gen-eral formula [C - 1] are illustrated as follows, however, the scope of the present invention is not limited only to these examples.

(t)HI ~Cs ~OCHCONH
CQ
C~ Z112 5 (n) - ~ll - 1313791 ~ NHCO ~ F

(t)ll~Cs ~ sN l(t) ~ F F
I CQ
C~Hs(n) C - 3 ~ F
~ NHCO ~ F

> NSO2NH ~ slll~(t) ~ F F
Cll 3 I CQ
C4Hs(n) C ~ 4 ~ NHCO

(t)H~Cs ~ OCHCONH C~
C2~s C - ~ F F
O H

CQ
(n)C~2112sso2NH

, NHCO ~ F
~ Csllll(t) ~ F
(t)iHIlCs ~ OCHCONH CQ
C2Hs sllll(t) C~Hs (n) C ~ 8 (t)CsRIl ~ OCHCONH
C~ Cslll3(n) C ~ 9 NHCO ~
~ CsHil(t) ~ NHSO2C2Hs (t)H~Cs ~ OCHCONH C~
C2Hs - 213 - i313791 ~ NHSO
(t)HsC~ ~ SO2CHCONH C~
Cl 2H2s(n) (t)}l~Cs ~ OCHCONH
CH(CH~)2 The examples for a coupler expressed by general formula [C - 2] are illustrated as follows, however, the scope of the present invention is not limited only to these examples.
General formula [C - 2]

OH
CQ ~ NHCORs R~ ~
z Coupler No . R ~ Z tC s 11 1 1 ~' "

C ~ 12 - C2Hs - O ~ ` - CHO ~ tCsH~
NHCOCH3 C 2 Hs C - 13 - C21~s - CQ - CllO ~ tCsll C2l~5 C - 14 - C2Hs - CQ - CHO ~ tCsH
C~H

C - 15 - C~Hs - F - CHO ~ tCsH
C2~Js tCsH~

C - 16 - C211s - C~ - (CH2)30 ~ tCsH

- 215 - 1~13791 C`oupler No. R4 Rs _ tCsl~" .
C-17 -Cll, i~ ~ ~

1 ~ ~

C--19 --C21~ 5 --C,Q C~II9 _ Cg~l~ g ~ -C10~C~

C--21 --C 4 H g --0~ * --CHO ~ CH 3 * C8H,7(t) C6H,3 - 216 - i313791 As a yellow dye forming coupler employed in the invention, the compounds expressed by the following general formula [Y]
are preferable.
General formula [Y]

R"--C--Cll--C--NH--R, 2 Il l 11 O Y' O

In the formula, above, Rl1 represents either an alkyl group or aryl group. Rl2 represents an aryl group, and, yl represents either a hydrogen atom or a group which may spilit off in the course of color development reaction.
Additionally, as a yellow dye forming coupler, the com-pounds expressed by the following general formula [y1] are most favored.
General formula [yl]

CH3 0 0 R,3 R,~
H 3C--C--C--Cll--C--NH ~$ R ~ s CH3 Y' R, 6 In the formula, above, Rl3 represents a halogen atom, alkoxy group or aryloxy group. R14, R15 and R1~ respectively represents any one of a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, carbonyl group, sulfonyl group, carboxyl group, alkoxycarbonyl group, carbamyl group, sulfon group, sulfamyl group, sulfon-amide group, acylamide group, ureide group and amino group.
Y~ means the same as before.
These examples are described, for examples, in Specifica-tions in U.S. Patents No. 2778658, No. 2875057, No. 2908573, No. 3227155, No. 3227550, No. 3253924, No. 3265506, No.
3277155, No. 3341331, No. 3369895, No. 3384657, No. 3408194, No. 3415652, No. 3447928, No. 3551155, No.,3582322, No.
3725072 and No. 3894875, West German OLS Patents No. 1547868, No. 2057941, No. 2162899, No. 2163812, No. 2213461, No.
2219917, No. 2261361 and No. 2263875, Japanese Patent Examined Publication No. 13576/1974, Japanese Patent O.P.I. Publica-tions No. 29432/1973, No. 66834/1973, No. 10736/1974, No.
122335/1974, No. 2883411975 and No. 132926/1975.
The typical examples for a yellow dye forming coupler expressed by general formula [Y] are illustrated as follows, however, the scope of the invention is not limited only to these examples.

CH3--C--COCHCONH ~ CsHI I (t) O ~ CH 3 C s N 1 1 ( t ) i313791 Cl13 CQ
CH3- C- COCHCONII ~ C 5 H 1 ~ ( t) ~ C s ll l l ( t ) llsC20 CQ

CH3 - C- COCIICONH ~ C5H,I(t) C~3 N NIICO(C112)30 ~ C511"(t) ¢ ~ COOC6H,3(n) N

C~

CH3 -C- COCHCONH ~ C5H" (t) ~ C5H" (t) 131~791 Cl13- C- COCHCONII ~ CsHIl(t) CH3 0 NIICO(CH2)30 ~ Csllll(t) ~D
SO2 ~ OCH

CH3 - C- COCIICONII ~
CH3 N Cooc~H2s~n) 0~0 CH3 - C- COCIICONH ~
CH3 N NHCOCHCH2SO2C,2H2s(n) N N- CH2 ~ CH3 Y ~ 8 C~l 3 CQ
CH 3--C--COCHCONH ~ C s H I I ( t ) C113 0 CQ NHCOCHO ~CsH~ I(t) CQ/~D
OH
y _ g CH ~ CQ
Cll a ~ C ~ COCIICONII

~ N--N--CH 2~

An anti-color-fogging agent is employed, in order to pre-vent a color stain, decrease in sharpness and outstanding grainess resulting from a transfer, from an emulsion layer to the other (from an emulsion layer to the other emulsion layer of an identical color sensitivity and/or to the layer of the different color sensitivity) within a color photographic light sensitive material of the invention, of an oxidant derived from a developing agent, or, of an electron transfer agent, an - 221 - 131379~

anti-color-fogging agent is employed.
The anti-color-fogging agent may be employed in emulsion layers themselves, or, intermediate layers may be provided be-tween neighboring emulsion layers so that such intermediate layres can hold the anti-color-fogging agent.
As an anti-color-fogging agent employed in the present invention, the compounds expressed by the following general formula [HQ] are preferable.
General formula [HQ]

OH

R Z ~ ~( R2 In the formula, above, R21, R22, R23 and R24 respectively represent any one of a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkylacylamino group, arylacylamino group, alkylcarba-moyl group, arylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, cyano group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylacyloxy group and arylacyloxy group.
At least one of R2l and R22 is a group, mentioned above, having more than total of six carbon atoms within itself and as its substituent.
Among the compounds employed in the invention and ex-pressed by the above general formula [HQ], the compounds ex-pressed by the following general formula [HQ'] are more pre-ferably used in the invention.
General formula [HQ']

OH

R
OH

In the formula, above, either R31 or R32 represents a hydrogen atom, alkyl group, alkenyl group, aryl group, acyl group, cycloalkyl group or heterocyclic group. At the same time, at least one of R31 and R32 is a group having more than 6 carbon atoms in total.
As for such a heterocycle group, an imidazolyl group, furyl group, pyridyl group, triazolyl group and others are available.
With the above-mentioned general formula [HQ'], a com-pound wherein at least one group among R31 and R32 has more than total of 8 carbon atoms is preferred. And, more favor-ably, both R31 and R32 are groups respectively having a total of 8 ~ 18 carbon atoms, and, most favorably, both R31 and R32 are of an identical alkyl group having a total of 8 ~ 18 car-bon atoms.
The examples for the compounds employed in the present invention and empressed by the above-mentioned general formula [HQ] are illustrated as follows, and, naturally, the scope of the invention is not limited only to these examples.

(HQ--1 ) Cl13 OH
Cl13 (HQ--2 ) OH
~C8H, 7(t) OH

(HQ--3 ) ,1~ CsHI7(t) (t)11l7Cs OH

(HQ- 4) ~ C, 2H2 5 (sec) (sec)N2scl 2 /~
01~ ' (Hq- 5 ) OH
~CI 6H33(sec) C~3 /~

OH

(HQ- 6) OH
,1~ ClaH37 (sec) (t)HsC~
OH

~313791 ~H~--7 ) ~D

~y,~ Otl (HQ- 8 ) OH
~ C}12CONHC~2H2s(ll) (n)H25C,211NOCH2C
OH

(HQ- 9) OH

(HQ- 10) Cl13 Cll,~ CH ~ C - CUz-CHz- CUz- CU /
~ CH- CH2-CH2-CH2- C
CH3 i OH
C2Hs For the silver halide emulsions employed in the silver photographic light sensitive materials of the invention, any of the silver halides, contained in ordinary silver halide emulsions, such as silver bromide, silver iodo-bromide, silver iodo-chloride, silver chloro-bromide, silver chloride and the like may be arbitrarily employed.
With the silver halide grains employed in the silver halide emulsion layer of the invention, while the grains are formed and/or developed, the interior and/or surface of the grains are allowed to contain metallic ions, by employing a cadmium salt, zinc salt, lead salt, thallium salt, iridum salt or complex salt, rhodium salt or complex salt, iron salt or complex salt, and, the interior and/or surface of the grains may be endowed with reducing sensitization cores by placing the grains under an adequate reducing atmosphere.
Unnecessary soluble salts may be whichever removed from or remained in the silver halide emulsion of the invention after silver halide grains have satisfactorily grown. If the salts are removed, the removal can be exercised by following the method mentioned in Research Disclosure No. 17643.
The silver halide grains employed in the silver halide emulsion of the invention may be the grains having whichever regular crystals or irregular crystals such as circular or sheet-shaped.
A silver halide emulsion of the invention is chemically sensitized with a conventional method.
~ . silver halide emulsion of the invention can be optical-ly sensitized to the required wavelength range by employing a dye known as a sensitizing dye in the photographic art. The sensitizing dyes may be whichever independently or combinedly employed. The emulsion may allowed to contain, in addition to a sensitizing dye, a supersensitizer which is a dye not having a light-sensitization capability or a compound not actually absorbing visible radiation and serving to enhance a sensiti-zation function of the sensitization dye.
Into a silver halide emulsion of the invention may be added a compound, known as an anti-fogging agent or a stabi-lizer in the photographic art, during and/or at the completion of the chemical ripening of a light sensitive material and/or after the chemical ripening before the coating of a silver halide emulsion, in order to prevent the fogging of the light sensitive material during the preparation, storage and photo-graphic treatment of the similar material.
In a silver halide photographic light sensitive material may be provided with auxiliary layers such as a filter layer, anti-hallation layer and/or anti-irradiation layer and others.
These layers and/or emulsion layers may contain a dye, which flows out of a color sensitive material during a development process, or which is bleached during the similar process.
In order to suppress a gloss of a light sensitive mate-- 228 - 131~791 rial, to improve retouchability, to prevent mutual adhesion of light sensitive materials, a matting agent may be added into silver halide emulsion layers derived from a silver halide photographic light sensitive material of the invention and/or the other hydophilic colloid layers.
The photographic emulsion layers derived from the silver halide photographic light sensitive material of the invention as well as other layers may be coated upon a flexible reflex support made of a paper or synthesized paper provided with a lamination of a baryta layer or a-olefin polymer and the like, or, upon a film comprising a semisynthesized or synthesized high molecule such as a cellulose acetate, cellulose intrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide and others, or, upon a rigid body such as a glass, metal, cetramic and others.
The silver halide photographic light sensitive material may form an image through a color development known in the art.
The aromatic primarine amine color forming developing agent employed in the color developer of the invention con-tains those known in the art and widely used for various color photographic processes.
According to the invention, after the color development treatment, the material is further treated with a processing solution which has a fixing capability. If the processing 13~79~

soluti~n having a fixing capability is a fixer, the bleaching process is exercised before the treatment with the processing solution.
As can be understood from the discussions, above, the silver halide photographic light sensitive material of the in-vention features an excellent color reproducibility as well as a decreased Y-stain, in the non-colored area, caused by light, heat or moisture, and, further, with the similar material, a light-resistance of a magenta dye image is remarkably improved and a discoloration due to light is successfully prevented.
The present invention is specifically described with the following Examples, however, the scope of this invention is not limited only to these Examples.
Example 1 The following layers were sequentially disposed upon a paper support which has lamination of polyethylene on the both sides.
First layer: Emulsion layer Those coated were the magenta coupler (44) according to the present invention at the rate of 6.0 mg/100 cm2, a silver chloro-bromide emulsion (containing 85 mol~ silver bromide) at the rate equal to 3.5 mg silver per 100 cm2, dibutylphthalate at the rate of 6.0 mg/cm2 and gelatin at the rate of lS.0 mg/
100 cm2.

econd layer: Intermediate layer (layer containing ultravio-let absorvent) I'hose coated were 2-(2-hydroxy-3-sec-butyl-5-tert-butylphenyl) benzotriazole working as an ultravio~et absorber at the rate of 5.0 mg/100 cm2, dibutylphthalate at the rate of 3.0 mg/cm2 and gelatin at the rate of 12.0 mg/cm2.
Third layer: Protective layer Gelatin was coated at the rate of 8.0 mg/100 cm2.
The sample, prepared as described above, was designated sample 1.
The samples 2, 3, 4, 5, 6, 7, 8 and 9 were prepared by respectively adding to sample 1 the example compounds of the inve,ntion, P - 1, P - 32, CH - 35, CH - 38, HI - 25, HI - 28 serving as magenta dye image stabilizers as well as the com-parison examples a and b, below, at the rate equinomolar with the magenta coupler.
Additionally, two among the above-mentioned eight magenta dye image stabilizers were combinedly employed in the combina-tions shown in Table 1, in order to prepare the samples 10 29.
The two magenta dye image stabilizers combinedly employed in the samples 10 ~ 29 were employed in such a manner that two stabilizers are equinomolar with each other and that the total mol of the two stabilizers is equinomolar with the magenta coupler.

Compar.ison compound a (Compound disclosed in Japanese Patent O.P.I. Publication No.
4853~/1979) OC8H~ 7(n?
p ~/C8HI 7(t) ( t)C8~ 1 7/~
OCsH, 7(n) Comparison compound b (Compound disclosed in Japanese Patent O.P.I. Publication No.
159644/lg81) (n)C~H70 ~ ,CH3 I~ I~ ~OC3117(n) (n,c3},70~ r 1l C~ ~OC3H7 (n) After exposing every sample, prepared above, to a light through an optical wedge, according to a conventional method, each sample was treated with the following processes.
[Treatment]Processing temperature Processing time Color development33C 3 min 30 sec Bleach-fixing 33C 1 min 30 sec Rinsing 33C 3 min Drying 50 ~ 80C 2 min The components of each processing agent are as follows.

[Color developer solution]
Benzyl alcohol 12 mQ
Diethylene glycol 10 mQ
Potas~;ium carbonate 25 g Sodium bromide 0.6 g Sodium sulfite anhydride 2.0 g Hydroxylamine sulfate 2.5 g N-ethyl-N-~-methanesulfonamidethyl-3-methyl-4-aminaniline sulfate 4.5 g Water was added to the components to make a 1 Q solution, wherein NaOH was added to adjust the PH value at 10.2.
lBleach-fixing solution]
Ammonium thiosulfate . 120 g Sodium metabisulfite 15 g Sodium sulfite anhidride 3 g EDTA ferric ammoniate 65 g Water was added to the components to make a 1 Q solution, wherein the PH value was adjusted to 6.7 ~ 6.8.
The densities of the samples 1 ~ 29, treated above, were measured with a densitometer ~model, KD - 7R; manufactured by Konishiroku Photo Industry Co., Ltd.) under the following conditions.
The samples already treated, mentioned above, were ex-posed to a xenon fade-ometer for 14 days, in order to test the light-resistance of the dye imayes. Additionally, the judging - 233 - 131379~

criteria of the light-resistance of the dye images are as follows.
[Survival ratio]
This is the residue percent of dye after the light-resistance and moisture-resistance tests, when assuming the initial density is 1Ø
[Discoloration degree]
This value is determined by assuming the initial density is 1.0 and by subtracting (yellow density)/(magenta density) before the light-resistance test from (yellow density)/(magenta density) after the light-resistance test. It means that the greater the value is, the more the magenta color is prone to turn to yellower tone.
Table 1 shows the results.

Table 1 _ Light resistance Samplo No.Coupler Dye im~ge stabili~er Survival DiscolorAtion ratio (li) degree 1 ~means COmpAriSOn s.~mple) 44 _ _ _ _ 15 0.85 2 (meons comp.lrison sample) 44 P-l 57 0.12 3 ~means comparlson sample) 44 P-32 58 0.13 4 tm~lm9 compari90n sample) __ Cll-35 55 0.16 S (means comparison sample) 44 Cll-38 56 0.15 ô (mean8 co~nparlson s~mple) 44 111-25 61 0.15 7 (means comparison sample) 44 111-28 60 0.15 8 (means comparison sample) 44Comparison compound a 46 0.73 9 (means comparlson 8ample) 44Comparlson compound b 52 0.69 (meanscomparlson 8ample) 44 P-l + Comparlson compound a 62 0.18 11 (meanscomparlson sample) 44 P-32 + Comparlson compovnd a 62 0.18 12 (meanscompilrlson sample) 44 CH-35 + Comparlson compound a 60 O.Zl 13 (meanscomparlson sample) 44 CH-38 + Comparlson compound ~ 62 0.20 14 (meanscompnrlson samplo) 49 ItI-25+ CompArl~on compound a 63 0.20 ~me~n~compArlson l~ample) 44 III-29 + Compllri~on compound 1 64 O.19 16 ~meanscomparlson sample) 44 P-l + Compari90n compound b 63 0.18 17 ~meanscomparison sample) 44 P-32 + Comparlson compound b 64 O.lô
lô ~means comparlson snmple) 44 Cll-35 + Comparlson compound b 61 0.19 19 ~meanscomparlson sample) 44 CH-38 + Comparison compound b 63 0.19 (meanscomparison sample) 44 HI-25 + Comparison compound b 63 0.20 21 ~meanscomparlson sample) 44 HI-28 + Comparlson compound b 66 0.18 2Z (means sample accordlng to 44 P-l + CH-35 7S 0.09 the present lnventlon) _ 23 (means ~ample according to 44 P-l + CH-38 74 0.09 the prese~t inventlon) 24 (mean~ sample accordlng to 44 P-l + HI-25 76 0.10 the present lnventlon) (means sample accordlng to 44 P-l + HI-28 78 0.09 the present lnvention) 26 (means 8ample accordlng to 44 P-32 + CU-35 74 0.11 the present lnvention) 27 (means sample according to 44 P-32 + CH-38 74 0.10 the present invention) 28 (means sample accordlng to 44 P-32 ~ UI-25 76 0.09 the present lnvention) 29 ~means sample according to 44 P-32 + III-28 75 0.09 the present lnvention) - 235 - 13~37~1 llhe results in Table 1 illustrate that the significantly improved dye image survival ratio in the light-resistance test, though accompanying a slightly greater discoloration, when compared with samples 2 ~ 9 prepared by singly adding one magenta dye image stabilizer into the magenta coupler of the invention, was attained with samples 10, ll, 16 and 17 which were prepared by combinedly adding a magenta dye image stabi-lizer comprising a piperazine or homopiperazine of the inven-tion and a conventional magenta dye image stabilizer into the magenta coupler of the invention, and, with samples 12, 13, 18 and 19 which were prepared by combinedly adding a magenta dye image stabilizer comprising a chroman of the invention, and a conventional magenta dye image stabilizer into the magenta coupler of the invention, and, with samples 14, 15, 20 and 21 which were prepared by combinedly adding a magenta dye image stabilizer comprising a hydroxyindane of the invention into a magenta coupler of the invention.
At the same time, the results also indicate that samples 22 ~ 29, of the invention, prepared by combinedly adding both a magenta dye image stabilizer comprising a piperazine or homo-piperazine of the invention and a magenta dye image stabilizer comprizing a chroman or hydroxyindane of the invention into a magenta coupler of the invention showed the excellent surviv-ing ratio of dye image, in the light-resistance test, which could not be expected in view of the results for samples 2 ~ 7 which were prepared by singly adding each magenta dye image stabilizer of the invention to a magenta coupler of the inven-tion, and that the above samples of the invention also feature effectively minimized discoloration of the dye image in the light-resistance test.
Example 2 The coupler and the magenta dye image stabilizer were, in accordance with the combinations shown in Table 2, coated in the same manner as for Exmaple 1 so as to prepare samples 30 ~ 58.
Samples 30 ~ 58 were treated with the same method des-cribed for Example 1. Further, the light-resistance test was exercised on these samples in the same manner as for Exmaple 1, obtaining the results shown in Table 2.
Additionally, the total amount employed of the dye i~age stabilizing agent contained in each sample was, whichever such an agent was used singly or in combination, equimolar with the coupler. When two dye image stabilizers were employed in one sample, the ratios of the amounts employed of both stabilizers were made equal to each other.

Table 2 Sample No.Coupler Dye imag~ st~oillzer Llght reslstance/
30 ~means compArlson sample) P-l9 44 31 (means compArison sA~plo) al-25 45 32 (meAnR comparlson sAmple) S HI-37 48 _ 33 (meAnS sAmplo nccordlng to 5 P-l9 + Cll-25 67 the presene lnventlon) _ 34 (means sAmple Accordlng to 5 P-l9 ~ HI-37 69 tho present~lnventlon) (meal~s sAmple Accordlng to 5 P-l9 + Cll-25 + HI-37 72 tho pre~ent inventlon) _ 36 (melms comparlson sample) 54 P-l9 49 37 (meAns comparison snmple) 54 CH-25 51 38 ~m~Ans comparlson sAmple) 54 HI-37 54 39 ~means sAmple accordlng to 54 P-l9 + Cll-25 73 the present lnventlon) ~means sample according to 54 P-l9 + HI-37 74 the present inventlon) 41 ~menns sAmple accordlng to 54 P-l9 + CH-25 + HI-37 76the pr0sent lnventlon) 42 ~mennri comp~rlson snmple) 130 P-l9 55 43 ~me~ns compArlson ~mple~ 130 CH-25 55 44 ~means compArlson snmple) 130 HI-37 57 ~meAns sample nccordlng to 130 p-lg + CH-25 76 the present lnvontlon) 46 ~me~ns snmple accordlng to 130 P-l9 + HI-37 77 the prosent inventlon) 47 ~means sAmple ~ccoralng to 130 P-l9 + aH-25 + HI-37 79the present inventlon) 48 ~means sample accoralng to 54 P-2 t CH-6 70 the present lnventlc.n) 49 ~means sample nccordlng to 54 P-2 + HI-3 73 the present lnventlon) _ ~means snmple Accoraing to 54 P-3 + CH-6 72 tho prosent lnventlon~
51 ~means sample accordlng to 54 P-3 + HI-3 71 thc present invention) _ 52 (means sample accordlng to 54 P-7 + CH-6 71 the present lnventlon) 53 (means sample accordlng to 54 P-7 + NI-3 70 the present inventlon) _ 54 (means sample according to 54 P-27 + aH-27 72 the present lnvention) (moans sample according to 54 P-26 + al-36 70 the present invention) _ 56 (means sample according to 54 P-31 + aH-47 71 the present inventlon) 57 (means sample accordlng to 54 P-33 + 8I-12 71 the present lnventlon) 58 (means sample accordlng to 54 P-34 + HI-44 73 the present lnventlon) - 238 - ~3~379~

The results in Table 2 illustrate that the samples pre-pared by simultaneously adding two or three types of the magenta dye image stabilizers of the present invention into the magenta coupler of the invention have a significantly improved light-resistance property, compared with the samples prepared by adding only one similar agent of the invention, into the magenta coupler of the invention.
Example 3 The following layers were sequentially disposed upon a paper support which has lamination of polyethylene on the both sides, in order to prepare a multi-color silver halide photo-graphic light sensitive material, thus obtaining sample 59.
Firlst layer: Blue-sensitive silver halide emulsion layer Those coated were ~-pivaloyl-~-(2,4-dioxo-1-benzylimida-zoline-3-yl)-2-chloro-5-[y-(2,4-di-t-amylphenoxy)butylamide]
acetanilide as a yellow coupler at the rate of 6.8 mg/100 cm2, a blue-sensitive silver chloro-bromide emulsion (containing 85 mol~ silver bromide) at the rate equal to 3.2 mg silver per 100 cm2, dibutylphthalate at the rate of 3.5 mg/100 cm2 and gelatin at the rate of 13.5 mg/100 cm2.
Second layer: Intermediate layer Those coated were 2,5-di-t-oxtylhydroquinone at the rate of 0.5 mg/100 cm2, dibutylphthalate at the rate of 0.5 mg/100 cm2 and gelatin at the rate of 9.0 mg/100 cm2.

Third layer: Green-sensitive silver halide emulsion layer Those coated were the magenta coupler 28 of the present invention at the rate of 3.5 mg/100 cm2, a green-sensitive silver chloro-bromide emulsion (containing 85 mol% silver bromide) at the rate equal to 2.5 mg silver per 100 cm2, dibutylphthalate at the rate of 3.0 mg/100 cm2 and gelatin at the ratio of 12.0 mg/cm2.
Fourth layer: Intermediate layer Those coated were 2-(2-hydroxy-3-sec-butyl-5-t-butyl-phenyl) benzotriazole working as an ultraviolet absorvent at the rate of 7.0 mgtlO0 cm2, dibutylphthalate at the rate of 6.0 mg/cm2, 2,5-di-t-octylhydroquinone at the rate of 0.5 mg/
cm2 and gelatin at the rate of 12.0 mg/100 cm2.
Fifth layer: Red-sensitive silver halide emulsion layer Those coated were 2-[c~-(2,4-di-t-pentylphenoxy)butan-amide]-4,6-dichloro-5-ethylphenol working as a cyan coupler at the rate of 4.2 mg/100 cm2, a red-sensitive silver chloro-bromide emulsion (containing 85 mol96 silver bromide) at the rate equal to 3.0 mg silver per 100 cm2, tricresylphosphate at the rate of 3.5 mg/cm2 and gelatin at the rate of 11.5 mg/100 cm2 .
Six layer: Intermediate layer A layer comprising the same contents as in the fourth layer.

Seventh layer: Protective layer Gelatin was coated at the rate of 8.0 mg/100 cm~.
The multi-layered samples 60 ~ 77 were prepared by adding each magenta dye image stabilizer of the invention, at the proportions shown in Table 3, into the above-mentioned sample 59. After the samples were exposed to light and were txeated in the same manner as in Example 1, the light-resistance test was exercised on every sample, where every sample was exposed to a xenon fade-ometer for 16 days. The results, too, are shown in Table 3.

Table 3 _ Magenta dye image Sample No Dye image Amount employed light resistance/
. stabilizer mol~/coupler survival ratio (~) 59 ~means comparison sample) _ 10 (means comparison sample) P-l 100 50 61 (means comparison sample) P-l 150 58 62 (means comparison sample) CH-35 100 49 63 (means comparison sample) CH-35 150 ` 57 64 (means comparison sample) HI-28 100 51 (means comparison sample) HI-28 150 58 66 (means sample according to P-l + CH-35 75 + 25 66 the present invention) 67 (means sample according to P-l + CH-35 50 + 50 72 the present invention) 68 (means sample according to P-l + CH-35 25 + 75 68 the present invention) 69 (means sample according to P-l + CH-35 100 + 50 69 the present invention) (means sample according to P-l + CH-35 75 + 75 77 the present invention) 71 (means sample according to P-l + CH-35 50 + 100 70 the present invention) 72 (means sample according to P-l + HI-28 75 + 25 68 the present invention) 73 (means sample according to P-l + HI-28 - 50 + 50 74 the present invention) 74 (means sample according to P-l + HI-28 25 + 75 70 the present invention) (means sample according to P-l + HI-28 100 + 50 73 the present invention) 76 (means sample according to P-l + HI-28 75 + 75 79 the present invention) 77 (means sample according to P-l + HI-28 50 + 100 72 the present invention) - 2~2 - 13137~1 The rsults in Table 3 illustrate that, when the total amount employed of the magenta dye image stabilizers of the invent:ion is kept constant, the combined employment of the magenta dye image stabilizers of the invention at a proper proportion can, rather than the single employment of the magenta dye image stabilizer of the invention, significantly improve the light-resistance of a magenta dye image.
Further, the samples, according to the invention, feature the excellent color reproducibility as well as the decreased Y-stain.
Example 4 Upon a support comprising a polyethylene-coated paper were disposed the previously mentioned example magenta coupler (5) at the rate of 4 mg/dm2, a green-sensitive silver chloro-bromide at the rate equivalent to 2 mg silver per dm2, dioctylphthalate at the rate of 4 mg/dm2 and gelatin at the rate of 16 mg/dm2.
Additionally, upon the layer, above, was disposed gelatin at the rate of 9 mg/dm2.
The sample thus prepared was designated sample lOl.
Then, samples 102 through 117 were prepared by modifying the composition among coupler, metal complex and a dye image sta-bilizer, as shown in Table 1, contained in the coupler-contained layer of sample 101, and, other than this, these samples were identical with sample 101. Additionally, a metal complex and a dye image stabilizer as well as a coupler were added into a solvent.
After these samples were exposed to a green light through an optical wedge, using a photogrpahic sensitometer (model, KS - 7, manufactured by Konishiroku Photo Industry Co., Ltd.), the following processes were conducted.
Standard treatment (processing temperature and processing time) [1] Color development38C3 min 30 sec [2] Bleach-fixing 33C1 min 30 sec [3] Rinsing 25 30C 3 min [4] Drying 75 80C Approx. 2 min [Color developer solution]
Benzyl alcohol 15 mQ
Ethylene glycol 15 mQ
Potassium sulfite 2.0 g Sodium bromide 0.7 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxylamine sulfate 3.0 g Polyphosphoric acid (TPPS) 2.5 g 3-methyl-4-amino-N-(~-methanesulfonamidethyl)-aniline sulfate 5.5 g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0 g - 244 - 1 3 1 3 7 9t Potassium hydroxide 2.0 g Water was added to prepare 1 Q solution, which was treat-ed so as to attain the pH value of 10.20.
[Bleach-fixing solution]
Ethylenediaminetetraacetic ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 mQ
Ammonium sulfite (40% solution) 27.5 mQ
Potassium carbonate or glacial acetic acid was added so as to attain the pH value of 7.1, wherein water was added in order to prepare 1 Q solution.
The light-resistance test was exercised on every sample in the following manner, after the above treatment. The re-sults are shown in Table 4.
[Light-resistance test]
Each sample was exposed to the sunray for 30 days, by employing an under-glass outdoor exposure rack, in order to measure the green densities before and after the color of a sample was allowed to fade. The fading degree due to light, that is, the fading ratio was determined with the following expression.
Fading ratio = (Do - D)/Do x 100 (~) WHere; Do = Pre-fading density D = Post-fading density - 245 - 131379i Table 4 Dye imaqe stabilizer Light Metallic resistance Sample No. Coupler complex Piperazine Chroman, ratlo) 101 (means comparison sample) 92 102 (means comparison sample) 5 16 _ _ 43 103 (means comparison sample) 5 _ P - 1 _ 51 104 (means comparison sample) 5 _ _ CH - 35 55 105 (means comparison sample) 5 _ _ HI - 28 56 106 (means comparison sample) 5 16 _ CH - 35 35 107 (means comparison sample) 5 _ P - 1 CH - 35 43 108 (means comparison sample) 5 16 P - 1 _ 36 109 (means sample according to 5 16 P - 1 CH - 35 24 the present invention) l 110 (means sample accordinq to 7 16 P - 1 CH - 35 25 the present invention) 111 (means sample accordinq to 28 16 P - 1 CH - 35 22 the present invention) 112 (means sample accordinq to 44 16 P - 1 CH - 35 21 the present invention) 113 (means sample accordinq to 99 16 P - 1 CH - 35 20 the present invention) .
114 (means sample according to 152 16 P - 1 CH - 35 22 the present invention) 115 (means sample according to 157 16 P - 1 CH - 35 23 the present invention) 116 (means sample according to 172 16 P - 1 CH - 35 21 the present invention) 117 (means sample accordinq to 5 16 P - 1 CH - 35 18 the present invention) HI - 28 - 2~6 - 131379i * The optical quenching rate constant of a singlet oxygen contianed in metal complex 16 is 2 x 108M~1 sec~1.
* Piperazine: a compound expressed by general formula [XII].
* Chroman : a compound expressed by general formula [XIIIa].
* Indane : a compound expressed by general formula [XIIIb].
* 0.5 mol metal complex, 1 mol piperazine, 1 mol chro-man and 1 mol indane were added to l mol coupler.
As illustrated by Table 4, when any one of piperazine, chroman or indane was added to a metal complex of the present invention, rather than the single employment of the metal complex of the invetion, the light-resistance property is ef-fectively improved, however, such a property is not yet satis-factory. Contrary, the samples, according to the invention, wherein three components, that is, a metal complex of the in-vention, piperazine, and whichever chroman or indane, were employed feature the significantly improved light-resistance property, and, additionally, such a property is deemed satis-factory.
Example 5 The following layers were sequentially disposed upon a paper support which has lamination of polyethylene on the both sides, in order to prepare a multi-color silver halide photo-graphic light sensitive material.
First layer: Blue-sensitive silver halide emulsion layer Those coated were ~-pivalyl-~-(l-benzyl-2,4-dioxy-imidalysine-3-yl)-2-chloro-5-[y-(2,4-di-t-amylphe~oxy)butyl-amido]-acetanilide as a yellow coupler at the rate of 8 mg/dm2, a blue-sensitive silver chloro-bromide emulsion at the rate equal to 3 mg silver per 100 dm2, 2-4-di-t-butylphenol-3',5'-di-t-amyl-4'-hydroxybenzoate at the rate of 3 mg/dm2, dioctyl-phthalate at the rate of 3 mg/dm2 and gelatin at the rate of 16 mg/dm2.
Second layer; Intermediate layer Gelatin was coated at the rate of 4 mg/dm2.
Third layer: Green-sensitive silver halide emulsion layer Those coated were the example magenta coupler (5), men-tioned previously, at the ratio of 4 mg/dm2, a green-sensitive silver chloro-bromide emulsion at the rate equal to 2 mg silver per dm2, dioctylphthalate at the rate of 4 mg/dm2 and gelatin at the rate of 16 mg/dm2.
Fourth layer: Intermediate layer Those coated were 2-hydroxy-3',5'-di-t-amylphenyl) benzo-triazole working as an ultraviolet absorver at the rate of 3 mg/dm2, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-benzotriazole at the rate of 3 mg/dm2, dioctylphthalate at the rate of 4 mg/
dm2 and gelatin at the rate of 14 mg/dm2.

FiEth layer: Red-sensitive silver halide emulsion layer I'hose coated were 2,4-dichloro-3-methyl-6-[~-(2,4-di-t-amylphenoxy) butylamido]-phenol working as a cyan coupler at the rate of 1 mg/dm2, 2-(2,3,4,5,6-pentafluoropenyl)acylamono-4-chloro-5-[~-(2,4-di-tert-amylphenoxy)pentylamido] at the rate of 3 mg/dm2, a red-sensitive silver chloro-bromide emul-sion at the rate equal to 2 mg silver per dm2.
Six layer: Intermediate layer Those coated were 2-(2'-hydroxy-3',5'-di-t-amylphenyl)-benzotriazole working as an ultraviolet absorvent at the rate of 2 mg/dm2, 2-(2'-hydroxy-3',5'-di-ti-butylphenyl-benzotria-zole at the rate of 2 mg/dm2, dioctylphthalate at the rate of 2 mg/dm2 and gelatin at the rate of 6 mg/dm2.
Seventh layer: Protective layer Gelatin was coated at the rate of 9 mg/dm2.
The sample so prepared was desiganted sample 101.
Then, samples 119 through 138 were prepared, by combined-ly providing the third layer of the above-mentioned sample 118 with a metal complex and a dye image stabilizer in accordance with the combinations shown in Table 2, and, other than this arrangement, these samples were identical with sample 101.
The samples so prepared, above, were exposed and treated in the same manner as in Example 4. The samples so treated were measured for the light-resistance property in the same manner as in Example 4.

- 24~ - 1313791 Additionally, as for the tone, the maximum absorption wavelength was determined in the following manner, and, each sample was examined with the naked eye whether it was bluer or not.
The results are shown in Table 5.
[Measurement of otne (maximum absorption wavelength)]
After each sample was exposed to green light through an optical wedge, by using a photogrpahic sensitometer (model, KS-7; manufactured by Konishiroku Photo Industry Co., Ltd.), then, the treatment, mentioned previously, was exercised.
Each magenta color-forming sample so prepared was meas-ured for a magenta tone, by employing a color analyzer model 607 manufactured by Hitachi.
In this case, the maximum absorption density around 535 nm ~ 545 nm was set at 1Ø
The maximum absorption wavelength, of each absorption spectrum measured in the above-mentioned manner, was read in order to use the wavelength as the index of a tone.

_ a~ , ~ ~ , , , , , , , , , , . , , , , , ~o ~ ~ m m m m c 2~ R ~ ~ o~ & ;~ 2 ~ ~ ~ N ~

3~
_ ~ _ - :

~ ~ O ~J 1~ ~ al N N N N N N N N N N N N N N N ~
N
_ _ ~ ii r) ~ ~ ") ~ ~.) ~) r)1'1 1.1 f'l r~ N N 1'1 ~ 1-1 1`'1 1~
I
3 ~.~ a ~q O ~
___. ~ .1 ~1 ~ I ~1 1` N N ~1 ~1 _I ~1 ~I r~ rl 5 ,~ ~ ~ I~IIIIIIIIIIIIIIII~,~I
e .
q ~ ,a, ~
E~ ~,3 ~ ~ O 0 ~0 ~ ~0 0 ~0 0 -O -O ~0 -O -O 0 ~ ~0 ~ 0 Ov. ~x~xxxxxxxxxxxxxxxxxx ~ N N N N 1~ 1') ~I N N N N N N N N N N N N
g~
X O . ~
3 ~ , rl , r~ N ~ U~ o ,, ,e 1~ ~ui O

~ 8 v ~ 9 J v ~ v ~ v 9 v ~ ~ ! Y ~ 2 2q ~5 a â 59 3c 28 3 2 55 5S ~2 S5 3 8 3 5 3 S 7 j 5 ~ e~ ~ e~ ~ x ~ ~0 ~ x ~ 50 ~ ab ~ 50 ~ 5~ ~ 5 ~ vS~ ~ S ~ a~ ~ b e~ e~ ~
u~ 7 0 ~, a o, la ~ n, c n~ D~ ~
æ j H 3 ~ 3 ~ 3 ~ 3 ~ 3 ~ 3 ~ 3 ~ E~ ~ 3 ~ ~ ~ H '5 H ~; H ~i H ~ ~i E
~I rl N N NN N N N N N N l O ~I N
_ rl - 251 - 131~791 Comparison metal complex ~H3(t) HO ~ C~l 22p ~ ~ N;

Comparison compound a OC8HI 7 (t) ~CsHI l(n) ( ) 1C8H, ~(t) * 0.5 mol metal complex, 1 mol piperazine, 1 mol chroman and 1 mol indane were added to 1 mol coupler.
As illustrated by Table 5, in the case of multi-layered samples, too, the samples of the invention comprising three components, that is, a metal complex of the invention, pipera-zine, and, chroman or indane whichever, feature the most ex-cellent light-resistance property.
Table 5 also indicates that the samples singly employing a metal complex of the invention, the samples singly employing chroman or indane and the samples employing both a metal com-plex and whichever chroman or indane, alike, have longer maxi-mum absorption wavelengths, rendering each magenta dye image bluer.

More specifically, it is apparent that the present inven-tion may not only significantly improve the light-resistance but effectively provide the correct tone.
Example 6 Samples 139 through 117 were prepaxed by modifying the combination between an image stabilizer and an organic solvent, as shown in Table 7, contained in the magenta coupler-contained layer, and by further adding another image stabilizer into the same layer, and, other than above, these samples were identi-cal with sample 121 in Example 5. These samples were examined for the light-resistance and the tone, in the same manner as for Example 5. The results are shown in Table 6.

131 37 9~
- 253 ~

,7~ ~,., , , ~ ;

u~ I
.
_ U '~ ~!
V a ~ ~ ~ o 1` ~D ~ O v~
' ~ ~` ~ (`I ~ ~I N ~`I ~ ~`I .

V C~
~ ~ v ~ ~ v ~0 ~
~ ~ V ~ V
C
~ ~ .e > C
u 0 o 3 a) _ a a a a a a ~ a a ~ l l l l l l l l l l E-~ ~' --~1 . In Ut U7 ~ U~ U7 ~ U7 a~
.
~ ~ l l l l l l l l l l l j~ H i~
!!l 8~ ~1 ~ ~ l l l l l l l l l l .~ P.
_ ~
~0 O
B B B B B B B B
co ,~ 8 .,C, co ., co .,~ co ~ o ~ o ~ ~ ~o " o C ~o 'c' ~o ~ ~o ~C ~o " o ~C ~o ~
2; c c U ~ U ~ o ~ ~ u ~ U ~ ~ s ,a ~
Ql ~ V
~ ~ e ~C~ ~C~ ~C~ C~
0 O~
~ C ~ ~ C ~ ~ ~ C C ~ ~ C C
co o~ n o ~1 ~ ~ ~ ~

-~ 1313791 - 254a -* 0.5 mol metal complex, 1 mol piperazine, 1 mol chroman and 1 mol indane were added to 1 mol coupler.
As illustrated by Table 6, it is apparent thàt samples 121, 139 ~ 145 employing not only a metal complex of the in-vention but image stabilizers have the excellent light-resistance property as well as the correct tone.
Additionally, the results for samples 122, 141 ~ 144 illustrate that the employment of an organic solvent having a low dielectric constant is especially effective in improving the light-resistance property.

Claims (14)

1. A silver halide photographic light sensitive material char-acterized in that said material comprises at least one magenta dye image-forming coupler expressed by the following general formula [1], at least one compound expressed by the following general formula [XII] and at least one compound selected from those expressed by the following general formulas [XIIIa] and [XIIIb]:
General formula [1]
[In the formula, above, Z represents a plurality of non-(to be continued) metal atoms necessary to complete a heterocyclic ring contain-ing a nitrogen atom; X represents a hydrogen atom or a substi-tuent capable of being split off upon reaction with an oxida-tion product of a color developing agent, and, R represents a hydrogen atom or a substituent.], and;
General formula [XII]
[In the formula, R1 represents an aliphatic group, a cycloalkyl group, an aryl group or a heterocyclic group. Y1 represents a group of nonmetal atoms, necessary to complete a piperazine ring or a homopiperazine ring together with a nitrogen atom], and;
General formula [XIIIa]
[In the formula, R2 and R5 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group; R3 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group or a heterocyclic group; R4 re-presents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acylamine group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group; provided that R3 and R4 may be combined with each other to form a 5- or 6-membered ring, and that R3 and R4 may form a methylenedioxy ring; Y2 represents a group of atoms necessary to complete a chroman ring or a coumarane ring.], and;
General formula [XIIIb]
In the formula, R12 and R14 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxy-carbonyl group; R13 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxy-carbonyl group provided that R13 and R14 may be combined with each other to form a 5- or a 6-membered hydrocarbon ring; and Y3 represents a group of atoms necessary to complete an indane ring.]

2. The silver halide photographic light sensitive material according to Claim 1, characterized in that said magenta dye image forming coupler is a compound expressed by the following general formula [VIII]:
General formula [VIII]
[In the formula, above, R1, X and Z1 respectively have the same meanings as R, X and Z in general formula [I]].

3. The silver halide photographic light sensitive material according to Claim 1, characterized in that said magenta dye image forming coupler is a compound expressed by any of the following general formulas [II] ~ [VII]:
General formula [II]
General formula [III]

General formula [IV]

General formula [V]

General formula [VI]

General formula [VII]

[In the formula, above, R1 ~ R8 as well as X have the same meanings as R and X in general formula [1], mentioned previously]

4. The silver halide photographic light sensitive material according to Claim 1, characterized in that said magenta dye image forming coupler is a compound expressed by the following general formula [XI]:
General formula [XI]

[In the formula, above R and X respectively have the same meanings as R and X in general formula [I], and R1 represents an alkylene group, and, R2 represents any one of an alkyl group, a cycloalkyl group and an aryl group.].

5. The silver halide light sensitive photographic material according to anyone of Claims 1, 2, 3 or 4, characterized in that R or R1 in general formulas [1] ~ [VII] as well as [VI] is a group expressed by general formula [IX]:
General formula [IX]

[In the formula, above, R9, R10 and R11 independently re-present a hydrogen atom, halogen atom, or any one of the fol-lowing groups which may have a substituent:
an alkyl group, a cycloalkyl group, an alkenyl group, a cyclo-alkenyl group, an alkinyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, residue of spiro compound, residue of bridged hydrocarbon compound, alcoxy group, aryloxy group, hetero-cyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureide group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group, provided that at least two of R9, R10 and R11 are atoms or groups other a hydrogen atom and that at least two of R9, R10 and R11, mentioned above, R9 and R10, for example, may cmobine with each other to form a ring, whichever saturated or unsatured (for example, a cycloalkane, cycloalkene and heterocycle), wherein R11 may further combine with the ring, above, to form a residue of a bridged-hydro-carbon compound.]

6. The silver halide photogrpahic light sensitive material according to Claim 1, characterized in that said compound ex-pressed by general formula [XII] is either a piperazine com-pound expressed by the following general formula [XII'] or a homopiperazine compound expressed by the following general formula [XII"]:
General formula [XII']

[In the formula, above, R1 represents an alkyl group, cycloalkyl group or aryl group; R1" represents a hydrogen atom, alkyl group, cycloalkyl group or aryl group.
General formula [XII"]

[In the formula, above, R1' and R1" respectively repre-sent the same atom or group as R1' and R1" in the above-mentioned general formula [II'.]

7. The silver halide photogrpahic light sensitive material according to Claim 1, characterized in that said compound ex-pressed by general formula [XIIIa] is selected from compounds expressed by general formulas [XIVa], [XVa], [XVIa], [XVIIa]
and [XVIIIa]:

General formula [XIVa]

General formula [XVa]

General formula [XVIa]

General formula [XVIIa]

General formula [XVIIIa]

R2, R3, R4 and R5 in general formulas [XIVa], [XVa¦, [XVIa], [XVIIa] and [XVIIIa] respectively have the same mean-ing as those in general formula [XIIIa], mentioned previously;
R6, R7, R8, R9, R10 and R11 independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group or a heterocyclic group, provided that R6 and R7, or, R7 and R8, or, R8 and R9, or, R9 and R10, or, R10 and R11, in the general formulas above, may mutually cyclize to form a hydrocarbon ring which may have an alkyl group as a substituent.

8. The silver halide photographic light sensitive material according to Claim 1, characterized in that said compound ex-pressed by general formula [XIIIb] is selected from compounds expressed by general formulas [XIVb] - [XVIb]:

General formula [XIVb]

General formula [XVb]

General formula [XVIb]

[Wherein, R12, R13 and R14 in general formulas [XIVb]~
[XVIb] have the same meanings as in general formula [XIIIb];
R15, R16 , R17, R18, R19 and R20 independently represent any one of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, a hydroxy group, an aryl group, an aryloxy group or a heterocyclic group provided that R15 and R16, or, R16 and R17, or, R17 and R18, or, R18 and R19, or, R19 and R20, may mutually cyclize to form a hydrocarbon ring which may have an alkyl group as a substituent.

9. The silver halide photographic light sensitive material according to Claim 1, characterized in that said material con-tains at least one metallic complex wherein an optical quench-ing rate of a singlet oxygen is more than 3 x 107M-1?sec-1;

10. The silver halide photogrpahic light sensitive material according to Claim 5, characterized in that said material con-tains at least one metallic complex wherein an optical quench-ing rate of a singlet oxygen is more than 1 x 108M-1?sec-1;

11. The silver halide photographic light sensitive material according to Claim 9, characterized in that said material com-plex is selected from compounds expressed by the following general formulas [L - I] - [L - IV];
General formula [L - I]

General formula [L - II]

General formula [L - III]

[In general formulas [L - I], [L - II] and [L - III], M
represents a metallic atom.]
X1 and X2 independently represent an oxygen atom, a sul-fur atom or a -NR7- (R7 represents a hydrogen atom, an alkyl group, an aryl group or a hydroxy group); X3 represents a hy-droxy group or a mercapto group; Y represents an oxygen atom or a sulfur atom. R3, R4, R5 and R6 independently represent any one of a hydrogen atom, a halogen atom, a cyano group, or, an alkyl group, an aryl group, a cycloalkyl group or a hetero-cyclic group which directly or via a bivalent bonding group connects with a carbon atom, provided that at least one com-bination of R3 and R4 or R5 and R6, may form a 5- or 6-membered ring by mutually combining with each other together with a carbon atom;
Z0 represents a compound which may be coordinated at the position M or a residue derived from such a compound.]

General formula [L - IV]

[In the formula, above, R21, R22, R23 and R24 independ-ently represent any one of a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an alkyl group, an aryl group, a cycloalkyl group or a heterocyclic group which may directly or indirectly via a divalent group combine to a carbon atom on a benzene ring, provided that R21 and R22, R22 and R23 or R23 and R24 may mutually be combine to form a 6-membered ring;
R25 represents a hydrogen atom, an alkyl group, or an aryl group; A represents a hydrogen atom, an alkyl group, an aryl group or a hydroxy group; and M represents a metallic atom.]

12. The silver halide photographic light sensitive material according to Claim 11, characterized in that the control metal (M) is a transitional metal.

13. The silver halide photographic light sensitive material according to Claim 12, characterized in that the central metal (M) is selected from metallic atoms, Fe, Co, Ni, Pd, Al and Pt.

14. The silver halide photographic light sensitive material according to Claim 13, characterized in that the central metal is Ni.