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Description  |
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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 compou | | |
