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Claims  |
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What is claimed is:
1. A method for processing a silver halide color photographic material
comprising a support having thereon at least one silver halide emulsion
layer and containing a magenta dye forming coupler represented by formula
(I) shown below and a compound represented by formula (II) shown below in
the same layer, wherein the silver halide color photographic material is
subjected to color development using a replenisher for a color developing
solution, whose concentration of bromide is not more than
3.times.10.sup.-3 mol per liter and an amount of the replenisher for a
color developing solution is not more than 900 ml per m.sup.2 of the
silver halide color photographic material, wherein formula (I) is
represented by
##STR19##
wherein R.sub.1 represents an aromatic group, an aliphatic group or a
heterocyclic group; R.sub.2 represents a substituent; Za, Zb, Zc and Zd,
which may be the same or different, each represents an unsubstituted
methine group, a substituted methine group or --N.dbd.; and formula (II)
is represented by
(R'--COO.sup.-).sub.n M.sup.n+ (II)
wherein R' represents a substituent which imparts a diffusion-resistant
property to the compound represented by formula (II); M.sup.n+ represents
a hydrogen ion, a metal ion, or an ammonium ion; and n represents an
integer from 1 to 4.
2. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein R.sub.1 represents a straight chain or
branched chain alkyl group having from 1 to 32 carbon atoms, an alkenyl
group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group,
each of which may be substituted with a substituent selected from a
halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy
group, an aryloxy group, a carboxy group, an alkylthiocarbonyl group, an
arylthiocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a
diacylamino group, a ureido group, a urethane group, a thiourethane group,
a sulfonamido group, a heterocyclic group, an arylsulfonyl group,
aralkylsulfonyl group, an arylthio group, an alkylthio group, an
alkylamino group, a dialkylamino group, an anilino group, an N-arylanilino
group, an N-alkylanilino group, an N-acylanilino group, a hydroxy group
and a mercapto group; an aryl group, which may be substituted with a
substituent selected from an alkyl group, an alkenyl group, a cyclic alkyl
group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro
group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a
carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo
group, a sulfamoyl group, a carbamoyl group, an acylamino group, a
diacylamino group, a ureido group, a urethane group, a sulfonamido group,
a heterocyclic group, an arylsulfonyl group, an alkylsulfonyl group, an
arylthio group, an alkylthio group, an alkylamino group, a dialkylamino
group, an anilino group, an N-alkylanilino group, an N-arylanilino group,
an N-acylanilino group, a hydroxy group and a mercapto group; a
heterocyclic group, which may be substituted with a substituent selected
from the substituents as defined for the above-described aryl group; an
aliphatic acyl group; an aromatic acyl group; alkylsulfonyl group; an
arylsulfonyl group; an alkylcarbamoyl group; an alkylcarbamoyl group; an
arylcarbamoyl group; an alkylthiocarbamoyl group; or an arylthiocarbamoyl
group; and R.sub.2 represents a hydrogen atom; a straight chain or
branched chain alkyl group having from 1 to 32 carbon atoms, an alkenyl
group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, an
aryl group or a heterocyclic group, each of which may be substituted with
a substituent selected from the substituent as defined for these groups of
R.sub.1 respectively; an alkoxycarbonyl group; an aryloxycarbonyl group;
an aralkyloxycarbonyl group; an alkoxy group; an aryloxy group; an
alkylthio group; an arylthio group; a carboxy group; an acylamino group; a
diacylamino group; N-alkylacylamino group; an N-arylacylamino group; a
ureido group; a thioureido group; a urethane group; a thiourethane group;
an arylamino group; an alkylamino group, a cycloamino group; a
heterocyclic amino group; an alkylcarbonyl group; an arylcarbonyl group; a
sulfonamido group; a carbamoyl group; a sulfamoyl group; an acyloxy group;
a sulfonyloxy group; a cyano group; a hydroxy group; a mercapto group; a
halogen atom; a nitro group; or a sulfo group.
3. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein R.sub.1 represents a phenyl group which is
substituted with an alkyl group, an alkoxy group or a halogen atom at at
least one of the o-positions.
4. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein R.sub.2 represents an anilino group, an
acylamino group or arylureido group; and R.sub.1 represents an aryl group
which is substituted with a chlorine atom at at least one of the
o-positions.
5. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein the nitrogen containing ring composed of Za,
Zb, Zc and Zd may further have a condensed ring excepting a
benzotriazolyl-1 group and a benzotriazolyl-2 group.
6. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein (1) the group of the formula
##STR20##
of formula (I) represents a 5-membered monocyclic nitrogen-containing
aromatic heterocyclic group which is composed of Za, Zb, Zc and Zd that
each represents a methine group, a substituted methine group or --N.dbd.,
or (2) the group of the formula
##STR21##
wherein Z represents a non-metallic atomic group forming a 5-membered or
6-membered ring.
7. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein the substituent represented by R, has from 8
to 40 carbon atoms in total and represents a straight chain or branched
chain alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl
group or a cyclic alkenyl group, each of which may be substituted with a
substituent selected from a halogen atom, a nitro group, a cyano group, an
aryl group, an alkoxy group, an aryloxy group, a carboxy group, an
alkylthiocarbonyl group, an arylthiocarbonyl group, an alkoxycarbonyl
group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a
carbamoyl group, an acylamino group, a diacylamino group, a ureido group,
a urethane group, a thiourethane group, a sulfonamido group, a
heterocyclic group, an arylsulfonyl group, an alkylsulfonyl group, an
arylthio group, an alkylthio group, an alkylamino group, a dialkylamino
group, an anilino group, an N-arylanilino group, an N-alkylanilino group,
an N-acylanilino group, a hydroxy group and a mercapto group; an aryl
group which may be substituted with a substituent selected from an alkyl
group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic
alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl
group, an alkoxy group, an aryloxy group, a carboxy group, an
alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl
group, a carbamoyl group, an acylamino group, a diacylamino group, a
ureido group, a urethane group, a sulfonamido group, a heterocyclic group,
an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an
alkylthio group, an alkylamino group, dialkylamino group, an anilino
group, an N-alkylanilino group, an N-arylanilino group, an N-acylanilino
group, a hydroxy group and a mercapto group; a heterocyclic group which
may be substituted with a substituent selected from the substituents as
defined for the above-described aryl group; an aliphatic acyl group; an
aromatic acyl group; alkylsulfonyl group; an arylsulfonyl group; an
alkylcarbamoyl group; an arylcarbamoyl group; an alkylthiocarbamoyl group;
or an arylthiocarbamoyl group.
8. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein the metal ion represented by M.sup.n+ is
selected from ions of the group I, the group II and the group VIII of the
Periodic Table.
9. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein the ammonium ion represented by M.sup.n+ is
represented by the following formula:
##STR22##
wherein R.sub.3, R.sub.4, R.sub.5 and R.sub.6, each represents a hydrogen
atom, an alkyl group, a substituted alkyl group, aralkyl group, a
substituted aralkyl group, an aryl group, a substituted aryl group, and
the total number of carbon atoms included in R.sub.3, R.sub.4, R.sub.5 and
R.sub.6 is up to 20; or each two of R.sub.3 to R.sub.6 are connected with
each other to form a ring.
10. A method for processing a silver halide color photographic material as
claimed in claim 9, wherein a substituent for the alkyl group, aralkyl
group or aryl group is selected from a nitro group, a hydroxy group, a
cyano group, a sulfo group, an alkoxy group, an aryloxy group, an acyloxy
group, an acylamino group, a sulfonamido group, a sulfamoyl group, a
halogen atom, a carboxy group, a carbamoyl group, an alkoxycarbonyl group
and a sulfonyl group.
11. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein M.sup.n+ is selected from H.sup.+, Na.sup.+,
K.sup.+, and NH.sub.4.sup.+.
12. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein the amount of the compound represented by
formula (II) is from 0.003 mol to 1 mol per mol of the magenta coupler
represented by formula (I).
13. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein the layer containing the magenta coupler
represented by formula (I) and the compound represented by formula (II) is
a silver halide emulsion layer or a layer adjacent thereto.
14. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein the replenisher for a color developing
solution contains bromide ount of not more than 2.times.10.sup.-3 mol per
liter, and the amount of the replenisher is from 50 ml/m.sup.2 to 700
ml/m.sup.2.
15. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein the replenisher for a color developing
solution does not contain bromide at all, and the amount of the
replenisher is from 100 ml/m.sup.2 to 500 ml/m.sup.2.
16. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein the color developing solution further contains
a chelating agent represented by formula (III), (IV) or (V):
##STR23##
wherein n represents 1 or 2; m represents 0 or 1; R represents a lower
alkyl group; and M which may be the same or different, each represents a
hydrogen atom or alkali metal.
17. A method for processing a silver halide color photographic material as
claimed in claim 1, wherein a processing time of the color development is
from 40 seconds to 3 minutes. |
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Claims |
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Description |
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FIELD OF THE INVENTION
The present invention relates to a method for processing a silver halide
color photographic material, and more particularly to a method for
processing a silver halide color photographic material wherein the amount
of a replenisher required for a color developing solution is reduced.
BACKGROUND OF THE INVENTION
In general, color photographic images can be formed by color development of
a photographic light-sensitive material, after imagewise exposure, with a
color developing solution containing an aromatic primary amine developing
agent such as a p-phenylenediamine, etc., followed by bleaching, fixing
and washing with water, etc. For the purpose of conducting a rapid
processing, a bleach-fixing step in which a bleaching step and a fixing
step are simultaneously carried out is also known.
In recent years, environmental conservation, saving and recovering of water
resources and silver resources have been regarded as important in
processing method wherein color photographic processing is conducted
automatically and continuously, and thus methods for preventing
environmental pollution, methods for efficiently recovering silver, and
methods for reduction and reuse of washing with water have been strongly
desired.
Further, from a standpoint of simplification of processing method, it has
been also strongly desired to conduct a method in which an amount of
replenisher for processing solution is small in a development processing
step using a replenishment system.
The amount of replenishment for a developing solution in a continuous
development processing can be somewhat varied depending on kinds of
photographic light-sensitive materials to be processed. However, it is
usually in a range from about 1100 ml to 1300 ml per m.sup.2 in the case
of silver halide color photographic materials for photographing.
It has been desired to reduce the amount of replenishment required from the
viewpoint described above. However, the reduction of the amount of
replenishment is generally very difficult to achieve since the reduction
leads to deterioration of photographic properties.
On the other hand, in order to satisfy the requirement for environmental
conservation, various regeneration methods of color developing solutions
have been proposed in color development processing steps. Examples of such
methods are described, for example, in J. Appl. Phot. Eng., Vol. 5, page
208 (1979); Gekkan Labo, Vol. 15, page 113 (1979); SMPTE. J., Vol. 88,
page 165 (1979); J. Appl. Phot. Eng., Vol. 5, page 32 (1974); SMPTE. J.,
Vol. 88, page 168 (1979); and Japanese Patent Application (OPI) Nos.
143018/77, 146236/77, 149331/78 and 9629/79 (the term "OPI" as used herein
means an "unexamined published application"), J. Appl. Phot. Eng., Vol. 5,
page 216 (1979), etc.
Further, when the amount of replenishment is reduced, it is generally the
case that substances dissolved from the silver halide photographic
materials (for example, halogen ions formed as the result of decomposition
of silver halide) relatively increase and thereby cause a problem of
decrease in sensitivity.
Against the problem of the decrease in sensitivity, there has been
attempted to reduce the amount of replenishment while preventing from the
decrease in sensitivity by means of increase in processing temperature.
Examples of these methods are described, for example, in a reference on
processing chemicals CP-LR for color paper of Hunt Co., Ltd.,
specifically, Photographic Bulletin, No. 49, page 6, "Color Print
Chemistries", published by Hunt Co., Ltd., Preprint A-7, "Reduced amount
of replenishment for processing color paper" published from The Society of
Photographic Science and Technology of Japan (1980), etc. The former
processing chemicals can be reduced the amount of replenishment for color
developing solution to a range of 1/2 to 2/3 of a conventional amount of
replenisher.
However, these methods relate to processing for color paper and can not be
immediately applied to processing of color photographic light-sensitive
materials for photographing in view of photographic characteristics such
as sensitivity, gradation, color reproducibility, etc.
With processing of color negative films, processing chemicals of Hunt Co.,
Ltd. are employed in a reduced replenishment system of 754 ml per m.sup.2,
as described in Photographic Bulletin, No. 55, published by Hunt Co., Ltd.
However, stability of processing is still insufficient. It is assumed as
reason of the above insufficient stability that the color photographic
light-sensitive materials themselves are easy to undergo an influence due
to variety of composition of a color developing solution which is
accompanied by the condensation and the oxidation, and in a running
process an initial concentration cannot be maintained, thereby an instable
condition is produced since a concentration of bromide in a replenisher
for a color developing solution exceeds 3.times.10.sup.-3 mol/l.
When the amount of replenishment for a color developing solution is
reduced, processing variation of color photographic light-sensitive
material becomes large. In the case of replenishing amount of not more
than 900 ml per m.sup.2, concentration of a color developing solution due
to evaporation and accumulation of the substances dissolved from
photographic light-sensitive materials as described above cause trouble,
and specifically result in increase in processing variation such as
variation in gradation and increase in stain, etc.
Furthermore, it is a general practice to raise processing temperature in
order to shorten a color developing time. In such a case, the above
described processing variation and concentration due to evaporation become
larger. In addition, other problems in that precipitates occur in the
color developing solution and in that scum adheres onto the photographic
light-sensitive materials accompany the use of a reduced amount of
replenisher and the rapid processing. These problems become particularly
severe when the color developing time is shortened.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to provide a method for
processing a silver halide color photographic material in which problems
regarding the photographic characteristics do not occur when an amount of
replenisher for a color developing solution is reduced.
Another object of the present invention is to provide a method for
processing a silver halide color photographic material in which
precipitates do not occur in a color developing solution and adhesion of
scum onto the photographic material is prevented.
Other objects of the present invention will become apparent from the
following detailed description and examples.
It has been found that these objects of the present invention can be
accomplished by a method for processing a silver halide color photographic
material comprising a support having thereon at least one silver halide
emulsion layer and containing a magenta dye forming coupler represented by
formula (I) shown below and a compound represented by formula (II) shown
below in the same layer, wherein the silver halide color photographic
material is subjected to color development using a replenisher for a color
developing solution, whose concentration of bromide is not more than
3.times.10.sup.-3 mol per liter and an amount of the replenisher for a
color developing solution is not more than 900 ml per m.sup.2 of the
silver halide color photographic material.
Formula (I) is represented by
##STR2##
wherein R.sub.1 represents an aromatic group, an aliphatic group or a
heterocyclic group; R.sub.2 represents a substituent; Za, Zb, Zc and Zd,
which may be the same or different, each represents an unsubstituted
methine group, a substituted methine group or --N.dbd.,
Formula (II) is represented by
(R'--COO.sup.-).sub.n M.sup.n+ (II)
wherein R' represents a substituent which imparts a diffusion-resistant
property to the compound represented by formula (II); M.sup.n+ represents
a hydrogen ion, a metal ion, or an ammonium ion; and n represents an
integer from 1 to 4.
DETAILED DESCRIPTION OF THE INVENTION
The magenta dye forming coupler (also referred to herein more as the
"magenta coupler") represented by formula (I) which can be used in the
present invention is described in more detail below.
In the above described formula (I), R.sub.1 represents a straight chain or
branched chain alkyl group having from 1 to 32 carbon atoms, and
preferably from 1 to 22 carbon atoms (e.g., a methyl group, an isopropyl
group, a tert-butyl group, a hexyl group, a dodecyl group, etc.), an
alkenyl group (e.g., an allyl group, etc.), a cyclic alkyl group (e.g., a
cyclopentyl group, a cyclohexyl group, a norbornyl group, etc.), an
aralkyl group (e.g., a benzyl group, a .beta.-phenylethyl group, etc.), a
cyclic alkenyl group (e.g., a cyclopentenyl group, a cyclohexenyl group,
etc.), etc., which roups each may be substituted with a halogen atom, a
nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy
group, a carboxy group, an alkylthiocarbonyl group, an arylthiocarbonyl
group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a
sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino
group, a ureido group, a urethane group, a thiourethane group, a
sulfonamido group, a heterocyclic group, an arylsulfonyl group, an
alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino
group, a dialkylamino group, an anilino group, an N-arylanilino group, an
N-alkylanilino group, an N-acylanilino group, a hydroxy group, a mercapto
group, etc.
R.sub.1 may further represent an aryl group (e.g., a phenyl group, an
.alpha.- or .beta.-naphthyl group, etc.). The aryl group may have one or
more substituents. Specific examples of the substituents include an alkyl
group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic
alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl
group, an alkoxy group, an aryloxy group, a carboxy group, an
alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl
group, a carbamoyl group, an acylamino group, a diacylamino group, a
ureido group, a urethane group, a sulfonamido group, a heterocyclic group,
an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an
alkylthio group, an alkylamino group, a dialkylamino group, an anilino
group, an N-alkylanilino group, an N-arylanilino group, an N-acylanilino
group, a hydroxy group, a mercapto group, etc. A more preferable group for
R.sub.1 is a phenyl group which is substituted with an alkyl group, an
alkoxy group, a halogen atom, etc., at at least one of the o-positions,
because it is effective to restrain coloration of couplers remaining in
film layers due to light or heat.
Furthermore, R.sub.1 may represent a heterocyclic group (e.g., a 5-membered
or 6-membered heterocyclic ring containing as a hetero atom at least one
of a nitrogen atom, an oxygen atom and a sulfur atom, or a condensed ring
thereof, with specific examples including a pyridyl group, a quinolyl
group, a furyl group, a benzothiazolyl group, an oxazolyl group, an
imidazolyl group, a naphthoxazolyl group, etc.), a heterocyclic group
substituted with one or more substituents as defined for the
above-described aryl group, an aliphatic acyl group, an aromatic acyl
group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl
group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an
arylthiocarbamoyl group.
In the above described formula (I), R.sub.2 represents a substituent such
as a hydrogen atom, a straight chain or branched chain alkyl group having
from 1 to 32 carbon atoms and preferably from 1 to 22 carbon atoms, an
alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl
group (each of which may have one or more substituents as defined above as
substituents for R.sub.1), an aryl group or a heterocyclic group (which
each also may have one or more substituents as defined above as
substituents for R.sub.1), an alkoxycarbonyl group (e.g., a
methoxycarbonyl group, an ethoxycarbonyl group, a stearyloxycarbonyl
group, etc.), an aryloxycarbonyl group (e.g., a phenoxycarbonyl group, a
naphthoxycarbonyl group, etc.), an aralkyloxycarbonyl group (e.g., a
benzyloxycarbonyl group, etc.), an alkoxy group (e.g., a methoxy group, an
ethoxy group, a heptadecyloxy group, etc.), an aryloxy group (e.g., a
phenoxy group, a tolyloxy group, etc.), an alkylthio group (e.g., an
ethylthio group, a dodecylthio group, etc.), an arylthio group (e.g., a
phenylthio group, an .alpha.-naphthylthio group, etc.), a carboxy group,
an acylamino group (e.g., an acetylamino group, a
3-[(2,4-di-tert-amylphenoxy)acetamido]benzamido group, etc.), a
diacylamino group, an N-alkylacylamino group (e.g., an
N-methylpropionamido group, etc.), an N-arylacylamino group (e.g., an
N-phenylacetamido group, etc.), a ureido group (e.g., a ureido group, an
N-arylureido group, an N-alkylureido group, etc.), a thioureido group
(e.g., a thioureido group, an N-alkylthioureido group, etc.), a urethane
group, a thiourethane group, an arylamino group (e.g., a phenylamino
group, an N-methylanilino group, a diphenylamino group, an N-acetylanilino
group, a 2-chloro-5-tetradecanamidoanilino group, etc.), an alkylamino
group (e.g., a n-butylamino group, a methylamino group, a cyclohexylamino
group, etc.), a cycloamino group (e.g., a piperidino group, a pyrrolidino
group, etc.), a heterocyclic amino group (e.g., a 4-pyridylamino group, a
2-benzoxazolylamino group, etc.), an alkylcarbonyl group (e.g., a
methylcarbonyl group, etc.), an arylcarbonyl group (e.g., a phenylcarbonyl
group, etc.), a sulfonamido group (e.g., an alkylsulfonamido group, an
arylsulfonamido group, etc.), a carbamoyl group (e.g., an ethylcarbamoyl
group, a dimethylcarbamoyl group, an N-methylphenylcarbamoyl group, an
N-phenylcarbamoyl group, etc.), a sulfamoyl group (e.g., an
N-alkylsulfamoyl group, an N,N-dialkylsulfamoyl group, an N-arylsulfamoyl
group, an N-alkyl-N-arylsulfamoyl group, an N,N-diarylsulfamoyl group,
etc.), an acyloxy group (e.g., a benzoyloxy group, etc.), a sulfonyloxy
group (e.g., a benzenesulfonyloxy group, etc.), a cyano group, a hydroxy
group, a mercapto group, a halogen atom, a nitro group or a sulfo group.
Of the magenta dye forming couplers represented by formula (I), those
wherein R.sub.2 represents an anilino group, an acylamino group or an
arylureido group and R.sub.1 represents an aryl group which is substituted
with a chlorine atom at at least one of the o-positions are particularly
preferred.
When Za, Zb, Zc or Zd represents a substituted methine group in formula
(I), the substituents may be selected from those as defined for R.sub.2.
The nitrogen-containing ring compound of Za, Zb, Zc and Zd may further form
another ring condensed therewith. For example, a 5-membered or 6-membered
ring containing two adjacent groups selected from Za to Zd and preferably
a hydrocarbon ring such as cyclohexene ring, a cyclopentene ring, a
benzene ring, a naphthalene ring, etc., or a heterocyclic ring such as
pyridine ring, a pyrimidine ring, a dihydrofuran ring, a dihydrothiophene
ring, etc. can be used. These rings may be substituted with one or more
substituents selected from those as defined for R.sub.2. Za, Zb, Zc and Zd
may be the same or different. However, a benzotriazolyl-1 group and a
benzotriazolyl-2 group are excluded from the condensed ring described
above.
Particularly preferred couplers among the couplers represented by formula
(I) used in the present invention are those wherein (1) the group of the
formula
##STR3##
represents a 5-membered monocyclic nitrogen-containing aromatic
heterocyclic group which is composed of Za, Zb, Zc and Zd that each
represents a methine group, a substituted methine group or --N.dbd., or
(2) the group of the formula
##STR4##
wherein Z represents a non-metallic atomic group forming a 5-membered or
6-membered ring. The substituted methine group has the same meaning as
defined in the formula (I). The groups of
##STR5##
may be substituted with one or more substituents selected from those as
defined for the substituted methine group. The 5-membered or 6-membered
condensed ring portion represented by Z has the same meaning as defined in
formula (I).
Specific examples of preferred nitrogen-containing heterocyclic groups
represented by the formula
##STR6##
include a 1-imidazolyl group, a 2-methyl-1-imidazolyl group, a
2-methylthio-1-imidazolyl group, a 2-ethylthio-1-imidazolyl group, a
2,4-dimethyl-1-imidazolyl group, a 4-methyl-1 imidazolyl group, a
4-nitro-1-imidazolyl group, a 4-chloro1-imidazolyl group, a
4-phenyl-1-imidazolyl group, a 4-acetyl-1-imidazolyl group, a
4-tetradecanamido-1-imidazolyl group, a 1-pyrolyl group, a
3,4-dichloro-1-pyrolyl group, a 2-isoindolyl group, a 1-indolyl group, a
1-pyrazolyl group, a 1-benzimidazolyl group, a 5-bromo-1-benzimidazolyl
group, a 5-octadecanamido-1-benzimidazolyl group, a
2-methyl-1benzimidazolyl group, a 5-methyl-1-benzimidazolyl group, a
7-purinyl group, a 2-indazolyl group, a 1,2,4,4-triazolyl group, a
1,2,3-1-triazolyl group, a 1-tetrazolyl group, etc. Among these,
particularly preferred nitrogen-containing heterocyclic groups are a
1-imidazolyl group, a 2-methyl-1imidazolyl group, a
2,4-dimethyl-1-imidazolyl group, a 4-methyl-1-imidazolyl group, a
4-chloro-1-imidazolyl group, a 1-benzimidazolyl group, and a 1-tetrazolyl
group.
The compound represented by formula (I) may be connected to a main chain of
a polymer at a portion of R.sub.1, R.sub.2 or
##STR7##
as described in Japanese Patent Application (OPI) Nos. 224352/83 and
35730/85, and U.S. Pat. No. 4,367,282.
Specific examples of preferred compounds represented by formula (I) are set
forth below, but the present invention is not to be construed as being
limited thereto.
##STR8##
In the above formulae (M-15), (M-16) and (M-22) to (M-36), numerical values
indicated mean a ratio of the component in a percent by weight.
The compounds represented by formula (I) can be synthesized according to
the methods as described in Japanese patent application (OPI) No.
40825/81, U.S. Pat. Nos. 4,241,168, 4,310,619, 4,301,235, 4,308,343,
4,367,282, etc.
The compound represented by formula (II) which can be used in the present
invention are described in more detail below.
In the above described formula (II), the group which imparts a
diffusion-resistant property to the compound and is represented by R' has
from 8 to 40 carbon atoms and preferably from 12 to 32 carbon atoms, in
total and represents a straight chain or branched chain alkyl group (e.g.,
a hexyl group, an octyl group, a dodecyl group, a pentadecyl group, etc.),
an alkenyl group (e.g., an allyl group, etc.), a cyclic alkyl group (e.g.,
a cyclopentyl group, a cyclohexyl group, a norbornyl group, etc.), an
aralkyl group (e.g., a benzyl group, a .beta.-phenethyl group, etc.), a
cyclic alkenyl group (e.g., a cyclopentenyl group, a cyclohexenyl group,
etc.), etc., of which groups each may be substituted with a halogen atom,
a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy
group, a carboxy group, an alkylthiocarbonyl group, an arylthiocarbonyl
group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a
sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino
group, a ureido group, a urethane group, a thiourethane group, a
sulfonamido group, a heterocyclic group, an arylsulfonyl group, an
alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino
group, a dialkylamino group, an anilino group, an N-arylanilino group, an
N-alkylanilino group, an N-acrylanilino group, a hydroxy group, a mercapto
group, etc.
R' may further represent an aryl group (e.g., a phenyl group, an .alpha.-
or .beta.-naphthyl group, etc.). The aryl group may have one or more
substituents. Specific examples of the substituents include an alkyl
group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic
alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl
group, an alkoxy group, an aryloxy group, a carboxy group, an
alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl
group, a carbamoyl group, an acylamino group, a diacylamino group, a
ureido group, a urethane group, a sulfonamido group, a heterocyclic group,
an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an
alkylthio group, an alkylamino group, a dialkylamino group, an anilino
group, an N-alkylanilino group, an N-arylanilino group, an N-acylanilino
group, a hydroxy group, a mercapto group, etc.
Furthermore, R' may represent a heterocyclic group (e.g., a 5-membered or
6-membered heterocyclic ring containing as a hetero atom at least one of a
nitrogen atom, an oxygen atom and a sulfur atom, or a condensed ring
thereof, with specific examples including a pyridyl group, a quinolyl
group, a furyl group, a benzothiazolyl group, an oxazolyl group, an
imidazolyl group, a naphthoxazolyl group, etc.), a heterocyclic group
substituted with one or more substituents defined for the above-described
aryl group, an aliphatic acyl group, an aromatic acyl group, an
alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an
arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl
group.
In the formula (II), M.sup.n+ can be selected from an ion of the group I
in the Periodic Table (e.g., H.sup.+, Na.sup.+, K.sup.+, Cs.sup.+, etc.),
an ion of the group II in the Periodic Table (e.g., Mg.sup.2+, Ca.sup.2+,
Ba.sup.2+, etc.), an ion of the group VIII in the Periodic Table (e.g.,
Fe.sup.2+, Fe.sup.3+, Co.sup.2+, Co.sup.3+, Ni.sup.2+, etc.), and an
ammonium ion which may be represented by the formula
##STR9##
Of these cations, an cation of the group I, a cation of the group II and
the ammonium ion are preferred. More preferred ions are H.sup.+, Na.sup.+,
K.sup.+ and NH.sub.4.sup.+, and H.sup.+ is most preferred.
In the above described formula, R.sub.3, R.sub.4, R.sub.5 and R.sub.6,
which may be the same or different, each represents a hydrogen atom, an
alkyl group (e.g., a methyl group, an ethyl group, a tert-butyl group,
etc.), a substituted alkyl group, an aralkyl group (e.g., a benzyl group,
a phenethyl group, etc.), a substituted aralkyl group, an aryl group
(e.g., a phenyl group, a naphthyl group, etc.) or a substituted aryl
group, the total number of carbon atoms included in R.sub.3, R.sub.4,
R.sub.5 and R.sub.6 being up to 20, or each two of R.sub.3, R.sub.4,
R.sub.5, and R.sub.6 may be connected with each other to form a ring.
Suitable examples of the substituents for the alkyl group, the aralkyl
group and the aryl group include a nitro group, a hydroxy group, a cyano
group, a sulfo group, an alkoxy group (e.g., a methoxy group, etc.), an
aryloxy group (e.g., a phenoxy group, etc.), an acyloxy group (e.g., an
acetoxy group, etc.), an acylamino group (e.g., an acetylamino group,
etc.), a sulfonamido group (e.g., a methylsulfonamido group, etc.), a
sulfamoyl group (e.g., a methylsulfamoyl group, etc.), a halogen atom
(e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), a carboxy
group, a carbamoyl group (e.g., a methylcarbamoyl group, etc.), an
alkoxycarbonyl group (e.g., a methoxycarbonyl group, etc.), and a sulfonyl
group (e.g., a methylsulfonyl group, etc.), etc. When two or more of these
substituents are present, they may be the same or different.
Specific examples of preferred compounds represented by formula (II) are
set forth below, but the present invention is not to be construed as being
limited thereto.
##STR10##
The magenta coupler represented by formula (I) used in the present
invention can be added to a light-sensitive silver halide emulsion layer
or a layer adjacent thereof of the silver halide color photographic
material. It is preferred to add the magenta coupler to a light-sensitive
silver halide emulsion layer.
The magenta coupler can preferably be added in a range from
5.times.10.sup.-4 mol to 1 mol and particularly preferably from
3.times.10.sup.-3 mol to 0.4 mol, per mol of silver halide present in the
silver halide emulsion layer or an adjacent layer thereof.
The compound represented by formula (II) used in the present invention is
added to a layer which contains the magenta coupler described above. The
amount of the compound added is preferably in a range from 0.003 mol to 1
mol, more preferably from 0.01 mol to 0.5 mol and most preferably from
0.03 to 0.3 mol, per mol of the magenta coupler.
The improvement in image stability, particularly magenta image after
processing by means of the combined use of the magenta dye forming coupler
represented by formula (I) and the compound represented by formula (II) is
described in Japanese Patent Application (OPI) No. 956/87. However, there
are no teachings in the above application as to solving problems occurred
in the case of reducing the amount of replenishment for a color developing
solution.
The present invention is to obtain peculiar stable characteristics which
are obtained by not only combining the photographic material of the
present invention with a conventional replenisher of which the amount of
replenisher is reduced, but also setting up a concentration of bromide in
the range of 3.times.10.sup.-3 mol/l or less which has not been used until
now.
Therefore, a effect of the present invention is accomplished by the
relation of the photographic material and the amount of the replenisher.
In the processing method of the present invention, the amount of
replenisher for color development is not more than 900 ml/m.sup.2,
preferably from 50 ml/m.sup.2 to 700 ml/m.sup.2, and more preferably from
100 ml/m.sup.2 to 500 ml/m.sup.2.
The replenishment of a color developing solution can be performed according
to a known method. It is preferred to employ a quantitative pump such as a
bellows pump.
The concentration of bromide in the replenisher for a color developing
solution according to the present invention is not more than
3.times.10.sup.-3 mol per liter, and preferably not more than
2.times.10.sup.-3 mol per liter. And it is particularly preferred that the
replenisher does not contain bromide at all.
Specific examples of the bromide include an alkali metal bromide such as
sodium bromide, potassium bromide, etc.
It is not desirable that the concentration of bromide in the replenisher
exceeds 3.times.10.sup.-3 mol per liter, since problems such as increase
in variation of gradation and decrease in sensitivity, etc. occur.
The color photographic light-sensitive material according to the present
invention can be subjected to development processing in a conventional
manner as described, e.g., in Research Disclosure, RD No. 17643, pages 28
to 29 (Dec., 1978) and ibid., RD No. 18716, page 651, left column to right
column (1979).
In order to carry out photographic processing of the light-sensitive
material according to the present invention, any of known processes can be
utilized. Also, known processing solution can be used. The processing
temperature is usually selected from a range of from 18.degree. C. to
50.degree. C., but a temperature lower than 18.degree. C. or a temperature
higher than 50.degree. C. may also be used.
A color developing solution which can be used in the present invention is
generally composed of an alkaline aqueous solution containing a color
developing agent. The useful color developing agent includes known primary
aromatic amine developing agents such as a phenylenediamine (for example,
4-amino-N,N-diethylaniline-3-methyl-4-amino-N,N-diethylaniline,
4-amino-N-ethyl-N-.beta.-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-.beta.-methanesulfonamidoethylaniline,
4-amino-3-methyl-N-ethyl-N-.beta.-methoxyethylaniline, etc.).
Furthermore, color developing agents as described, for example, in L. F. A.
Mason, Photographic Processing Chemistry, pages 226-229 (published by
Focal Press, 1966), U.S. Pat. Nos. 2,193,015 and 2,592,364, and Japanese
Patent Application (OPI) No. 64933/73, etc. may be used in the present
invention.
The color developing solution used in the present invention can further
contain pH buffers such as sulfites, carbonates, borates, and phosphates
of alkali metals and development inhibitors and antifoggants such as
bromides, iodides, and organic antifoggants. Also, if desired, the color
developing solution may further contain hard water softing agents;
preservatives such as hydroxylamine, etc.; organic solvents such as benzyl
alcohol, diethylene glycol, etc.; development accelerators such as
polyethylene glycol, quaternary ammonium salts, amines, etc.; dye-forming
couplers; competing couplers; fogging agents such as sodium borohydride,
etc.; auxiliary developing agents such as 1-phenyl-3-pyrazolidone, et al;
viscosity imparting agents; polycarboxylic acid series chelating agents as
described in U.S. Pat. No. 4,083,723; and antioxidants as described in
West German Patent Application (OLS) No. 2,622,950, etc.
In particular, when a chelating agent represented by formula (III), (IV),
or (V) shown below is added to the color developing solution, more
preferred effects can be achieved in view of prevention of variation of
gradation and increase in stain in a running process.
##STR11##
wherein n represents 1 or 2; m represents 0 or 1; R represents a lower
alkyl group; and M (which may be the same or different) each represents a
hydrogen atom or an alkali metal.
Specific examples of the chelating agents represented by formula (III),
(IV) or (V) are set forth below, but the present invention is not to be
construed as being limited thereto.
##STR12##
The chelating agent represented by formula (III), (IV) or (V) used in the
present invention can be added to the color developing solution in a range
of from 1.times.10.sup.-4 mol to 2.times.10.sup.-1 mol per liter, and
prefer | | |
