Silver halide color photographic material containing a magenta color image-forming coupler

A silver halide color photographic material is disclosed which contains a magenta color image-forming coupler represented by the following formula (I) and a compound represented by the following formula (II): ##STR1## wherein Z represents the group of nonmetallic atoms necessary for forming a nitrogen-containing heterocyclic ring, provided that the ring to be formed by said Z may have a substitutent; PA0 X represents a hydrogen atom or a substituent capable of leaving upon reaction with the oxidized product of a color developing agent; and PA0 R represents a hydrogen atom or a substituent. ##STR2## wherein R.sub.1 is an aliphatic group, a cycloalkyl group or an aryl group; and Y represents the group of nonmetallic atoms necessary for forming a 5- to 7-membered heterocyclic ring taken together with the nitrogen atom, provided that at least two hetero atoms among the heterocyclic ring-forming nonmetallic atoms including the nitrogen atom are not adjacent to each other.

FIELD OF THE INVENTION 
The present invention relates to a silver halide color photographic 
material, and more particularly, to a silver halide color photographic 
material that forms a dye image which is stable against heat or light and 
in which no stain is likely to occur. 
BACKGROUND OF THE INVENTION 
As is well known, in color development following the image-wise exposure of 
a silver halide color photographic material, the oxidized product of an 
aromatic primary amine color developing agent enters into coupling 
reaction with a color former to form a color image composed of, for 
example, indophenol, indoaniline, indamine, azomethine, phenoxazine, 
phenazine or other dyes similar thereto. In this photographic process, 
color reproduction is usually achieved by the substractive process using a 
silver halide color photographic material wherein blue-, green- and 
red-sensitive silver halide emulsion layers contain color formers, or 
couplers that will develop colors which are the respective complements of 
blue, green and red, namely, yellow, magenta and cyan colors. 
An illustrative coupler used to form a yellow color image is 
acylacetanilide compound. Exemplary magenta image forming couplers include 
pyrazolone, pyrazolobenzimidazole, pyrazolotriazole and indazolone 
compounds. Among the couplers commonly used for cyan image formation are 
included phenolic and naphtholic compounds. 
The dye image formed by the coupling reaction with such color formers and 
the oxidation product of aromatic primary amine color developing agent are 
required to undergo no discoloration or fading even if they are exposed to 
light or stored under hot and humid atmosphere for a prolonged period. It 
is also required that the background of a silver halide color photographic 
material (to be hereunder referred to simply as a color photographic 
material) or the areas where no color has formed should not undergo any 
yellow staining (hereunder Y staining) as a result of exposure to light or 
moist heat. 
Magenta couplers are much more sensitive than yellow and cyan couplers to Y 
staining in the background caused by heat or moist heat as well as to the 
fading of the image areas resulting from prolonged exposure to light, and 
this has often caused serious problems in conventional color photography. 
Couplers extensively used for magenta dye formation are 
1,2-pyrazolo-5-ones. Dyes produced from such compounds generally have 
primary absorption at about 550 nm but they also have secondary absorption 
at about 430 nm. In order to minimize such secondary absorption, various 
efforts have been made. For example magenta couplers having an anilino 
group at 3-position of 1,2-pyrazolo-5-ones have relatively small degree of 
secondary absorption and are particularly useful for obtaining color image 
in print format. Details of this technique are found in U.S. Pat. No. 
2,343,703 and British Pat. No. 1,059,994. However, such substituted 
magenta couplers are very poor in image keeping quality, especially in the 
fastness of color image to light. In addition, the background is highly 
sensitive to Y staining. 
Other magenta couplers that have been proposed as means capable of reducing 
the secondary absorption at about 430 nm include pyrazolobenzimidazoles 
(British Pat. No. 1,047,612), indazolones (U.S. Pat. No. 3,770,447) and 
pyrazolotriazoles (U.S. Pat. No. 3,725,067 and British Pat. Nos. 1,252,418 
and 1,334,515). Dyes formed from the 1H-pyrazolo-[3,2-C]-s-triazole type 
couplers described in U.S. Pat. No. 3,725,067 and British Pat. Nos. 
1,252,418 and 1,334,515 are preferred in terms of color reproduction over 
dyes formed from the 1,2-pyrazolo-5-ones having an anilino group at 
3-position because the former has a far smaller secondary absorption at 
about 430 nm. Furthermore, the background of photographic materials using 
the 1H-pyrazolo-[3,2-C]-s-triazole type couplers as magenta couplers has 
extremely low sensitivity to Y staining resulting from exposure to light, 
heat or moisture. 
However, the azomethine dye formed from the 1H-pyrazolo-[3,2-C]-s-triazole 
type couplers has a very small degree of fastness to light. In addition, 
such azomethine dye is highly likely to discolor upon exposure to light 
and has yet to be used commercially in color photographic materials, 
especially in color prints which are subject to considerable degradation 
resulting from the discoloration of azomethine dyes. 
Unexamined Published Japanese Patent Application No. 125732/1984 proposes a 
technique for improving the light fastness of the magenta dye image from 
the 1H-pyrazolo-[3,2-C]-s-triazole type coupler by using it in combination 
with a phenolic compound or a phenyl ether compound. However, even this 
technique is not completely satisfactory in preventing the magenta dye 
image from fading upon exposure to light, and is practically incapable of 
preventing the light discoloration of such dye image. 
SUMMARY OF THE INVENTION 
One object, therefore, of the present invention is to provide a color 
photographic material that is capable of faithful color reproduction and 
which exhibits a highly improved light fastness in magenta dye image. 
Another object of the invention is to provide a color photographic material 
producing a magenta dye image that experiences a minimal degree of 
discoloration upon exposure to light. 
A further object of the invention is to provide a color photographic 
material that is protected against the occurrence of Y stain in the 
background resulting from exposure to light or moist heat. 
These objects of the invention can be achieved by a silver halide color 
photographic material containing a magenta color image-forming coupler 
represented by the following formula (I) and a compound represented by the 
following formula (II): 
##STR3## 
wherein Z represents the group of nonmetallic atoms necessary for forming 
a nitrogen-containing heterocyclic ring, provided that the ring to be 
formed by said Z may have a substituent; 
X represents a hydrogen atom or a substituent capable of leaving upon 
reaction with the oxidized product of a color developing agent; and 
R represents a hydrogen atom or a substituent. 
##STR4## 
wherein R.sub.1 is an aliphatic group, a cycloalkyl group or an aryl 
group; and 
Y represents the group of nonmetallic atoms necessary for forming a 5- to 
7-membered heterocyclic ring taken together with the nitrogen atom, 
provided that at least two hereto atoms among the heterocyclic 
ring-forming nonmetallic atoms including the nitrogen atom are not 
adjacent to each other. 
In the magenta coupler of formula (I), the substituent represented by R 
includes, for example, a halogen atom, an alkyl group, a cycloalkyl group, 
an alkenyl group, a cycloalkenyl 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, a 
spirocompound residue, a bridged hydrocarbon compound residue, an alkoxy 
group, an aryloxy group, a heterocyclicoxy group, a siloxy group, an 
acyloxy group, a carbamoyloxy group, an amino group, an acylamino group, a 
sulfonamide group, an imido group, a ureido group, a sulfamoylamino group, 
an alkoxycarbonylamino group, an aryloxycarbonylamino group, an 
alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an 
arylthio group and a heterocyclicthio group. 
The halogen atom includes, for example, chlorine and bromine atoms, the 
chlorine atom being particularly preferable. 
The alkyl group represented by R is preferably one having 1 to 32 carbon 
atoms, the alkenyl group and the alkinyl group are preferably those having 
2 to 32 carbon atoms, and the cycloalkyl group and the cycloalkenyl group 
are preferably those having 3 to 12, particularly 5 to 7, carbon atoms, 
the alkyl, alkenyl and alkinyl groups each including those having a 
straight or branched chain. 
These alkyl, alkenyl, alkinyl, cycloalkyl and cycloalkenyl groups each may 
have one or more substituents. Such substituents include, in addition to 
an aryl group, a cyano group, a halogen atom, a heterocyclic group, a 
cycloalkyl group, a cycloalkenyl group, a spiro-compound residue and a 
bridged hydrocarbon compound residue, for example, those substituted 
through the carbonyl group, such as acyl, carboxy, carbamoyl, 
alkoxycarbonyl and aryloxycarbonyl groups, and those substituted through 
the hetero atom, for example, those substituted through the oxygen atom, 
such as hydroxy, alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy and 
carbamoyloxy groups, those substituted through the nitrogen atom, such as 
nitro, amino (including dialkylamino and the like), sulfamonylamino, 
alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfoneamido, imido 
and ureido groups, those substituted through the sulfur atom, such as 
alkylthio, arylthio, heterocyclicthio, sulfonyl, sulfinyl and sulfamoyl 
groups, and those substituted through the phosphorus atom, such as a 
phosphonyl group and the like. 
Examples of the alkyl group represented by R include, for example, methyl, 
ethyl, isopropyl, t-butyl, pentadecyl, heptadecyl, 1-hexylnonyl, 
1,1'-dipentylnonyl, 2-chloro-t-butyl, trifluoromethyl, 1-ethoxytridecyl, 
1-methoxyisopropyl, methanesulfonylethyl, 2,4-di-t-amylphenoxymethyl, 
anilino, 1-phenylisopropyl, 3-m-butanesulfonaminophenoxypropyl, 
3-4'-{.alpha.-[4"(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino}phenylp 
ropyl, 3-{4'-[.alpha.-(2",4"-di-t-amylphenoxy)butaneamido]phenyl}-propyl, 
4-[.alpha.-(O-chlorophenoxy)tetradecanamidophenoxy]-propyl, allyl, 
cyclopentyl and cyclohexyl groups. 
The aryl group represented by R is preferably a phenyl gruop, and may have 
a substituent such as an alkyl, alkoxy or acylamino group. 
Examples of the aryl group include phenyl, 4-t-butylphenyl, 
2,4-di-t-amylphenyl, 4-tetradecaneamidophenyl, hexadecyl-oxyphenyl and 
4'-[.alpha.-(4"-t-butylphenoxy)tetoradecaneamido]phenyl groups. 
The heterocyclic group represented by R is preferably a 5- to 7-membered 
heterocyclic ring, and may be substituted or may be condensed. Examples of 
the heterocyclic group include 2-furyl, 2-thienyl, 2-pyrimidinyl and 
2-benzothiazonyl groups. 
The acyl group represented by R includes, for example, an alkylcarbonyl 
group such as acetyl, phenylacetyl, dodecanoyl and 
.alpha.-2,4-di-t-amylfenoxybutanoyl groups, and an arylcarbonyl group such 
as benzoyl, 3-pentadecycloxybenzoyl and p-chlorobenzoyl groups. 
The sulfonyl group represented by R includes, for example, an alkylsulfonyl 
group such as methylsulfonyl and dodecylsulfonyl groups, and an 
arylsulfonyl group such as benzenesulfonyl and p-toluenesulfonyl groups. 
The sulfinyl group represented by R includes, for example, an alkylsulfinyl 
group such as ethylsulfinyl, octylsulfinyl and 3-fenoxybutylsulfinyl 
groups and an arylsulfinyl group such as phenylsulfinyl and 
m-pentadecylphenylsulfinyl groups. 
The phosphonyl group represented by R includes, for example, an 
alkylphosphonyl group such as butyloxyoctyl phosphonyl group, an 
alkoxyphosphonyl group such as octyloxyphosphonyl group, an 
aryloxyphosphonyl group such as phenoxyphosphonyl group and an 
arylphosphonyl group such as phenylphosphonyl group. 
The carbamoyl group represented by R includes, for example, those 
substituted with an alkyl or aryl (preferably phenyl) group, such as, 
N-methylcarbamoyl, N,N-dibutylcarbamoyl, 
N-(2-pentadecyloctylethyl)carbamoyl, N-ethyl-N-dodecylcarbamoyl and 
N-{3-(2,4-di-t-amylphenoxy)-propyl}carbamoyl group. 
The sulfamoyl group represented by R includes, for example, those 
substituted with an alkyl or aryl (preferably phenyl) group, such as 
N-propylsulfamoyl, N,N-diethylsulfamoyl, 
N-(2-pentadecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl and 
N-phenylsulfamoyl groups. 
The spiro-compound residue represented by R includes, for example 
spiro[3,3]heptan-1-yl and the like. 
The bridged hydrocarbon compound residue represented by R includes, for 
example, bicyclo[2,2,1]heptane-1-yl, tricyclo[3,3,1,1.sup.3,7 ]decane-1-yl 
and 7,7-dimethyl-bicyclo[2,2,1]heptane-1-yl. 
The alkoxy group reprented by R includes, for example, those substituted 
further with such a substituent(s) as is shown above with the alkyl group, 
such as methoxy, propoxy, 2-ethoxyethoxy, pentadecyloxy, 
2-dodecyloxyethoxy and phenethyloxyethoxy. 
The aryloxy group represented by R is preferably a phenyloxy group, and 
includes, for example, those of which aryl nucleus is further subsituted 
with such a substituent(s) or an atom(s) as is shown above with the aryl 
group, such as phenoxy, p-t-butylphenoxy and m-pentadecylphenoxy groups. 
The heterocyclicoxy group represented by R is preferably one having a 5- to 
7-membered heterocyclic ring, and includes those of which heterocyclic 
ring has a substituent, such as 3,4,5,6-tetrahydropyranyl-2-oxy and 
1-phenyltetrazole-5-oxy groups. 
The siloxy group represented by R includes those substituted with an alkyl 
group, for example, trimethylsiloxy, triethylsiloxy and 
dimethylbutylsiloxy groups. 
The acyloxy group represented by R includes, for example, alkylcarbonyloxy 
and arylcarbonyloxy groups, and further includes those having a 
substituent(s) such as acetyloxy, .alpha.-chloroacetyloxy and benzoyloxy 
groups. 
The carbamoyloxy group represented by R includes those substituted with an 
alkyl or aryl group, such as N-ethylcarbamoyloxy, N,N-diethylcarbamoyloxy 
and N-phenylcarbamoyloxy groups. 
The amino group represented by R includes those substituted with an alkyl 
or aryl (preferably phenyl) group, such as ethylamino, anilino, 
m-chloroanilino, 3-pentadecyloxycarbonylanilino and 
2-chloro-5-hexadecaneamidoanilino groups. 
The acylmaino group represented by R includes alkylcarbonylamino and 
arylcarbonylamino (preferably phenylcarbonylamino) groups, and further 
includes those having a substituent(s) such as acetamido, 
.alpha.-ethylpropaneamido, N-pnenylacetamido, dodecaneamido, 2,4-di-t- 
amylphenoxyacetamido and .alpha.-3-t-butyl-4-hydroxyphenoxybutaneamido 
groups. 
The sulfonamido group represented by R includes alkylsulfonylamino and 
arylsulfonylamino groups, and further includes those having a 
substituent(s), such as methylsulfonylamino, pentadecylsulfonylamino, 
benzensulfonamido, p-toluenesulfonamido and 
2-methoxy-5-t-amylbenzenesulfonamido groups. 
The imido group represented by R includes those which are open-chained or 
close-chained, and further includes those having a substituent(s), such 
as, succinimido, 3-heptadecylsuccinimido, phthalimido and glutarimido 
groups. 
The ureido group represented by R includes those substituted with an alkyl 
or aryl (preferably phenyl) group, such as N-ethylureido, 
N-methyl-N-decylureido, N-phenylureido and N-p-tolylureido groups. 
The sulfamoylamino group represented by R includes those substituted with 
an alkyl or aryl (preferably phenyl) group, such as 
N,N-dibutylsulfamoylamino, N-methylsulfamoylamino and 
N-phenylsulfamoylamino groups. 
The alkoxycarbonylamino group represented by R includes those having a 
substituent(s), such as methoxycarbonylamino, methoxyethoxycarbonylamino 
and octadecyloxycarbonylamino groups. 
The aryloxycarbonylamino group represented by R includes those having a 
substituent(s), such as phenoxycarbonylamino and 
4-methylphenoxycarbonylamino groups. 
The alkoxycarbonyl group represented by R includes those having a 
substituent(s), such as methoxycarbonyl, butyloxycarbonyl, 
dodecyloxycarbonyl, octadecyloxycarbonyl, ethoxymethoxycarbonyloxy and 
benzyloxycarbonyl groups. 
The aryloxycarbonyl group represented by R includes those having a 
substituent(s), such as phenoxycarbonyl, p-chlorophenoxycarbonyl and 
m-pentadecyloxyphenoxycarbonyl groups. 
The alkylthio group represented by R includes those having a 
substituent(s), such as ethylthio, dodecylthio, octadodecylthio, 
phenethylthio and 3-phenoxypropylthio groups. 
The arylthio group represented by R is preferably a phenylthio group, and 
includes those having a substituent(s), such as phenylthio, 
p-methoxyphenylthio, 2-t-octylphenylthio, 3-octadecylphenylthio, 
2-carboxyphenylthio and p-acetaminophenylthio groups. 
The heterocyclicthio group, represented by R is preferably a 5- to 
7-membered heterocyclicthio group, and includes those having a condensed 
ring or having a substituent(s). Examples of such heterocyclicthio group 
include 2-pyridylthio, 2-benzothiazolylthio and 
2,4-diphenoxy-1,3,5-triazol-6-thio groups. 
The substituent represented by X that is capable of leaving upon reaction 
with the oxidized product of a color developing agent includes, for 
example, those substituted through the carbon, oxygen, sulfur or nitrogen 
atom other than the halogen atom (chlorine, bromine or fluorine atom). 
The groups which are substituted through the carbon atom include, in 
addition to the carboxyl group, a group represented by the following 
formula: 
##STR5## 
(wherein R.sub.1 ' is the same in meaning as said R; Z' is the same in 
meaning as said Z; and R.sub.2 ' and R.sub.3 ' each represents a hydrogen 
atom, an aryl, alkyl or heterocyclic group), a hydroxymethyl group and a 
triphenylmethyl group. 
The groups which are substituted through the oxygen atom include, for 
example, alkoxy, aryloxy, heterocyclicoxy, acyloxy, sulfonyloxy, 
alkoxycarbonyloxy, aryloxycarbonyloxy, alkyloxalyloxy and alkoxyoxalyloxy 
groups. 
The alkoxy group includes those having a substituent(s), such as ethoxy, 
2-phenoxyethoxy, 2-cyanoethoxy, phenethyloxy, and p-chlorobenzyloxy 
groups. 
The aryloxy group is preferably a phenoxy group, and includes those having 
a substituent(s). Examples of such aryloxy group include phenoxy, 
3-methylphenoxy, 3-dodecylphenoxy, 4-methanesulfoneamidophenoxy, 
4-[.alpha.-(3'-pentadecylphenoxy)butaneamido]phenoxy, 
hexadecylcarbamoylmethoxy, 4-cyanophenoxy, 4-methanesulfonylphenoxy, 
1-naphthyloxy and p-methoxyphenoxy groups. 
The heterocyclicoxy group is preferably a 5- to 7-membered heterocyclicoxy 
group, and may be a condensed ring or include those having a 
substituent(s). Examples of such heterocyclicoxy group include 
1-phenyltetrazolyloxy and 2-benzothiazolyloxy groups. 
The acyloxy group includes, for example, an alkylcarbonyloxy group such as 
acetoxy and butanoyloxy groups, an alkenylcarbonyloxy group such as a 
cinnamoyloxy group, and an arylcarbonyloxy group such as a benzoyloxy 
group. 
The sulfonyloxy group includes, for example, butanesulfonyloxy and 
methanesulfonyloxy groups. 
The alkoxycarbonyloxy group includes, for example, ethoxycarbonyloxy and 
benzyloxycarbonyloxy groups. 
The aryloxycarbonyloxy group includes a phenoxycarbonyloxy group and the 
like. 
The alkyloxyalyloxy group includes, for example, a methyloxyalyloxy group. 
The alkoxyoxalyloxy group includes an ethoxyoxalyloxy group and the like. 
The group which is substituted through the sulfur atom includes, for 
example, alkylthio, arylthio, heterocyclicthio and 
alkyloxythiocarbonylthio groups. 
The alkylthio group includes butylthio, 2-cyanoethylthio, phenetylthio and 
benzylthio groups. 
The arylthio group includes phenylthio, 4-methanesulfoneamidophenylthio, 
4-dodecylphenetylthio, 4-nonafluoropentaneamidophenetylthio, 
4-carboxyphenylthio and 2-ethoxy-5-t-butylphenylthio groups. 
The heterocyclicthio group includes, for example, 
1-phenyl-1,2,3,4-tetrazolyl-5-thio and 2-benzothiazolylthio groups. 
The alkyloxythiocarbonylthio group includes a dodecyloxythiocarbonylthio 
group and the like. 
The group which is substituted through the nitrogen atom includes, for 
example, one represented by the formula 
##STR6## 
wherein R.sub.4 ' and R.sub.5 ' each represents a hydrogen atom, an alkyl, 
aryl, heterocyclic, sulfamoyl, carbamoyl, acryl, sulfonyl, aryloxycarbonyl 
or alkoxycarbonyl group, and R.sub.4 ' and R.sub.5 ' may cooperate to form 
a heterocyclic ring, provided that R.sub.4 ' and R.sub.5 ' are not 
hydrogen atoms at the same time. 
The alkyl group may be straight-chained or branced and is preferably one 
having 1 to 22 carbon atoms. Also, the alkyl group may include those 
having a substituent(s). Examples of such substituent include, for 
example, aryl, alkoxy, aryloxy, alkylthio, arylthio, alkylamino, 
arylamino, acylamino, sulfoneamido, imino, acyl, alkylsulfonyl, 
arylsulfonyl, carbamoyl, sulfamoyl, alkoxycarbonyl, aryloxycarbonyl, 
alkyloxycarbonylamino, aryloxycarbonylamino, hydroxy, carboxyl and ciano 
groups and halogen atom. Examples of such alkyl group includes, for 
example, ethyl, octyl, 2-ethylhexyl and 2-chloroethyl group. 
The aryl group represented by R.sub.4 ' or R.sub.5 ' is preferably one 
having 6 to 32 carbon atoms, particularly a phenyl or naphtyl group, and 
may include those having a substituent(s). Such substituent includes a 
substituent for the alkyl group represented by R.sub.4 ' or R.sub.5 ' and 
an alkyl group. Examples of the aryl group include, for example, phenyl, 
1-naphtyl and 4-methylsulfonylphenyl groups. 
The heterocyclic group represented by R.sub.4 ' or R.sub.5 ' is preferably 
a 5- or 6-membered ring, and may be a condensed ring or include those 
having a substituent(s). Examples of such heterocyclic group include 
2-furyl, 2-quinolyl, 2-pyrimidyl, 2-benzothiazolyl and 2-pyridyl groups. 
The sulfamoyl group represented by R.sub.4 ' or R.sub.5 ' includes 
N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl and 
N,N-diarylsulfamoyl groups, and these alkyl and aryl groups may have such 
a substituent(s) as is mentioned with respect to the alkyl and aryl 
groups. Examples of such sulfamoyl group includes, for example, 
N,N-diethylsulfamoyl, N-methylsulfamoyl, N-dodecylsulfamoyl and 
N-p-tolylsulfamoyl groups. 
The carbamoyl group represented by R.sub.4 ' or R.sub.5 ' includes 
N-alkylcarbamoyl, N,N-dialkylcarbamoyl, N-arylcarbamoyl and 
N,N-diarylcarbamoyl groups, and these alkyl and aryl groups may have such 
a substituent(s) as is mentioned with respect to the alkyl and aryl 
groups. Examples of such carbamoyl group include, for example, 
N,N-diethylcarbamoyl, N-methylcarbamoyl, N-dodecylcarbamoyl, 
N-p-cianophenylcarbamoyl and N-p-tolylcarbamoyl groups. 
The acyl group represented by R.sub.4 ' or R.sub.5 ' includes, for example, 
alkylcarbonyl, arylcarbonyl and heterocycliccarbonyl groups, and the 
alkyl, aryl and heterocyclic groups may have a substituent(s). Examples of 
such acyl group include, for example, hexafluorobutanoyl, 
2,3,4,5,6-pentafluorobenzoyl, acetyl, benzoyl, naphtoyl and 
2-furylcarbonyl groups. 
The sulfonyl group represented by R.sub.4 ' or R.sub.5 ' includes 
alkylsulfonyl, arylsulfonyl and heterocyclicsulfonyl groups, and may have 
a substituent(s). Examples of such sulfonyl group include, for example, 
ethanesulfonyl, benzenesulfonyl octanesulfonyl, naphthalenesulfonyl and 
p-chlorobenzenesulfonyl groups. 
The aryloxycarbonyl group represented by R.sub.4 ' or R.sub.5 ' may have 
such a substituent(s) as is mentioned with respect to the aryl group, and 
includes a phenoxycarbonyl group and the like. 
The alkoxycarbonyl group represented by R.sub.4 ' or R.sub.5 ' may have 
such a substituent(s) as is mentioned with respect to alkyl group, and 
includes methoxycarbonyl, dodecyloxycarbonyl and benzyloxycarbonyl groups. 
The heterocyclic ring which is formed through cooperation of R.sub.4 ' and 
R.sub.5 ' is preferably a 5- or 6-membered ring, may be saturated or 
unsaturated, may or may not be an aromatic ring, or may be a condensed 
ring. Examples of such heterocyclic ring include, for example, 
N-phthalimido, N-succinimide, 4-N-urazolyl, 1-N-hydantoinyl, 
3-N-2,4-dioxooxazolidinyl, 2-N-1,1-dioxo-3-(2H)-oxo-1,2-benzthiazolyl, 
1-pyrrolyl, 1-pyrrolidinyl, 1-pyrazolyl, 1-pyrazolidinyl, 1-piperidinyl, 
1-pyrrolinyl, 1-imidazolyl, 1-imidazolinyl, 1-indolyl, 1-isoindolinyl, 
2-iso-indolyl, 2-isoindolinyl, 1-benzotriazolyl, 1-benzoimidiazolyl, 
1-(1,2,4-triazolyl), 1-(1,2,3-triazolyl), 1-(1,2,3,4-tetrazolyl), 
N-morpholinyl, 1,2,3,4-tetrahydroquinolyl, 2-oxo-1-pyrrolidinyl, 
2-1H-pyridone, phthalazione and 2-oxo-1-piperidinyl groups. These 
heterocyclic groups may be substituted by alkyl, aryl, alkyloxy, aryloxy, 
acyl, sulfonyl, alkylamino, arylamino, acylamino, sulfoneamino, carbamoyl, 
sulfamoyl, alkylthio, arylthio, ureido, alkoxycarbonyl, aryloxycarbonyl, 
imido, nitro, cyano, carboxyl groups as well as by a halogen atom and the 
like. 
The nitrogen-containing heterocyclic ring which is formed by Z or Z' 
includes pyrazol, imidazol, triazol and tetrazol rings, and may have such 
a substituent(s) as is mentioned with respect to R. 
When the substituent(s) (for example either of R and R.sub.1 to R.sub.8) on 
the heterocyclic ring in formula (I) and in formulas (III) to (IX) to be 
mentioned later has the following formula: 
##STR7## 
(wherein R", X and Z" are the same in meaning as R, X and Z in formula 
(I), respectively), the coupler formed is the so-called bis-type coupler, 
which is included in the present invention. The ring which is formed by Z, 
Z', Z" as well as by Z.sub.1 to be stated later may be condensed with 
another ring (for example 5- to 7-membered cycloalkene). For example, in 
formula (VI), R.sub.5 and R.sub.6, and in formula (VII), R.sub.7 and 
R.sub.8, may cooperate to form a ring (for example, 5- to 7-membered 
cycloalkene, or benzene), respectively. 
The coupler represented by formula (I) preferably includes, for example, 
those represented by the following formulas (III) to (VIII): 
##STR8## 
wherein R.sub.1 to R.sub.8 and X are the same in meaning as R and X 
mentioned above. 
The coupler of formula (I) is preferably one represented by the following 
formula (IX): 
##STR9## 
wherein R.sub.1, X and Z.sub.1 are the same in meaning as R, X and Z in 
formula (I). 
Of the magenta couplers represented by formulas (III) to (VIII), those 
represented by formula (III) are particularly preferable. 
With respect to the substituent(s) on the heterocyclic ring in formulas (I) 
and (II) to (IX), R in formula (I) and R.sub.1 in formulas (III) to (IX) 
are preferable when they satisfy the following requirement 1, the same R 
and R.sub.1 are more preferable when they satisfy the following 
requirements 1 and 2, and the same R and R.sub.1 are most preferable when 
they satisfy all of the following requirements 1, 2 and 3: 
Requirement 1: The root atom bonded directly to the heterocyclic ring is a 
carbon atom. 
Requirement 2: Said carbon atom has only one hydrogen atom or has no 
hydrogen atom at all, bonded thereto. 
Requirement 3: The bonds between said carbon atom and adjacent atoms are 
all single bonds. 
The most preferable substituents R and R.sub.1 on the heterocyclic ring are 
those represented by the following formula (X): 
##STR10## 
wherein R.sub.9, R.sub.10 and R.sub.11 each represents a hydrogen atom, a 
halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a 
cycloalkenyl group, an alkinyl group, an aryl group, a heterocyclic group, 
an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, 
carbamoyl group, a sulfamoyl group, a cyano group, a spiro-compound 
residue, a bridged hydrocarbon compound residue, an alkoxy group, an 
aryloxy group, a heterocyclicoxy group, a siloxy group, an acyloxy group, 
a carbamoyloxy group, an amino group, an acylamino group, a sulfonamide 
group, an imido group, a ureido group, a sulfamoylamino group, an 
alkoxycarbonylamino group, an aryloxycarbonylamino group, an 
alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an 
arylthio group or a heterocyclicthio group, provided that at least two of 
R.sub.9, R.sub.10 and R.sub.11 are not hydrogen atoms. 
Two of R.sub.9, R.sub.10 and R.sub.11, for example, R.sub.9 and R.sub.10 
may cooperate to form a saturated or unsaturated ring (e.g. cycloalkane, 
cycloalkene or heterocyclic ring), and further R.sub.11 may cooperate with 
said ring to form a bridged hydrocarbon compound residue. 
The group represented by R.sub.9 to R.sub.11 may have a substituent(s). 
Examples of said group and said substituent(s) are the same as the 
examples of the group represented by R in formula (I) and the 
substituent(s) mentioned with respect thereto. 
Examples of the ring formed by the cooperation of, for example, R.sub.9 and 
R.sub.10, as well as of the bridged hydrocarbon compound residue which is 
formed by R.sub.9 to R.sub.11 and the substituent(s) which said residue 
may have, are the same as the examples of the cycloalkyl, cycloalkenyl, 
and heterocyclic groups represented by R in formula (I), and the 
substituent(s) mentioned with respect thereto. 
The preferable substituents in formula (X) are as follows: 
(i) Two of R.sub.9 to R.sub.11 are alkyl groups. 
(ii) One of R.sub.9 to R.sub.11, for example, R.sub.11 is a hydrogen atom, 
and the other two, R.sub.9 and R.sub.10, cooperate with the root carbon 
atom to form a cycloalkyl group. 
Further, the preferable substituent(s) in (i) above is such that two of 
R.sub.9 to R.sub.11 are alkyl groups, and the other one is a hydrogen atom 
or an alkyl group. 
The alkyl and cycloalkyl groups each may have a substituent(s). Examples of 
such alkyl and cycloalkyl groups as well as of their substituents are the 
same as the examples of the alkyl and cycloalkyl groups represented by R 
in formula (I) and the substituents mentioned with respect thereto. 
Typical, but by no means limiting, examples of the magenta color 
image-forming coupler that can be used in the present invention are listed 
below. 
ILLUSTRATIVE MAGENTA COLOR IMAGE-FORMING COUPLERS 
##STR11## 
These couplers were synthesized by reference to Journal of the Chemical 
Society, Perkin I (1977), pages 2047 to 2052, U.S. Pat. No. 3,725,067 and 
Unexamined Published Japanese Patent Application Nos. 99437/1984, 
42045/1983, 162548/1984, 59171956/1984, 33552/1985 and 43659/1985. 
A magenta dye image stabilizer having the formula (I) which is used in 
combination with the magenta coupler of the present invention has the 
effect of not only preventing a magenta dye image from fading upon 
exposure to light but also preventing light discoloration of said image. 
In formula (II), R' represents an aliphatic group, a cycloalkyl group or an 
aryl group, and these may have substituents. Examples of the aliphatic 
group represented by R' include saturated and unsaturated alkyl groups. 
Illustrative saturated aliphatic groups include methyl, ethyl, butyl, 
octyl, dodecyl, tetradecyl and hexadecyl. Exemplary unsaturated aliphatic 
groups include ethenyl and propenyl. 
Examples of the cycloalkyl group represented by R.sup.1 include optionally 
substituted 5- to 7-membered cycloalkyl groups such as cyclopentyl and 
cyclohexyl. 
Examples of the aryl group represented by R.sup.1 are a phenyl and naphthyl 
that may have a substituent. 
Examples of the substituent for the aliphatic group, cycloalkyl group and 
aryl group represented by R.sup.1 include alkyl, aryl, alkoxy, carbonyl, 
carbamoyl, acylamino, sulfamoyl, sulfonamido, carbonyloxy, alkylsulfonyl, 
arylsulfonyl, hydroxyl, hetero ring, alkylthio and arylthio. These 
substituents may be optionally substituted. 
In formula (II), Y represents the group of nonmetallic atoms necessary for 
forming a 5- to 7-membered hetero ring taken together with the nitrogen 
atom. At least two of the hetero ring forming nonmetallic atoms including 
the nitrogen atom must be hetero atoms and these two hetero atoms should 
not be adjacent to each other. Compounds of formula (II) having two 
adjacent hetero atoms in the hetero ring are not desirable since they are 
not effective as the magenta dye image stabilizer. 
The 5- to 7-membered hetero ring in the compounds of formula (11) may have 
a substituent such as an alkyl or aryl group. The 5- to 7-membered hetero 
ring may be saturated or unsaturated but a saturated hetero ring is 
preferred. 
Typical, but by no means limiting, examples of the compounds of formula 
(11) are listed below. 
EXEMPLARY COMPOUNDS OF FORMULA (11) 
(A) Piperazine compounds: 
##STR12## 
(B) Morpholine compounds: 
##STR13## 
(C) Thiamorpholine compounds: 
##STR14## 
(D) Imidazolidine compounds: 
##STR15## 
(E) Homopiperazine compounds: 
##STR16## 
(H) Others: 
##STR17## 
Among the magenta dye image stabilizers of formula (11) used in the present 
invention, piperazine and homopiperazine compounds are particularly 
preferred. Among the piperazine and homopiperazine compounds, those 
represented by the following formulas (XI) and (XII) are preferred: 
##STR18## 
wherein R.sup.2 is a hydrogen atom, an alkyl group or an aryl group 
R.sup.3 is a hydrogen atom, an alkyl group, an acyl group on an aryl 
group, R.sup.3 being preferably a hydrogen atom, an alkyl group or an aryl 
group, provided that R.sup.2 and R.sup.3 are not both hydrogen atoms; and 
R.sup.4 to R.sup.13 are each a hydrogen atom, an alkyl group or an aryl 
group. 
In formulas (XI) and (XII), R.sup.2 represents a hydrogen atom, an alkyl 
group or an aryl group; and R.sup.3 represents a hydrogen atom, an alkyl 
group, an acyl group or an aryl group. Examples of the alkyl group 
represented by R.sup.2 or R.sup.3 include methyl, ethyl, butyl, octyl, 
dodecyl, tetradecyl, hexadecyl and octadecyl. Examples of the acyl group 
represented by R.sup.3 include an alkyl carbonyl group such as acetyl, 
dodecanoyl and the like, and an aryl carbonyl group such as benzoyl and 
the like. An example of the aryl group represented by R.sup.2 or R.sup.3 
is a phenyl group. The alkyl group and aryl group represented by R.sup.2 
or R.sup.3 may have a substituent such as a halogen atom, an alkyl group, 
an aryl group, an alkoxy group, an aryloxy group or a heterocyclic group. 
The sum of carbon atoms in R.sup.2 and R.sup.3 (including substituents) is 
preferably in the range of 6 to 40. 
In formula (XI) and (XII), R.sup.4 to R.sup.13 each represents a hydrogen 
atom, an alkyl group or an aryl group. Examples of the alkyl group 
represented by R.sup.4 to R.sup.13 include methyl and ethyl. An example of 
the aryl group represented by R.sup.4 to R.sup.13 is a phenyl group. 
Specific examples of the compounds represented by formula (XI) have been 
listed above as illustrative piperazine compounds (A-1) to (A-30), while 
specific examples of the compounds represented by formula (XII) have been 
listed as illustrative homopiperazine compounds (E-1) to (E-12). 
Typical examples of the magenta dye image stabilizer having formula (11) 
used in the present invention may be synthesized by the following methods. 
SYNTHESIS 1 
Synthesis of Compound (A-2): 
Piperazine (9.0 g) and myristyl bromide (55 g) are dissolved in 100 ml of 
acetone. To the acetone solution, 15 g of anhydrous potassium carbonate is 
added and the mixture is refluxed for 10 hrs. After the reaction, the 
reaction mixture is poured into 500 ml of water and subjected to 
extraction with 500 ml of ethyl acetate. The ethyl acetate layer is dried 
over magnesium sulfate and the ethyl acetate is distilled off so as to 
obtain the end compound as a white crystal. The crystal is recrystallized 
with 300 ml of acetone to obtain white flakes in an amount of 34 g (yield: 
70%). m.p. 55.degree.-58.degree. C. 
SYNTHESIS 2 
Synthesis of Compound (B-4): 
Eighteen grams of 4-morpholinoaniline is dissolved in 100 ml of ethyl 
acetate. To the stirred solution while held at 20.degree. C., 12 ml of 
acetic anhydride is added in small portions. After completion of the 
addition of acetic anhydride, the mixture is cooled with ice. The 
resulting crystal is recovered by filtration and recrystallized with ethyl 
acetate to obtain the end compound as a white powder in an amount of 16.5 
g (yield: 75%). m.p. 207.degree.-210.degree. C. 
The color photographic material of the present invention preferably 
contains the magenta coupler in amounts ranging from 1.5.times.10.sup.-3 
to 7.5.times.10.sup.-1 moles per mole of silver, more preferably from 
1.times.10.sup.-2 to 5.times.10.sup.-1 moles per mole of silver. 
The magenta dye image stabilizer of formula (11) is preferably used in 
amounts ranging from 5 to 300 mole%, more preferably 10-200 mole%, of the 
magenta coupler of formula (I). 
The magenta dye image stabilizer of formula (11) may be used in combination 
with another magenta dye image stabilizer that is represented by the 
following formula (XIII), namely a phenolic or phenylether compound: 
##STR19## 
wherein R.sup.14 is a hydrogen atom, an alkyl group, an aryl group or a 
heterocyclic group; R.sup.15, R.sup.16, R.sup.18 and R.sup.19 are each a 
hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy 
group or an acylamino group; R.sup.17 is an alkyl group, a hydroxyl group, 
an aryl group or an alkoxy group; R.sup.14 and R.sup.15 may be fused to 
form a 5- or 6-membered ring when R.sup.17 represents a hydroxy or alkoxy 
group; R.sup.14 and R.sup.15 may be fused to form a methylenedioxy ring; 
and R.sup.16 and R.sup.17 may be fused to form a 5-membered carbon ring 
when R.sup.14 represents an alkyl, aryl or heterocyclic group. 
Several of the compounds of formula (XIII) are described in U.S. Pat. Nos. 
3,935,016, 3,982,944, and 4,254,216; Unexamined Published Japanese Patent 
Application Nos. 21004/1980 and 145530/1979; Published British Patent 
Application Nos. 2,077,455 and 2,062,888; U.S. Pat. Nos. 3,764,337, 
3,432,300, 3,574,627 and 3,573,050; Unexamined Published Japanese Patent 
Application Nos. 152225/1977, 20327/1978, 17729/1978 and 6321/1980; 
British Pat. No. 1,347,556; Published British Patent Application No. 
2,066,975; Japanese Patent Publication Nos. 12337/1979 and 31625/1973; and 
U.S. Pat. No. 3,700,455. 
Specific examples of the compounds of formula (XIII) are listed below. 
##STR20## 
The phenolic or phenylether compound of formula (XIII) is preferably used 
in an amount not more than 200 mole% of the magenta dye image stabilizer 
of formula (II), with the amount not exceeding 140 mole% being more 
preferred. 
The phenolic compound and phenylether compound of formula (XIII) are 
effective in preventing the fading of the magenta dye image produced from 
the magenta coupler of the present invention, but they are little 
effective in preventing such magenta dye image from becoming discolored. 
Therefore, it is not preferred that the phenolic or phenylether compound 
is used in an excess amount with respect to the magenta dye image 
stabilizer of formula (II). 
The magenta dye image formed from the magenta coupler of the present 
invention generally undergoes considerable fading upon exposure to light. 
Furthermore, discoloration resulting from exposure to light is so great 
that the color of the image changes from the pure magenta to yellowish 
magenta. The magenta dye image stabilizer of formula (II) is capable of 
exhibiting the effects unattainable by the phenolic or phenylether 
compound, i.e., prevention of fading and discoloration of the magenta dye 
image produced from the magenta coupler used in the present invention. 
Accordingly, when the magenta dye image stabilizer of formula (II) is used 
in admixture with the conventional magenta dye image stabilizer, i.e., 
phenolic or phenylether compound, said conventional stabilizer must be 
used in such an amount that the discoloration upon exposure to light is 
not remarkable. 
When such conventional stabilizer, i.e., phenolic or phenylether compound, 
of formula (XIII) is used in a suitable amount in combination with the 
magenta dye image stabilizer of formula (II), a synergistic effect is 
sometimes observed which is due probably to their compensating for the 
mutual defective points each other. 
The magenta coupler and magenta dye image stabilizer in accordance with the 
present invention are preferably used in the same photographic layer, but 
if desired, they may be incorporated in two different layers such that the 
stabilizer in a layer adjacent the one containing the magenta coupler. 
The silver halide photographic material of the present invention may be, 
for example, color negative and positive films and color photographic 
paper, but particularly when color photographic paper for viewing the 
printed color image directly is used, the effect of the present invention 
is produced strikingly. 
The silver halide photographic material of the present invention including 
such color photographic paper may be either for monochrome or multicolor 
use. The silver halide photographic material for multicolor use has a 
structure such that silver halide emulsion layers usually containing 
magenta, yellow and cyan couplers, respectively, as photographic couplers, 
and nonsensitive layers are superimporsed in appropriate number of layers 
and in appropriate sequence on the support in order to effect subtractive 
color reproduction, but such number of layers and sequence may be changed 
appropriately according to use object. 
The silver halide emulsion used in the silver halide photographic material 
of the present invention may be selected from among the silver halides 
commonly used in silver halide photography, such as silver bromide, silver 
chloride, silver iodobromide, silver chlorobromide and silver 
chloroiodobromide. 
The silver halide grains used in the silver halide emulsions of the present 
invention may be those obtained by any of the acid method, neutral method, 
and ammoniacal method. These grains may be grown at one time or may be 
grown after preparing seed grains. The method of preparing seed grains and 
the method of growing them may be the same or different. 
In preparing the silver halide emulsion, halide ions and silver ions may 
admixed at the same time, or either one may be admixed with the other one 
present in the emulsion. Also, while considering the critical speed of 
growth of silver halide crystals, halide ions and silver ions may be added 
one by one or at the same time into a mixing bath while controlling the pH 
and pAg in said bath to grow the crystals. 
In preparing the silver halide of the present invention, it is possible, by 
using a silver halide solvent optionally, to control the grain size, 
shape, grain size distribution and speed of growth of the silver halide 
grains. 
The silver halide grains to be used in the silver halide emulsions of the 
present invention may have metal ions incorporated inside the grains 
and/or in the grain surfaces in the course of forming and/or growing the 
grains by using cadmium salt, zinc salt, lead salt, thallium salt, or 
iridium salt or its complex salt, rhodium salt or its complex salt, or 
iron salt or its complex salt. Said grains may also be placed in an 
appropriate reduction atmosphere to have reduction-sensitized specks 
imparted inside the grains and/or into the grain surfaces. 
The silver halide emulsions of the present invention may be removed of 
unnecessary soluble salts after completion of the growth of the silver 
halide grains or may be left as they are containing such salts. In 
removing said salts; the method described in "Research Disclosure No. 
17643" may be used. 
The silver halide grains to be used in the silver halide emulsions of the 
present invention may have a homogeneous structure throughtoug the 
crystal, or the structure of the core may be different from that of the 
shell. These silver halide grains may be of the surface type where latent 
images are predominantly formed on the grain surface or of the internal 
type where latent images are formed within the grain. 
The silver halide grains may be regular crystals or irregular crystals such 
as inspherical or plane form. They may have any proportions of (100) and 
(111) planes, and may also be in composite form of these crystals or may 
be admixed with various crystal grains. 
The silver halide emulion of the present invention may be a mixture of two 
or more silver halide emulsions prepared separately. 
The silver halide emulsion of the present invention is chemically 
sensitized by an ordinary method, such as the sulfur sensitization using a 
compound containing sulfur capable of reaction with silver ions or using 
active gelatin, the selenium sensitization using a selenium compound, the 
reduction sensitization using reducible material, or the noble metal 
sensitization using gold and other noble metal compounds. Such methods may 
be used each independently or in combination. 
The silver halide emulsion of the present invention may be spectrally 
sensitized by suitably selected sensitizing dye in order to provide 
sensitivity for the desired spectral wavelength regions. A variety of 
spectral sensitizing dyes may be used either individually or in 
combination. The silver halide emulsion may contain, together with the 
sensitizer, a dye which itself has no spectral sensitizing action or a 
supersensitizer which, being a compound which substantially does not 
absorb visible light, strengthens the sensitizing action of the 
sensitizer. 
In order to prevent the occurrence of fog and/or keep the photographic 
properties stable, in the course of preparing the photographic material, 
in storage or in processing thereof, a compound known in the photographic 
industry as an anti-foggant or stabilizer may be added to the silver 
halide emulsion of the present invention in the course of chemical 
ripening and/or upon completion of chemical ripening and/or after 
completion of chemical ripening but before coating of the silver halide 
emulsion. 
The binder (or protective colloid) advantageously used in the silver halide 
emulsion of the present invention is gelatin, but other hydrophilic 
colloids such as gelatin derivative, glaft polymer of gelatin with other 
polymer, protein, sugar derivative, cellulose derivative, and synthesized 
hydrophillic polymer may be used. 
The photographic emulsion layer and other hydrophilic colloidal layer(s) of 
the photographic material using the silver halide emulsion of the present 
invention are hardened by using hardeners either alone or in combination 
that bridge the binder (or protective colloid) molecules to enhance the 
film strength. The hardener is desirably added in such an amount as is 
capable of hardening the photographic material to the extent that there is 
no need to add the hardener in the processing solution, but such hardener 
may be added in the processing solution. 
A plasticizer can be added with a view to enhancing the flexibility of the 
silver halide emulsion layer and/or other hydrophilic colloidal layer(s) 
of the photographic material using the silver halide emulsion of the 
present invention. 
A water-insoluble or hardly soluble synthesized polymer latex can be 
incorporated for the purpose of improving the dimentional stability of the 
photographic emulsion layer and other hydrophilic colloidal layer(s) of 
the photographic material using the silver halide emulsion of the present 
invention. 
In the emulsion layer of the silver halide color photographic material of 
the present invention, a dye-forming coupler is used which forms a dye 
upon coupling reaction with the oxidized product of an aromatic primary 
amine developing agent (e.g., p-phenylenediamine derivative or aminophenol 
derivative) in the color developing processing. The color-forming coupler 
is usually selected so that a dye is formed which absorbs the spectral 
wavelength sensitive to the emulsion layer containing said dye; that is, a 
yellow dye-forming coupler is used in the blue-sensitive emulsion layer, a 
magenta dye-forming coupler in the green-sensitive emulsion layer, and a 
cyan dye-forming coupler in the red-sensitive emulsion layer. However, the 
respective couplers may be used in different combinations from those 
mentioned above according to the object. 
The yellow dye-forming coupler includes acylacetamido couplers (e.g. 
benzoylacetanilides and pivaloyl acetanilides), the magenta dye-forming 
coupler includes, in addition to the couplers of the present invention, 
5-pyrazolone, pyrazolobenzimidazole, pyrazolotriazole and open chained 
acylacetonitrile couplers, and the cyan dye-forming coupler includes 
naphthol and phenol couplers. 
These dye-forming couplers desirably have a group having 8 or more carbon 
atoms in the molecule that, being called a ballast group, renders the 
coupler non-diffusible. These couplers may be 4-equivalent couplers such 
that four silver ions need be reduced for the formation of one mole of 
dye, or may be 2-equivalent couplers such that only two silver ions 
suffice to be reduced for the formation of one mole of dye. 
Hydrophobic compounds such as dye-forming coupler that need not be 
adsorpted onto the silver halide crystal surfaces can be dispersed into 
the emulsion by means of solid dispersion, latex dispersion or 
oil-in-water drop type emulsion dispersion. Such dispersion method can be 
appropriately selected according to the chemical structure and the like of 
the hydrophobic compounds. The oil-in-water drop type emulsion dispersion 
method may be any conventional method of dispersing hydrophobic additives 
such as coupler, which usually comprises dissolving such hydrophobic 
additives in a high-boiling organic solvent having a boiling point higher 
than about 150.degree. C. by optionally using low-boiling and/or 
water-soluble organic solvents together, then emulsion-dispersing the 
dissolved hydrophobic additives by using a surfactant in a hydrophilic 
binder such as aqueous gelatin solution with such means of dispersion as a 
stirrer, homogenizer, colloid mill, flow-jet mixer or ultrasonic 
disperser, and thereafter adding the resulting dispersion into the 
hydrophilic colloidal layer. In that case, the step of removing the 
low-boiling organic solvent after or simultaneously with dispersion may be 
added. 
The high-boiling organic solvent is one having a boiling point higher than 
150.degree. C. that does not react with the oxidized product of a 
developing agent, such as a phenol derivative, phthalate ester, phosphate 
ester, citrate ester, benzoate ester, alkylamido, fatty acid ester or 
trimesic acid ester. 
Dispersion aids used in dissolving hydrophobic compounds in a low-boiling 
solvent alone or mixed with a high-boiling solvent and dispersing the 
dissolved hydrophobic compounds into water by using a mixer or ultrasonic 
disperser include anionic surfactants, nonionic surfactants and cationic 
surfactants. 
Anti-color foggants may be used in order to prevent occurrence of color 
stain, deterioration of sharpness and coarse graininess due to moving of 
the oxidized product of a developing agent or the electron transporting 
agent between the emulsion layers (the same color-sensitive layers and/or 
different color-sensitive layers) of the color photographic material of 
the present invention. 
The anti-color foggants may be incorporated in the emulsion layer itself or 
in the intermediate layer provided between adjacent emulsion layers. 
Image stabilizers can be incorporated in the color photographic material 
using silver halide emulsion layers of the present invention in order to 
prevent deterioration of color images. 
The hydrophilic colloidal layers such as protective layer and intermediate 
layer of the photographic material of the present invention may have 
incorporated therein UV absorbers in order to prevent occurrence of 
fogging due to discharge resulting from the photographic material being 
charged by its friction or the like, or to prevent deterioration of images 
due to UV light. 
The color photographic material using a silver halide emulsion of the 
present invention can be provided with auxiliary layers such as filter 
layer, anti-halation layer and/or anti-irradiation layer. These auxiliary 
layers and/or the emulsion layers may have incorporated therein dyes 
flowing out of the color photographic material or being bleached during 
the color developing processing. 
Matting agents can be incorporated in the silver halide emulsion layers 
and/or other hydrophilic colloidal layers of the silver halide 
photographic material using a silver halide emulsion of the present 
invention, with a view to reducing the surface gloss to render writing in 
pencil possible and to preventing adhesion of photographic materials to 
each other. 
The light-sensitive material using the silver halide emulsion of the 
present invention may contain a lubricant that is capable of reducing its 
sliding friction. 
The light-sensitive material may also contain an antistat for the purpose 
of preventing static buildup. The antistat may be incorporated in an 
antistatic layer on the side of the support where no emulsion layer is 
formed. Alternatively, the antistat may be incorporated in an emulsion 
layer and/or a protective layer other than an emulsion layer which is on 
the side of the support where said emulsion layer is formed. 
Photographic emulsion layer and/or other hydrophilic colloidal layers in 
the light-sensitive material using the silver halide emulsion of the 
present invention may contain a variety of surfactants for attaining such 
purposes as improved coating property, prevention of antistatic buildup, 
improved slipping property emulsification/disperson, antiblocking and 
improved photographic characteristics in terms of accelerated development, 
hard tone and sensitization. 
Photographic emulsion layers and other layers for making a light-sensitive 
material using the silver halide emulsion of the present invention may be 
coated onto flexible reflecting supports such as paper or synthetic paper 
laminated with baryta layer or .alpha.-olefin polymer, films made of 
semi-synthetic or synthetic polymers such as cellulose acetate, cellulose 
nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, 
polycarbonate and polyamide, and rigid materials such as glass, metals and 
ceramics. 
After optional surface treatment of the support by suitable techniques such 
as corona discharge, UV irradiation and flame treatment, the silver halide 
light-sensitive material of the present invention may be coated onto the 
support either directly or with one or more subbing layers formed thereon. 
The subbing layers are provided for improving the adhesive strength, 
anti-static property, dimensional stability, frictional resistance, 
hardness, anti-halation property, frictional characteristics and/or other 
characteristics of the surface of the support. 
A thickener may be used in order to facilitate the coating of the 
photographic material using the silver halide emulsion of the present 
invention. Particularly useful coating techniques are extrusion coating 
and curtain coating, both of which will enable simultaneous application of 
two or more layers. 
The light-sensitive material of the present invention may be exposed to 
electromagnetic waves in the spectral region to which the emulsion layers 
that make up the light-sensitive material have sensitivity. Any known 
light sources may be used and they include daylight (sunshine), tungsten 
lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc 
lamps, xenon flash lamps, CRT flying spot, light from a variety of lasers, 
LED emitted light, and light emitted from fluorescent materials upon 
excitation by electron beams, X-rays, gamma-rays or alpha-rays. 
The exposure time may range from 1 millisecond to 1 second as is usually 
the case with cameras. Periods shorter than 1 microsecond, such as one 
ranging from 100 microseconds to 1 microsecond may be employed with CRTs 
or xenon flash lampls. Exposure longer than 1 second would also be 
possible. The exposure may be continuous or intermittent. 
The silver halide photographic material of the present invention may form 
an image by any techniques of color development that are known in the art. 
The color developer used to process this photographic material may contain 
any of the known aromatic primary amine color developing agents that are 
extensively used in various color photographic processes. Such developing 
agents include aminophenolic and p-phenylenediamine derivatives. These 
compounds are generally used in salt forms, such as hydrochlorides or 
sulfates, which are stabler than the free state. These compounds are used 
in concentrations that generally range from about 0.1 to about 30 g, 
preferably from about 1 g to about 1.5 g per liter of the color developer. 
Illustrative aminophenolic developing agents include o-aminophenol, 
p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, and 
2-oxy-3-amino-1,4-dimethylbenzene. 
Particularly useful primary aromatic amino color developing agents are 
N,N-dialkyl-p-phenylenediamine compounds wherein the alkyl or phenyl group 
may have a suitable substituent. Among these compounds, the following are 
particularly advantageous: N,N'-di-ethyl-p-phenylenediamine hydrochloride, 
N-methyl-p-phenylenediamine hydrochloride, 
N,N'-dimethyl-p-phenylenediamine hydrochloride, 
2-amino-5-(N-ethyl-N-dodecylamino)-toluene, 
N-ethyl-N-.beta.-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, 
N-ethyl-N-.beta.-hydroxyethylaminoaniline, 
4-amino-3-methyl-N,N'-diethylaniline, and 
4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluene sulfonate. 
In addition to these primary aromatic amino color developing agents, the 
color developer used in the processing of the photographic material of the 
present invention may contain a variety of additives that are commonly 
incorporated in color developers and such additives include alkali agents 
(e.g. sodium hydroxide, sodium carbonate and potassium carbonate), alkali 
metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali 
metal halides, benzyl alcohol, water softeners and thickeners. The pH of 
the color developer is usually at least 7 and most generally ranges from 
about 10 to about 13. 
After color development, the photographic material of the present invention 
is processed by a solution having the fixing ability. If this solution is 
a fixing bath, its use is preceded by a bleaching step. The bleaching 
agent used in the bleaching bath is a metal complex salt of an organic 
acid. This metal complex salt has the ability not only to oxidize metallic 
silver (i.e., formed as a result of development) into silver halide but 
also to ensure complete color formation by a color former. The structure 
of this metal complex salt is such that an organic acid such as an 
aminopolycarboxylic acid, oxalic acid or citric acid is coordinated to a 
metal ion such as iron, cobalt or copper. The organic acids most preferred 
for use in forming metal complex salts are polycarboxylic acids or 
aminopolycarboxylic acids. The polycarboxylic acids or aminopolycarboxylic 
acids may be in the form of alkali metal salts, ammonium salts or 
water-soluble amine salts. 
Typical examples of polycarboxylic acids or aminopolycarboxylic acids are 
lited below: 
(1) ethylenediaminetetraacetic acid; 
(2) nitrilotriacetic acid; 
(3) iminodiacetic acid; 
(4) ethylenediaminetetraacetic acid disodium salt; 
(5) ethylenediaminetetraacetic acid tetra(trimethylammonium) salt; 
(6) ethylenediaminetetraacetic acid tetrasodium salt; and 
(7) nitrilotriacetic acid sodium salt. 
In addition to metal complex salts of these organic acids which are used as 
bleaching agents, the bleaching bath used in processing the color 
photographic material of the present invention may contain a variety of 
additives, and preferred additives are rehalogenating agents such as 
alkali or ammonium halides (e.g., potassium bromide, sodium bromide, 
sodium chloride and ammonium bromide), metal salts and chelating agents. 
Any other additives that are conventionally incorporated in bleaching 
baths may also be used and they include pH buffers (e.g., borate, oxalate, 
acetate, carbonate and phosphate salts), alkylamines and polyethylene 
oxides. 
The fixing bath and bleach-fixing bath may also contain one or more pH 
buffers that are selected from among sulfites (e.g., ammonium sulfite, 
potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium 
bisulfite, ammonium metabisulfite, potassium metabisulfite, and sodium 
metabisulfite), and a variety of acids or salts (e.g., boric acid, borax, 
sodium hydroxide, potassium hydroxide, sodium carbonate, potassium 
carbonate, sodium bicarbonate, sodium bisulfite, potassium bicarbonate, 
acetic acid, sodium acetate and ammonium hydroxide). 
If the photographic material of the present invention is processed in a 
bleach-fixing bath as it is supplied with a blix replenisher, 
thiosulfates, thiocyanates, sulfites or other salts may be incorporated 
either in the bleach-fixing bath or in the replenisher that is fed to said 
blix bath. 
In order to increase the activity of the bleach-fixing bath used in 
processing the photographic material of the present invention, air or 
oxygen may be blown into a tank containing the bleach-fixing bath or its 
replenisher. Alternatively, a suitable oxidant such as hydrogen peroxide, 
bromate or persulfate may be added into the tank. 
ADVANTAGES OF THE INVENTION 
Color photographic materials containing the magent coupler of the present 
invention and a magenta dye image stabilizer represented by formula (II) 
are improved in the fastness of magenta dye images particularly against 
light, heat and humidity; that is, the discoloration and fading of color 
against light as well as the occurrence of yellow stain in the background 
due to light, heat and humidity are satisfactorily prevented. 
The advantages of the present invention are hereunder described in greater 
detail by reference to working examples which are given here for 
illustrative purposes only and are by no means intended as limiting the 
invention.

EXAMPLE 1 
Gelatin (15.0 mg/100 cm.sup.2) and comparative magenta coupler (1) (6.0 
mg/100 cm.sup.2) were dispersed in 2,5-di-tert-octylhydroquinone (0.8 
mg/100 cm.sup.2). The dispersion was mixed with a silver chlorobromide 
emulsion (containing 80 mol% of silver bromide) and the mixture was coated 
onto a paper support laminated with polyethylene on both surfaces, so as 
to provide a silver deposit of 3.8 mg/100 cm.sup.2. The so formed emulsion 
layer was dried to prepare sample No. 1. 
To sample No. 1, a magenta dye image stabilizer in accordance with the 
invention (PH-13) was added in an amount equimolar to that of the magenta 
coupler, thereby preparing sample No. 2. 
Sample Nos. 3, 6 and 9 were prepared as in the case of sample No. 1 except 
that cmparative magenta coupler (1) was replaced by PC-10, PC-11 an PC-12, 
three of the triazole type magenta couplers defined in the present 
invention. 
Samples Nos. 4,7 and 10 were prepared by modifying sample Nos. 3, 6 and 9 
with PH-13 added in an amount equimolar to that of the magenta coupler. 
Sample Nos. 5, 8 and 11 were prepared by modifying sample Nos. 3, 6 and 9 
with A-1, another magenta dye image stabilizer within the scope of the 
invention, added in an amount equimolar to that of the magenta coupler. 
Each of the samples thus prepared was exposed through an optical wedge by 
the conventional method and subsequently processed by the following 
scheme. 
______________________________________ 
Steps Temperature, .degree.C. 
Time 
______________________________________ 
Color development 
33 3 min and 30 sec 
Bleach-fixing 
33 1 min and 30 sec 
Washing 33 3 min 
Drying 50-80 2 min 
______________________________________ 
The processing solutions used had the following compositions. 
______________________________________ 
Color developer: 
Benzyl alcohol 12 ml 
Diethylene glycol 10 ml 
Potassium carbonate 25 g 
Sodium bromide 0.6 g 
Anhydrous sodium sulfite 2.0 g 
Hydroxylamine sulfate 2.5 g 
N--ethyl-N--.beta.-methanesulfonamidoethyl- 
4.5 g 
3-methyl-4-aminoaniline sulfate 
Water to make 1,000 ml 
pH adjusted to 10.2 with NaOH. 
Bleach-fixing bath: 
Ammonium thiosulfate 120 g 
Sodium metabisulfite 15 g 
Anhydrous sodium sulfite 3 g 
EDTA iron (III) ammonium salt 
65 g 
Water to make 1,000 ml 
pH adjusted to 6.7-6.8. 
______________________________________ 
Each of the processed samples was placed under illumination in a xenon 
fadeometer for 8 days so as to examine the light fastness of the dye image 
and Y staining in the background. Another set of the processed samples 
were left for 14 days in a hot and humid atmosphere (60.degree. 
C..times.80% RH) so as to examine the resistance of the dye image to 
moisture and Y staining in the background. The results are shown in Table 
1. 
The light fastness and moisture resistance of each sample were evaluated on 
the following bases. 
Residual dye: 
The density of the dye remaining after each of the tests on light fastness 
and moisture resistance was indicated as a percentage of the initial 
density (1.0). 
YS: 
The density of Y stain before each test was subtracted from the value after 
testing. 
Discoloration: 
The ratio of yellow density to magenta density as measured before testing 
for an initial density of 1.0 was subtracted from the value after testing. 
The greater the value obtained, the greater the discoloration from the 
pure magenta to a yellowish magenta color. 
TABLE 1 
__________________________________________________________________________ 
Moisture 
Light fastness 
resistance 
Dye image 
Residual 
Discolor- 
Residual 
Sample No. 
Coupler 
stabilizer 
dye (%) 
YS ation 
dye (%) 
YS 
__________________________________________________________________________ 
1 (Comparative) 
Comparative 
-- 56 0.53 
0.31 88 0.59 
magenta 
coupler (1) 
2 (Comparative) 
Comparative 
PH-13 85 0.54 
0.27 89 0.60 
magenta 
coupler (1) 
3 (Comparative) 
PC-10 -- 23 0.04 
0.83 101 0.07 
4 (Comparative) 
" PH-13 75 0.10 
0.79 100 0.06 
5 (Sample of 
" A-1 81 0.05 
0.09 101 0.07 
the invention) 
6 (Comparative) 
PC-11 -- 14 0.05 
0.89 100 0.08 
7 (Comparative) 
" PH-13 72 0.12 
0.81 100 0.07 
8 (sample of 
" A-1 80 0.05 
0.10 99 0.07 
the invention) 
9 (comparative) 
PC-12 -- 24 0.05 
0.79 98 0.07 
10 
(comparative) 
" PH-13 75 0.10 
0.72 100 0.08 
11 
(Sample of 
" A-1 82 0.06 
0.07 100 0.08 
the invention) 
__________________________________________________________________________ 
Comparative magenta coupler (1) 
##STR21## 
As is clear from Table 1, Sample Nos. 3, 6 and 9, using the magenta 
couplers within the scope of the invention, were highly resistant to Y 
staining as compared with sample No. 1 using the conventional 
four-equivalent 3-anilino-1,2-pyrazolo-5-one coupler. However, the results 
of the light fastness test with respect to residual dye and discoloration 
show that sample Nos. 3, 6 and 9 discolored and faded quite easily upon 
exposure to light. Sample Nos. 4, 7 and 10 used the magenta couplers of 
the present invention in combination with PH-13, a conventional magenta 
dye image stabilizer. These samples exhibited an appreciable reduction in 
the fading of dye image resulting from exposure to light, but their 
resistance to discoloration was not improved at all. 
Sample Nos. 5, 8 and 11 using magenta couplers and a magenta dye image 
stabilizer, both in accordance with the present invention, experienced 
small degrees of discoloration and fading upon exposure to light, heat and 
moisture, and the Y staining occurring in the background was negligible. 
These results were certainly unobtainable by sample No. 2 using the 
conventional four-equivalent 3-anilino-1,2-pyrazolo-5-one magenta coupler 
and PH-13 (conventional magenta dye image stabilizer). 
EXAMPLE 2 
Sample Nos. 12-35 were prepared as in Example 1 except that the 
combinations of magenta coupler and magenta dye image stabilizer were 
changed to those indicated in Table 2. These samples were processed as in 
Example 1 and subsequently tested for their light-fastness and moisture 
resistance as in Example 1. The results are shown in Table 2. 
TABLE 2 
__________________________________________________________________________ 
Moisture 
Light fastness 
resistance 
Dye image 
Residual 
Discolor- 
Residual 
Sample No. 
Coupler 
stabilizer 
dye (%) 
YS ation 
dye (%) 
YS 
__________________________________________________________________________ 
12 
(Comparative) 
Comparative 
A-1 54 0.61 
0.32 87 0.53 
magenta 
coupler (2) 
13 
(Comparative) 
Comparative 
A-2 51 0.58 
0.33 85 0.60 
magenta 
coupler (2) 
14 
(Comparative) 
Comparative 
E-2 53 0.67 
0.34 83 0.57 
magenta 
coupler (2) 
15 
(Comparative) 
Comparative 
PH-8 82 0.51 
0.27 88 0.59 
magenta 
coupler (2) 
16 
(Comparative) 
Comparative 
A-19 56 0.63 
0.37 82 0.61 
magenta 
coupler (3) 
17 
(Comparative) 
Comparative 
PH-10 83 0.54 
0.27 86 0.52 
magenta 
coupler (3) 
18 
(Comparative) 
PC-15 PH-8 72 0.13 
0.87 101 0.08 
19 
(Comparative) 
" PH-10 69 0.14 
0.81 100 0.09 
20 
(Comparative) 
PC-18 PH-8 73 0.11 
0.79 98 0.07 
21 
(Comparative) 
" PH-10 73 0.16 
0.76 97 0.09 
22 
(Sample of 
PC-15 A-1 77 0.04 
0.10 100 0.07 
the invention) 
23 
(Sample of 
" A-2 78 0.03 
0.09 101 0.08 
the invention) 
24 
(Sample of 
" A-19 81 0.05 
0.09 98 0.09 
the invention) 
25 
(Sample of 
" E-2 76 0.05 
0.12 102 0.08 
the invention) 
26 
(Sample of 
PC-18 A-1 81 0.04 
0.08 100 0.08 
the invention) 
27 
(Sample of 
" A-2 77 0.06 
0.07 103 0.07 
the invention) 
28 
(Sample of 
" A-19 76 0.05 
0.09 100 0.09 
the invention) 
29 
(Sample of 
" E-2 81 0.04 
0.08 98 0.08 
the invention) 
30 
(Sample of 
" B-2 73 0.05 
0.10 100 0.08 
the invention) 
31 
(Sample of 
" C-4 75 0.04 
0.11 101 0.09 
the invention) 
32 
(Sample of 
" D-1 70 0.05 
0.10 100 0.07 
the invention) 
33 
(Sample of 
" H-1 72 0.06 
0.09 99 0.09 
the invention) 
34 
(Sample of 
" E-3 80 0.05 
0.10 101 0.08 
the invention) 
35 
(Sample of 
" E-4 81 0.04 
0.10 100 0.08 
the invention) 
__________________________________________________________________________ 
Comparative magenta coupler (2) 
##STR22## 
As Table 2 clearly shows, sample Nos. 12, 13, 14 and 16 using the 
conventional four-equivalent 3-anilino-1,2-pyrazolo-5-one coupler in 
combination with magenta dye image stabilizers within the scope of the 
invention, and sample Nos. 18, 19, 20 and 21 using the combination of 
magenta couplers falling within the scope of the invention and commonly 
employed magenta dye image stabilizers were unable to give satisfactory 
results in all aspects of the light-fastness test and moisture resistance 
test. The intended results were obtained only when the magenta couplers 
within the scope of the invention were combined with magenta dye image 
stabilizers within the scope of the invention. Particularly good results 
were obtained when magenta dye image stabilizers of formula (XI) or (XII) 
were used. 
EXAMPLE 3 
A paper support laminated with polyethylene on both sides was coated with 
the following photographic layers in sequence, with the first layer 
(blue-sensitive silver halide emulsion layer) positioned closest to the 
support. As a result, sample No. 36 of multi-colored silver halide 
photographic material was obtained. 
First layer: blue-sensitive silver halide emulsion layer 
This layer was formed by coating 6.8 mg/100 cm.sup.2 of 
.alpha.-pivaloyl-(2,4-dioxo-1-benzylimidazolidin-3-yl)-2-chloro-5-[.gamma. 
-(2,4-di-t-amylphenoxy)butylamido]acetanilide (yellow coupler), 3.2 mg/100 
cm.sup.2, in terms of silver, of a blue-sensitive silver chlorobromide 
emulsion (85 mol% silver bromide), 3.5 mg/100 cm.sup.2 of dioctyl 
phthalate and 13.5 mg/100 cm.sup.2 of gelatin. 
Second layer: intermedite layer 
This layer was formed by coating 0.5 mg/100 cm.sup.2 of 
2,5-di-t-octylhydroquinone, 0.5 mg/100 cm.sup.2 of dinonyl phthalate and 
9.0 mg/100 cm.sup.2 of gelatin. 
Third layer: green-sensitive silver halide emulsion layer 
This layer was formed by coating 3.5 mg/100 cm.sup.2 of PC-10 (a magenta 
coupler included in the scope of the invention), 2.5 mg/100 cm.sup.2, in 
terms of silver, of a blue-sensitive silver chlorobromide emulsion (80 
mol% silver bromide), 3.0 mg/100 cm.sup.2 of dioctyl phthalate and 12.0 
mg/100 cm.sup.2 of gelatin. 
Fourth layer: intermediate layer 
This layer was formed by coating 7.0 mg/100 cm.sup.2 of 
2-(2-hydroxy-3-sec-butyl-5-t-butylphenyl)benzotriazole (UV absorber), 6.0 
mg/100 cm.sup.2 of dibutyl phthalate, 0.5 mg/100 cm.sup.2 of 
2,5-di-t-octylhydroquinone and 12.0 mg/100 cm.sup.2 of gelatin. 
Fifth layer: red-sensitive silver halide emulsion layer 
This layer was formed by coating 4.2 mg/100 cm.sup.2 of 
2-[.alpha.-(2,4-di-t-pentylphenoxy)butanamido]-4,6-dichloro-5-ethylphenol, 
3.5 mg/100 cm.sup.2 of tri-2-ethylhexyl phosphate and 11.5 mg/100 cm.sup.2 
of gelatin. 
Sixth layer: protective layer 
This layer was formed by coating 8.0 mg/100 cm.sup.2 of gelatin. 
Sample Nos. 37 to 45 were prepared by modifying sample No. 36 with magenta 
dye image stabilizers of the present invention that were incorporated in 
the 3rd layer in the amounts indicated in Table 3. Sample Nos. 36 to 45 
were processed as in Example 1 and subjected to a light-fastness test 
under illumination in a xenon fedeometer for 15 days. The test results are 
shown in Table 3. 
TABLE 3 
______________________________________ 
Amount of Residual 
Dye image stabilizer magenta 
Sample No. stabilizer (mol %/coupler) 
dye (%) 
______________________________________ 
36 (Comparative) 
-- -- 17 
(Samples of the 
invention) 
37 A-2 50 58 
38 " 100 67 
39 " 150 85 
40 A-19 50 55 
41 " 100 73 
42 " 150 88 
43 E-2 50 57 
44 " 100 69 
45 " 150 84 
______________________________________ 
The data in Table 3 show that the magenta dye image stabilizers in 
accordance with the present invention are effective in stabilizing the dye 
image formed by the triazole type magenta coupler of the present invention 
and that this effectiveness is increased as the amounts in which these 
stabilizers are incorporated is increased. Sample Nos. 37 to 45 
experienced a very small amount of discoloration in the magenta image as a 
result of exposure to light. Furthermore, these samples of the present 
invention suffered an extremely small degree of fading in the magenta dye. 
Therefore, they struck a good color balance between yellow, cyan and 
magenta couplers and displayed a highly satisfactory color reproduction. 
EXAMPLE 4 
Gelatin (15.0 mg/100 cm.sup.2) and comparative magenta coupler (1) (6.0 
mg/100 cm.sup.2) were dispersed in dibutylphthalate (0.8 mg/100 cm.sup.2) 
together with 2,5-di-tert-octylhydroquinone (0.8 mg/100 cm.sup.2). The 
dispersion was mixed with a silver chlorobromide emulsion (containing 80 
mol% of silver bromide) and the mixture was coated onto a paper support 
laminated with polyethylene on both surfaces, so as to provide a silver 
deposit of 3.8 mg/100 cm.sup.2. The so formed emulsion layer was dried to 
prepare sample No. 46. 
To sample No. 46, a magenta dye image stabilizer in accordance with the 
invention (PH-13) was added in an amount equimolar to that of the magenta 
coupler, thereby preparing sample No. 47. 
Sample Nos. 48, 51 and 54 were prepared as in the case of sample No. 46 
except that comparative magenta coupler (1) was replaced by PC-39, PC-41 
and PC-130, three of the magenta couplers defined in the present 
invention. 
Sample Nos. 49, 52 and 55 were prepared by modifying sample Nos. 48, 51 and 
54 with PH-13 added in an amount equimolar to that of the magenta coupler. 
Sample Nos. 50, 53 and 56 were prepared by modifying sample Nos. 48, 51 
and 54 with A-1 in place of PH-13, another magenta dye image stabilizer 
within the scope of the invention, added in an amount equimolar to that of 
the magenta coupler. 
Comparative magenta coupler (1) 
##STR23## 
Each of the samples thus prepared was exposed through an optical wedge by 
the conventional method and subsequently processed by the following 
scheme. 
______________________________________ 
Step Temperature, .degree.C. 
Time 
______________________________________ 
Color development 
33 3 min and 30 sec 
Bleach-fixing 
33 1 min and 30 sec 
Washing 33 3 min 
Drying 50-80 2 min. 
______________________________________ 
The processing solutions used had the following compositions. 
______________________________________ 
Color developer: 
Benzyl alcohol 12 ml 
Diethylene glycol 10 ml 
Potassium carbonate 25 g 
Sodium bromide 0.6 g 
Anhydrous sodium sulfite 2.0 g 
Hydroxylamine sulfate 2.5 g 
N--ethyl-N--.beta.-methanesulfonamidoethyl- 
4.5 g 
3-methyl-4-aminoaniline sulfate 
Water to make 1,000 ml 
pH adjusted to 10.2 with NaOH 
Bleach-fixing bath: 
Ammonium thiosulfate 120 g 
Sodium metabisulfite 15 g 
Anhydrous sodium sulfite 3 g 
EDTA iron (III) ammonium salt 
65 g 
Water to make 1,000 ml 
pH adjusted to 6.7-6.8. 
______________________________________ 
Each of the processed samples was placed under illumination in a xenon 
fadeometer for 8 days so as to examine the light fastness of the dye image 
and Y staining in the background. Another set of the processed samples 
were left for 14 days in a hot and humid atmosphere (60.degree. 
C..times.80% RH) so as to examine the resistance of the dye image to 
moisture and Y staining in the background. The results are shown in Table 
1. 
The light fastness and moisture resistance of each sample were evaluated on 
the following bases. 
Residual dye: 
The density of the dye remaining after each of the tests on light fastness 
and moisture resistance was indicated as a percentage of the initial 
density (1.0). 
YS: 
The density of Y stain before each test was subtracted from the value after 
testing. 
Discoloration: 
The ratio of yellow density to magenta density as measured before testing 
for an initial density of 1.0 was subtracted from the value after testing. 
The greater the value obtained, the greater the discoloration from the 
pure magenta to a yellowish magenta color. 
TABLE 4 
__________________________________________________________________________ 
Moisture 
Light fastness 
resistance 
Dye image 
Residual 
Discolor- 
Residual 
Sample No. 
Coupler 
stabilizer 
dye (%) 
YS ation 
dye (%) 
YS 
__________________________________________________________________________ 
46 
(Comparative) 
Comparative 
-- 50 0.54 
0.34 88 0.53 
magenta 
coupler (1) 
47 
(Comparative) 
Comparative 
PH-13 79 0.51 
0.27 89 0.56 
magenta 
coupler (1) 
48 
(Comparative) 
PC-39 -- 22 0.06 
0.78 101 0.07 
49 
(Comparative) 
" PH-13 70 0.10 
0.74 102 0.08 
50 
(Sample of 
" A-1 77 0.05 
0.14 101 0.06 
the invention) 
51 
(Comparative) 
PC-41 -- 23 0.06 
0.74 102 0.06 
52 
(Comparative) 
" PH-13 69 0.07 
0.70 100 0.07 
53 
(Sample of 
" A-1 76 0.07 
0.14 98 0.08 
the invention) 
54 
(Comparative) 
PC-130 
-- 15 0.08 
0.88 100 0.09 
55 
(Comparative) 
" PH-13 63 0.11 
0.80 97 0.10 
56 
(Sample of 
" A-1 69 0.09 
0.17 101 0.10 
the invention) 
__________________________________________________________________________ 
As is clear from Table 4, sample Nos. 48, 51 and 54, using the magenta 
couplers within the scope of the invention, were highly resistant to Y 
staining as compared with sample No. 46 using the conventional 
four-equivalent 3-anilino-5-pyrazolone coupler. However, the results of 
the light fastness test with respect to residual dye and discoloration 
show that sample Nos. 48, 51 and 54 discolored and faded quite easily upon 
exposure to light. Sample Nos. 49, 52 and 53 used the magenta couplers of 
the present invention in combination with PH-13, a conventional magenta 
dye image stabilizer. These samples exhibited an appreciable reduction in 
the fading of dye image resulting from exposure to light, but their 
resistance to discoloration was not improved at all. 
Sample Nos. 50, 53 and 56 using magenta couplers and a magenta dye image 
stabilizer, both in accordance with the present invention, experienced 
small degrees of discoloration and fading upon exposure to light, heat and 
moisture, and the Y staining occurring in the background was negligible. 
These results were certainly unobtainable by sample No. 47 using the 
conventional four-equivalent 3-anilino-5-pyrazolone coupler and PH-13 
(conventional magenta dye image stabilizer). 
EXAMPLE 5 
Sample Nos. 57-72 were prepared as in Example 4 except that the 
combinations of magenta coupler and magenta dye image stabilizer were 
changed to those indicated in Table 5. These samples were processed as in 
Example 4 and subsequently tested for their light-fastness and moisture 
resistance as in Example 4. The results are shown in Table 5. 
TABLE 5 
__________________________________________________________________________ 
Moisture 
Light fastness 
resistance 
Dye image 
Residual 
Discolor- 
Residual 
Sample No. 
Coupler 
stabilizer 
dye (%) 
YS ation 
dye (%) 
YS 
__________________________________________________________________________ 
57 
(Comparative) 
Comparative 
A-2 46 0.57 
0.36 87 0.51 
magenta 
coupler (2) 
58 
(Comparative) 
Comparative 
D-2 44 0.52 
0.32 89 0.54 
magenta 
coupler (2) 
59 
(Comparative) 
Comparative 
PH-8 70 0.51 
0.30 88 0.54 
magenta 
coupler (2) 
60 
(Comparative) 
Comparative 
PH-10 71 0.55 
0.29 86 0.50 
magenta 
coupler (2) 
61 
(Comparative) 
PC-52 PH-8 63 0.13 
0.88 100 0.09 
62 
(Comparative) 
" PH-10 65 0.14 
0.85 98 0.10 
63 
(Comparative) 
PC-90 PH-8 67 0.16 
0.83 100 0.10 
64 
(Comparative) 
" PH-10 68 0.15 
0.81 97 0.11 
65 
(Sample of 
PC-52 A-25 74 0.07 
0.13 101 0.08 
the invention) 
66 
(Sample of 
" D-2 68 0.06 
0.14 99 0.09 
the invention) 
67 
(Sample of 
PC-90 A-2 74 0.05 
0.14 98 0.07 
the invention) 
68 
(Sample of 
" D-2 67 0.05 
0.14 98 0.09 
the invention) 
69 
(Sample of 
" E-3 72 0.07 
0.10 99 0.10 
the invention) 
70 
(Sample of 
" A-2 78 0.08 
0.20 101 0.09 
the invention) 
PH-8 
71 
(Sample of 
" A-2 81 0.10 
0.20 100 0.10 
the invention) 
PH-10 
72 
(Sample of 
" A-2 81 0.11 
0.19 100 0.10 
the invention) 
PH-13 
__________________________________________________________________________ 
Comparative magenta coupler (2) 
##STR24## 
(In Table 5, A-2 and PH compounds were used in a molar ratio of 2:1 for 
sample Nos. 70, 71 and 72, and the total amount of dye image stabilizers 
was the same amount of mole as those used for other samples.) 
As Table 5 clearly shows, sample Nos. 57 and 58 using the conventional 
four-equivalent 3-anilino-5-pyrazolone coupler in combination with magenta 
dye image stabilizers within the scope of the invention, and sample Nos. 
61, 62, 63 and 64 using the combination of magenta couplers falling within 
the scope of the invention and commonly employed magenta dye image 
stabilizers were unable to give satisfactory results in all aspects of the 
light-fastness test and moisture resistance test. The intended results 
were obtained only when the magenta couplers within the scope of the 
invention were combined with magenta dye image stabilizers within the 
scope of the invention. 
In sample Nos. 70, 71 and 72 using the magenta couplers within the scope of 
the invention in combination with the magenta dye image stabilizers within 
the scope of the invention and the conventional dye image stabilizers, it 
is clearly observed that, in the light-fastness test, the discoloration 
somewhat increases and the residual dye (%) also increases due to a 
synerdistic effect resulting from the joint use of the two stabilizers. 
EXAMPLE 6 
A paper suppot laminated with polyethylene on both sides was coated with 
the following photographic layers in sequence from the support to obtain 
sample No. 73 of multi-colored silver halide photographic material. 
First layer: blue-sensitive silver halide emulsion layer 
This layer was formed by coating 6.8 mg/100 cm.sup.2 of 
.alpha.-pivaloyl-.alpha.-(2,4-dioxo-1-benzylimidazolidin-3-yl)-2-chloro-5- 
[.gamma.-(2,4-di-t-amylphenoxy)butylamido]acetanilide (yellow coupler), 3.2 
mg/100 cm.sup.2, in terms of silver, of a blue-sensitive silver 
chlorobromide emulsion (85 mol% silver bromide), 3.5 mg/100 cm.sup.2 of 
dibutyl phthalate and 13.5 mg/100 cm.sup.2 of gelatin. 
Second layer: intermediate layer 
This layer was formed by coating 0.5 mg/100 cm.sup.2 of 
2,5-di-t-octylhydroquinone, 0.5 mg/100 cm.sup.2 of dibutyl phthalate and 
9.0 mg/100 cm.sup.2 of gelatin. 
Third layer: green-sensitive silver halide emulsion layer 
This layer was formed by coating 3.5 mg/100 cm.sup.2 of PC-70 (a magenta 
coupler included in the scope of the invention), 2.5 mg/100 cm.sup.2, in 
terms of silver, of a blue-sensitive silver chlorobromide emulsion (80 
mol% silver bromide), 3.0 mg/100 cm.sup.2 of dibutyl phthalate and 12.0 
mg/100 cm.sup.2 of gelatin. 
Fourth layer: intermediate layer 
This layer was formed by coating 7.0 mg/100 cm.sup.2 of 
2-(2-hydroxy-3-sec-butyl-5-t-butylphenyl)benzotriazole (UV absorber), 6.0 
mg/100 cm.sup.2 of dibutyl phthalate, 0.5 mg/100 cm.sup.2 of 
2,5-di-t-octylhydroquinone and 12.0 mg/100 cm.sup.2 of gelatin. 
Fifth layer: red-sensitive silver halide emulsion layer 
This layer was formed by coating 4.2 mg/100 cm.sup.2 of 
2-[.alpha.-(2,4-di-t-pentylphenoxy)butanamido]-4,6-dichloro-5-ethylphenol 
(cyan coupler), 3.0 mg/100 cm.sup.2, in terms of silver, of red-sensitive 
silver chlorobromide emulsion (80 mol% silver bromide), 3.5 mg/100 
cm.sup.2 of tricresyl phosphate and 11.5 mg/100 cm.sup.2 of gelatin. 
Sixth layer: protective layer 
This layer was formed by coating 8.0 mg/100 cm.sup.2 of gelatin. 
Sample Nos. 74 to 82 were prepared by modifying sample No. 73 with magenta 
dye image stabilizers of the present invention that were incorporated in 
the 3rd layer in the amounts indicated in Table 6. Sample Nos. 73 to 82 
were processed as in Example 4 and subjected to a light-fastness test 
under illumination in a xenon fadeometer for 15 days. The test results are 
shown in Table 6. 
TABLE 6 
______________________________________ 
Amount of Residual 
Dye image stabilizer magenta 
Sample No. stabilizer (mol %/coupler) 
dye (%) 
______________________________________ 
73 (Comparative) 
-- -- 21 
(Samples of the 
Invention) 
74 A-19 50 51 
75 " 100 66 
76 " 150 82 
77 B-2 50 46 
78 " 100 60 
79 " 150 74 
80 E-11 50 48 
81 " 100 64 
82 " 150 79 
______________________________________ 
The data in Table 6 show that the magenta dye image stabilizers in 
accordance with the present invention are effective in stabilizing the dye 
image formed by the magenta coupler of the present invention and that this 
effectiveness is increased as the amounts in which these stabilizers are 
incorporated are increased. Sample Nos. 74 to 82, as compared with sample 
No. 73, experienced a very small amount of discoloration in the magenta 
image as a result of exposure to light. Furthermore, these samples of the 
present invention suffered an extremely small degree of discoloration and 
fading in the magenta dye. Therefore, they struck a good color balance 
between yellow, cyan and magenta couplers and displayed a highly 
satisfactory color reproduction.