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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 in particularly to a method wherein the
stability of the color developer is improved, the coloring property of the
material is also improved, and the increase of the fog is remarkably
reduced during continuous processing.
BACKGROUND OF THE INVENTION
A color developer containing an aromatic primary amine color developing
agent has hitherto been utilized for the formation of photographic color
images, and at present, and continues to have a main role in image
formation methods in color photography. However, the color developer has a
problem in that it is extremely easily oxidized in the presence of air or
metals, and it is well known that the use of the oxidized developer for
the formation of color images can cause an increase of fog and fluctuation
of the sensitivity or gradation, with the result that the desired
photographic characteristics can not be obtained.
Under the situation, various means have heretofore been investigated so as
to improve the preservability of color developers, and among them, a
method of using both hydroxylamine and a sulfite ion is most general.
However, the hydroxylamine yields ammonia, which, when decomposed, causes
the generation of fog, while the sulfite ion also is a problem, in that it
acts as a competing compound for the developing agent, to interfere with
the coloring property thereof. Accordingly, it is difficult to say that
both of these compounds are preferred as the compound (preservative) for
improving the preservability of the color developer. In particular, when
the sulfite ion is used in a system not containing benzyl alcohol, which
is harmful during preparation of the developing solution (developer) in
view of environmental pollution problems, this causes an extreme lowering
of the color density of the image formed.
As a compound capable of being used in place of sulfites, the alkanolamines
described in Japanese Patent Application (OPI) No. 3532/79 (the term "OPI"
as used herein means a "published unexamined Japanese patent application")
and the polyethylene imines described in Japanese Patent Application (OPI)
No. 94349/81 have been proposed, but even these compounds could not attain
a fully satisfactory result.
In particular, a color photographic material having a silver chlorobromide
emulsion with a high chlorine content is often fogged during color
development (Japanese Patent Application (OPI) Nos. 95345/83 and
232342/84. Accordingly, when such emulsion is used, a preservative is
indispensable which has a low solubility in the emulsion and which has a
higher preserving function. However, a fully effective preservative has
not yet been found.
SUMMARY OF THE INVENTION
One object of the present invention is to provide a method for processing a
silver halide color photographic material with a color developer in which
the stability of the color developer is elevated.
Another object of the present invention is to provide a method for
processing a silver halide color photographic material with a color
developer in which the elevation of the fog of the material during
continuous processing can be remarkably reduced.
Still another object of the present invention is to provide a method for
processing a silver halide color photographic material with a color
developer in which the coloring property of the matrial is excellent even
when the color developer does not substantially contain benzyl alcohol.
The above-mentioned objects can be attained by a method for processing a
silver halide color photographic material, which comprises treating said
material after imagewise exposure with a color developer containing an
aromatic primary amine color developing agent and at least one compound
represented by formula (I)
##STR2##
in which X.sub.1 and X.sub.2 (which may be same or different) each
represents a divalent organic group.
DETAILED DESCRIPTION OF THE INVENTION
More preferably, X.sub.1 and X.sub.2 each represents an alkylene group
having from 2 to 10 carbon atoms (e.g., a dimethylene group, a
trimethylene group, a tetramethylene group, a methyltrimethylene group,
etc.); an alkenylene group having from 2 to 10 carbon atoms (e.g., an
ethylene group, a propenylene group, a butenylene group, etc.); an arylene
group having from 6 to 10 carbon atoms (e.g., a phenylene group); or a
group comprising a combination of said groups (e.g.,
##STR3##
or X.sub.1 and X.sub.2 together with sulfur atoms form a 6- to 10-membered
ring.
X.sub.1 and X.sub.2 may have substituent(s), which are, for example,
selected from a halogen atom (e.g., a fluorine atom, a chlorine atom, a
bromine atom, etc.), an alkyl group (e.g., a methyl group, an ethyl group,
a t-butyl group, a methoxyethyl group, etc.), an aryl group (e.g., a
phenyl group, a tolyl group, etc.), an alkoxy group (e.g., a methoxy
group, an ethoxy group, a methoxyethoxy group, etc.), an aryloxy group
(e.g., a phenoxy group, a p-nitrophenoxy group, etc.), a sulfonyl group
(e.g., a methanesulfonyl group, a phenylsulfonyl group, etc.), a
sulfonamido group (e.g., a methanesulfonamido group, a benzenesulfohamido
group, etc.), a sulfamoyl group (e.g., an unsubstituted sulfamoyl group, a
dimethylsulfamoyl group, etc.), a carbamoyl group (e.g., an unsubstituted
carbamoyl group, a methylcarbamoyl group, a dimethylcarbamoyl group,
etc.), an amido group (e.g., an acetamido group, a benzamido group, etc.),
a ureido group (e.g., a methylureido group, a phenylureido group, etc.),
an alkoxycarbonylamino group (e.g., a methoxycarbonylamino group, etc.),
an acyl group (e.g., an acetyl group, a benzoyl group, etc.), a formyl
group, a cyano group, a carboxyl group, a sulfo group, a hydroxyl group, a
nitro group, an alkylthio group (e.g., a methylthio group, a
carboxymethylthio group, etc.), an arylthio group (e.g., a phenylthio
group, etc.), an amino group (e.g., an unsubstituted amino group, a
dimethylamino group, etc.), etc. When X.sub.1 and/or X.sub.2 has(have) two
or more substituents, the substituents may be same or different. In
addition, these substituents may further be substituted.
Among the divalent organic groups for X.sub.1 and X.sub.2, the alkylene
group having from 2 to 10 carbon atoms is preferred.
Among the compounds of the formula (I), especially preferred are those
represented by formula (I-I)
##STR4##
in which R.sub.1 to R.sub.12 each represents a hydrogen atom or a
substituent as defined for X.sub.1 and X.sub.2, and R.sub.1 to R.sub.12
each is preferably a hydrogen atom, a halogen atom, an alkyl group, an
alkoxy group, a hydroxyl group, a carboxyl group, a sulfo group, a nitro
group or an alkylthio group. The carbon number of each of R.sub.1 to
R.sub.12 is preferably from 1 to 10 and more preferably from 1 to 5.
Specific examples of the compounds represented by formula (I) are shown
below, which, however, are not limitative.
##STR5##
The compounds represented by formula (I) can be produced in accordance with
the methods described in Aust. J. Chem., 1979, No. 32, pp. 2777-81; Inorg.
Chem., 1984, No. 23, pp. 3266-3269; J. Amer. Chem. Soc., 1978, 100 (20),
pp. 6416-21; J. Org. Chem., 1983, No. 48, pp. 3707-3712; Indian. J. Chem.,
10 (8), pp. 812-14; etc.
The content of the compound of formula (I) in the color developer is
preferably from 0.05 g to 50 g, and more preferably from 0.1 g to 20 g,
per liter of the developer.
It is preferred that the compound of formula (I) is incorporated into the
developer in an amount of from 0.1 to 100 mols per mol of the aromatic
primary amine developing agent.
The color developer for use in the present invention is explained in detail
hereinafter.
The color developer for use in the present invention contains a known
aromatic primary amine color developing agent. Preferred examples of the
developing agent are p-phenylenediamine derivatives, and specific examples
thereof are mentioned below, which are not limitative.
D-1: N,N-diethyl-p-phenylenediamine
D-2: 4-{N-ethyl-N-(.beta.-hydroxyethyl)amino}aniline
D-3: 2-Methyl-4-{N-ethyl-N-(.beta.-hydroxyethyl)amino}aniline
D-4: 4-Amino-3-methyl-{N-ethyl-N-(.beta.-methanesulfonamidoethyl)}aniline
These p-phenylenediamine derivatives can be in the form of salts thereof,
such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, etc. The
amount of aromatic primary amine developing agent in the developer is
preferably from about 0.1 g to about 20 g, and more preferably from about
0.5 g to about 10 g, per liter of the developer.
In particular, the developer D-4 is preferred, since the increase of fog is
small and a good photographic characteristic can be obtained when this is
used in the presence of the compound of formula (I).
The compounds of the present invention have excellent preserving capacity
in the processing system using an aromatic primary amine color developing
agent, when used together with a compound capable of directly stabilizing
the developing agent. As a compound capable of directly stabilizing the
developing agent, a watersoluble antioxidant is generally known, and,
examples include hydroxylamines and other compounds which are described
below.
As the compound which can be incorporated into the color developer for use
in the present invention, hydroxylamines are preferred, and especially
preferred compounds represented by formula (II) are especially preferred.
##STR6##
in which R.sup.21 and R.sup.22 each represents a hydrogen atom, an
unsubstituted or substituted alkyl group, an unsubstituted or substituted
alkenyl group, or an unsubstituted or substituted aryl group.
It is preferred that R.sup.21 and R.sup.22 each represents an alkyl group
or an alkenyl group, and it is more preferred that at least one of them
has substituent(s). R.sup.21 and R.sup.22 may be bonded to form a
heterocyclic ring together with the nitrogen atom in the formula.
The alkyl group and alkenyl group may be straight chain, branched chain, or
cyclic, and as the substituents for the said groups include a halogen
atom, an aryl group (e.g., a phenyl group, a p-chlorophenyl group, etc.),
an alkoxy group (e.g., a methoxy group, an ethoxy group, a methoxyethoxy
group, etc.), an aryloxy group (e.g., a phenoxy group, etc.), a sulfonyl
group (e.g., a methanesulfonyl group, a p-toluenesulfonyl group, etc.), a
sulfonamido group (e.g., a methanesulfonamido group, a benzenesulfonamido
group, etc.), a sulfamoyl group (e.g., diethylsulfamoyl group, an
unsubstituted sulfamoyl group, etc.), a carbamoyl group (e.g., an
unsubstituted carbamoyl group, a diethylcarbamoyl group, etc.), an amido
group (e.g., an acetamido group, a benzamido group, etc.), a ureido group
(e.g., a methylureido group, a phenylureido group, etc.), an
alkoxycarbonylamino group (e.g., a methoxycarbonylamino group, etc.), an
aryloxycarbonylamino group (e.g., a phenoxycarbonylamino group, etc.), an
alkoxycarbonyl group (e.g., a methoxycarbonyl group, etc.), an
aryloxycarbonyl group (e.g., a phenoxycarbonyl group, etc.), a cyano
group, a hydroxyl group, a carboxyl group, a sulfo group, a nitro group,
an amino group (e.g., an unsubstituted amino group, a diethylamino group,
etc.), an alkylthio group (e.g., methylthio group, etc.), an arylthio
group (e.g., a phenylthio group, etc.) and a heterocyclic group (e.g., a
morpholyl group, a pyridyl group, etc.). R.sup.21 and R.sup.22 may be same
or different, and the substituent(s) for R.sup.21 and R.sup.22 also may be
same or different.
The carbon number of each of R.sup.21 and R.sup.22 is preferably from 1 to
10, and more preferably from 1 to 5. As the nitrogen-containing
heterocyclic ring to be formed by the combination of R.sup.21 and
R.sup.22, there are a piperidyl group, a pyrrolidyl group, an
N-alkylpiperazyl group, a morpholyl group, an indolinyl group, a
benztriazolyl group, etc.
Preferred substituents for R.sup.21 and R.sup.22 are a hydroxyl group, an
alkoxy group, a sulfonyl group, an amido group, a carboxyl group, a cyano
group, a sulfo group, and a nitro group.
Specific examples of compound represented by formula (II) which can be used
in the present invention are set forth below, which, however, are not
intended to limit the scope of the present invention.
##STR7##
Other examples of the compounds represented by formula (II) are described
in the following patent publications, and the compounds represented by
formula (II) can be produced by known methods, for example, the methods
described in these patent publications. The patent publications are U.S.
Pat. Nos. 3,661,996, 3,362,961 and 3,293,034, Japanese Patent Publication
No. 2794/67, U.S. Pat. Nos. 3,491,151, 3,655,764, 3,467,711, 3,455,916,
3,287,125, and 3,287,124.
These compounds can be in the form of salts of various acids, such as
hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic
acid, acetic acid, etc. Other "compounds capable of directly stabilizing
developing agents" which are preferably used together with the compounds
of the present invention (i.e., other than the said hydroxylamines)
include, for example, hydrazines, hydrazides, phenols, saccharides,
hydroxamic acids, .alpha.-aminoketones, .alpha.-hydroxyketones, etc.
These compounds are described in further detail hereinafter.
The hydroxamic acids are preferably those represented by formula (III)
##STR8##
in which A.sup.31 represents a hydrogen atom, an alkyl group, an aryl
group, an amino group, a heterocyclic group, an alkoxy group, an aryloxy
group, a carbamoyl group, a sulfamoyl group, an acyl group, a carboxyl
group, a hydroxyamino group or a hydroxyaminocarbonyl group.
These groups may be substituted, and examples of the substituents for the
said groups include a halogen atom, an aryl group, an alkyl group, an
alkoxy group, an aryloxy group, a hydroxyl group, a sulfonyl group, a
sulfonamido group, a sulfamoyl group, a sulfo group, an amido group, a
ureido group, a cyano group, a hydroxyaminocarbonyl group, a carboxyl
group, a nitro group, an amino group, an alkoxycarbonyl group, an
aryloxycarbonyl group, an alkylthio group, an arylthio group, a
heterocyclic group (e.g., a pyridyl group, a morpholino group, etc.), etc.
Preferably, A.sup.31 represents a substituted or unsubstituted alkyl, aryl,
amino, alkoxy, or aryloxy group. Especially preferably, A.sup.31
represents a substituted or unsubstituted amino, alkoxy, or aryloxy group.
The carbon number of A.sup.31 is preferably from 1 to 10.
X.sup.31 represents
##STR9##
--SO.sub.2 --, or --SO--. Preferably, X.sup.31 represents
##STR10##
R.sup.31 represents a hydrogen atoms, an alkyl group or an aryl group.
A.sup.31 and R.sup.31 may optionally be bonded together to form a cyclic
structure. R.sup.31 may have a substituent(s), and as examples of such
substituents, the same substituents as those described for A.sup.31 can be
noted. Most preferably, R.sup.31 represents a hydrogen atom.
Y.sup.31 represents a hydrogen atom or a group capable of becoming a
hydrogen atom by hydrolysis.
Specific examples of the group for Y.sup.31, which can become a hydrogen by
hydrolysis, are as follows:
(1) Y.sup.31 is protected by an ester bond or a urethane bond, that is,
Y.sup.31 represents
##STR11##
in which R.sup.32 represents for example, an alkyl group, an aryl group,
or an amino group.
(2) Y.sup.31 is protected by the imidomethyl-blocking group described in
Japanese Patent Application (OPI) No. 158638/82, or, that is, Y.sup.31
represents
##STR12##
in which J represents
##STR13##
and Z represents a group of atoms completing a heterocyclic ring having at
least one 5- or 6-membered ring.
Examples of such compound are shown below, which, however, are not
limitative.
##STR14##
Other examples of the compound represented by formula (III) are described,
e.g., in Japanese Patent Application No. 186559/86, and these can be
obtained in accordance with the method described in said patent
application.
The hydrazines and hydrazides which can be used in the present invention
are preferably represented by formula (IV)
##STR15##
in which
R.sup.41, R.sup.42, and R.sup.43 each represents a hydrogen atom, an alkyl
group (preferably having from 1 to 20 carbon atoms, such as a methyl
group, an ethyl group, a sulfopropyl group, a carboxybutyl group, a
hydroxyethyl group, etc.), an aryl group (preferably having from 6 to 20
carbon atoms, such as a phenyl group, a 2,5-dimethoxyphenyl group, a
4-hydroxyphenyl group, a 2-carboxyphenyl group, etc.), or a heterocyclic
group (preferably having from 1 to 20 carbon atoms, such as a pyridin-4-yl
group, etc.);
R.sup.44 represents a hydroxyl group, a hydroxylamino group, an alkyl group
(preferably having from 1 to 20 carbon atoms, such as a methyl group, an
ethyl group, a sulfopropyl group, a carboxybutyl group, a hydroxyethyl
group, a cyclohexyl group, a benzyl group, etc.), an aryl group
(preferably having from 6 to 20 carbon atoms, such as a phenyl group, a
2,5-dimethoxyphenyl group, a 4-hydroxyphenyl group, a 2-carboxyphenyl
group, etc.), a heterocyclic group (preferably having from 1 to 20 carbon
atoms, such as a pyridin-4-yl group, etc.), an alkoxy group (preferably
having from 1 to 20 carbon atoms, such as a methoxy group, an ethoxy
group, a methoxyethoxy group, a benzyloxy group, a cyclohexyloxy group,
etc.), an aryloxy group (preferably having from 6 to 20 carbon atoms, such
as a phenoxy group, a p-methoxyphenoxy group, etc.), a carbamoyl group,
(preferably having from 1 to 20 carbon atoms, such as a carbamoyl group,
an N,N-diethylcarbamoyl group, a hydrazinocarbonyl group, etc.), or an
amino group (preferably having 20 or less carbon atoms, such as an amino
group, an N-phenylamino group, a hydrazino group, etc.);
X.sup.41 represents a divalent group selected from --CO--, --SO.sub.2 --,
or
##STR16##
n.sup.40 represents 0 or 1, and, in particular, when n.sup.40 is 0, then
R.sup.44 represents a group selected from an alkyl group, an aryl group,
and a heterocyclic group; or
R.sup.43 and R.sup.44 together form a heterocyclic ring, and such R.sup.43
and R.sup.44 may further be substituted by substituent(s).
In formula (IV), preferably R.sup.41, R.sup.42, and R.sup.43 each is a
hydrogen atom or an alkyl group; and most preferably, R.sup.41 and
R.sup.42 are hydrogen atoms.
In the formula (IV), R.sup.44 preferably represents an alkyl group, an aryl
group, an alkoxy group, a carbamoyl group, or an amino group; X.sup.41 is
more preferably --CO-- or --SO.sub.2 --, and is most preferably --CO--.
Specific examples of the compound of formula (IV) are shown below, which,
however, are not limitative.
##STR17##
Other examples of the compound represented by formula (IV) are described,
e.g., in Japanese Patent Application No. 170756/86, and these can be
obtained in accordance with the method described in said patent
application.
The phenols which can be used in the present invention are preferably
represented by formula (V)
##STR18##
Therein R.sup.51 represents a hydrogen atom, a halogen atom, an alkyl group
(e.g., a methyl group, an ethyl group, a t-butyl group, etc.), an aryl
group (e.g., a phenyl group, etc.), an alkoxy group (e.g., a methoxy
group, an ethoxy group, etc.), an aryloxy group (e.g., a phenoxy group,
etc.), a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl
group, an amido group (e.g., an acetamido group, a benzamido group, etc.),
a sulfonamido group (e.g., a methanesulfonamido group, a
benzenesulfonamido group, etc.), a ureido group, an alkylthio group (e.g.,
a methylthio group, etc.), an arylthio group (e.g., a phenylthio group,
etc.), a nitro group, a cyano group, an amino group, a formyl group, an
acyl group (e.g., an acetyl group, etc.), a sulfonyl group.(e.g., a
methanesulfonyl group, a benzenesulfonyl group, etc.), an alkoxycarbonyl
group (e.g., a methoxycarbonyl group, etc.), an aryloxycarbohyl group
(e.g., a phenoxycarbonyl group, etc.), an alkoxysulfonyl group (e.g., a
methoxysulfonyl group, etc.), or an aryloxysulfonyl group (e.g., a
phenoxysulfonyl group, etc.). When R.sup.51 is further substituted, the
substitutents include a halogen atom, an alkyl group, an aryl group, a
hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, a
sulfo group, a carbamoyl group, a sulfamoyl group, an amido group, a
sulfonamido group, a ureido group, an alkylthio group, an arylthio group,
a nitro group, a cyano group, an amino group, a formyl group, an acyl
group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl
group, an alkoxysulfonyl group, an aryloxysulfonyl group, a heterocyclic
group (e.g., a morpholyl group, a pyridyl group, etc.), etc. R.sup.51 may
have two or more same or different kinds of these substituents. When
R.sup.51 have two or more substituents (that is, when m is two or more),
the kind of the substituents may be same or different, and when the
substituents are adjacent to each other, these may be bonded to form a
ring. The ring structure is a 5- or 6-membered ring, which is composed of
carbon, hydrogen, halogen, oxygen, nitrogen and/or sulfur atoms, etc., and
the ring may be saturated or unsaturated. In the group R.sup.51 and the
substituent(s), the carboxyl group and the sulfo group may be in the form
of a salt with an alkali metal (e.g., Na, K, etc.), and the amino group
may also form a salt with various kinds of acids, such as hydrochloric
acid, etc.
Also in the formula (V), R.sup.52 represents a hydrogen atom or a
hydrolyzable group. The hydrolyzable group means a group which can be
hydrolyzed to a hydrogen atom, and examples of the group include
##STR19##
(in which R.sup.53 represents an alkyl group, an aryl group, or an amino
group). That is, the hydrolyzable group is a group as protected by an
ester bond or an urethane bond. Another example of the group is a group as
protected by the imidomethyl-blocking group described in Japanese Patent
Application (OPI) No. 158638/82. That is, the group is represented by the
formula
##STR20##
in which R.sup.54 represents
##STR21##
R.sup.55 represents a group of atoms completing a heterocyclic ring having
at least one 5- or 6-membered ring. In formula (V), m.sup.50 and n.sup.50
each represent an integer of from 1 to 5.
In formula (V), R.sup.51 is preferably an alkyl group, halogen atom, an
alkoxy group, an alkylthio group, a carboxyl group, a sulfo group, a
carbamoyl group, a sulfamoyl group, an amino group, an amido group, a
sulfonamido group, a nitro group or a cyano group, and among these, an
alkoxy group, an alkylthio group, an amino group and a nitro group are
particularly preferred as R.sup.51. R.sup.51 is more preferably positioned
at ortho- or para-position to the group --OR.sup.52. The carbon number of
the group R.sup.51 is preferably from 1 to 10, and especially preferably
from 1 to 6.
Preferably, R.sup.52 represents a hydrogen atom or a hydrolyzable group
having from 1 to 5 carbon atoms. When two or more groups OR.sup.52 are
present in the benzene nucleus (that is, when n.sup.50 is two or more),
these are preferably ortho- or para-positioned to each other.
Specific examples of the compound represented by formula (V) are shown
below, which, however, are not limitative.
##STR22##
Other examples of the compound of the formula (V) are described in Japanese
Patent Application Nos. 188742/86 and 203253/86, and these can be obtained
in accordance with the method described in the said patent applications.
The .alpha.-hydroxyketones and .alpha.-aminoketones which can be used in
the present invention are preferably represented by formula (VI)
##STR23##
in which
R.sup.61 represents a hydrogen atom, an alkyl group (preferably having from
1 to 20 carbon atoms, such as a methyl group, an ethyl group, a
hydroxymethyl group, a methoxyethyl group, a cyclohexyl group, etc.), an
aryl group (preferably having from 6 to 20 carbon atoms, such as a phenyl
group, a 2-hydroxyphenyl group, etc.), an alkoxy group (preferably having
from 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, a
methoxyethoxy group, etc.), an aryloxy group, (preferably having from 6 to
20 carbon atoms, such as a phenoxy group, a 4-methoxyphenoxy group, etc.),
or an amino group (preferably having 20 or less carbon atoms, such as an
amino group, an N,N-diethylamino group, an N-phenylamino group, etc.);
R.sup.62 represents a hydrogen atom, an alkyl group (preferably having from
1 to 20 carbon atoms, such as a methyl group, an ethyl group, a
hydroxymethyl group, etc.), or an aryl group (preferably having from 6 to
20 carbon atoms, such as a phenyl group, a 2-hydroxyphenyl group, etc.);
or R.sup.61 and R.sup.62 together form a carbocyclic ring or a
heterocyclic ring;
X.sup.61 represents a hydroxyl group or an amino group (preferably having
20 or less carbon atoms, such as an amino group, an N,N-diethylamino
group, a morpholino group, etc.).
In formula (VI), R.sup.61 is preferably a hydrogen atom, an alkyl group, an
aryl group, or an alkoxy group; and R.sup.62 is preferably a hydrogen atom
or an alkyl group.
Specific examples of the compound of the formula (VI) are shown below,
which, however, are not limitative.
##STR24##
Other examples of the compound of the formula (VI) are described, e.g., in
Japanese Patent Application No. 188741/86, and these can be obtained in
accordance with the method described in said patent application.
Next, the "saccharides" which can be used in the present invention is
explained in detail hereunder.
The saccharides (which are also called "carbohydrate") include
monosaccharides and polysaccharides, and most of them are represented by
formula C.sub.n H.sub.2n O.sub.m. The monosaccharides generically include
aldehydes or ketones of polyhydric alcohols (which are called "aldoses"
and "ketoses," respectively) as well as the reduced derivatives, oxidized
derivatives and dehydrated derivatives, thereof, aminosaccharides and
thio-saccharides, and other derivatives of a broad range.
"Polysaccharides" as used herein refers to reaction products formed by
dehydration condensation of two or more of the said monosaccharides.
Among these saccharides, reducing aldehyde group-containing aldoses and
derivatives thereof are preferred, and in particular, the corresponding
monosaccharides are more preferred.
Specific examples of the saccharides which can be used in the present
invention are described below, which, however, are not limitative. In
addition, the optical isomers of the saccharides can also be used in the
same manner.
##STR25##
The above-mentioned compounds are readily avaiable as commercial products.
The amount (total) of the compounds represented by formulae (III) to (VII)
to be added to the color developer is preferably from 0.01 g to 20 g, and
more preferably from 0.5 g to 10 g, per liter of the color developer.
As preservatives, sulfites such as sodium sulfite, potassium sulfite,
sodium bisulfite, potassium bisulfite, sodium metabisulfite, potassium
metabisulfite, etc., as well as carbonyl-sulfite adducts can also be added
to the color developer, if desired. The amount of the said preservatives
to be added to the color developer may be 20 g/liter or less, and
preferably 5 g/liter or less, and the amount is preferred to be smaller,
provided that the preservation of the color developer can be ensured to be
good.
In addition, the color developer may further contain other preservatives,
such as various kinds of metals described in Japanese Patent Application
(OPI) Nos. 44148/82 and 53749/82, etc.; various kinds of saccharides
described in Japanese Patent Application (OPI) No. 102727/77, etc.; the
.alpha.,.alpha.'-dicarbonyl compounds described in Japanese Patent
Application (OPI) No. 160141/84, etc.; the salicyclic acids described in
Japanese Patent Application (OPI) No. 180588/84, etc.; the gluconic acid
derivatives described in Japanese Patent Application (OPI) No. 75647/81,
etc., if desired. Two or more kinds of these preservatives may be used
together, if desired. In particular, the addition of aromatic polyhydroxy
compounds is preferred.
The color developer for use in the present invention preferably has a pH
value of from 9 to 12, and more preferably from 9 to 11.0, and the color
developer can contain various known developer components in addition to
the above-mentioned ingredients.
In order to maintain the a proper pH value, the color developer preferably
contains various kinds of buffers. The buffers which are usable include,
for example, carbonic acid salts, phosphoric acid salts, boric acid salts,
tetraboric acid salts, hydroxy-benzoic acid salts, glycine salts,
N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts,
3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyric acid salts,
2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts,
tris-hydroxyaminomethane salts, lysine salts, etc. In particular, carbonic
acid salts, phosphoric acid salts, tetraboric acid salts and
hydroxybenzoic acid salts are advantageous in that these are excellent in
solubility and have an excellent buffering capacity in a high pH range of
pH 9.0 or more, and therefore even when they are added to the color
developer, these have no bad influence on the photographic properties (for
example, fog. etc.). In addition, they are inexpensive. Accordingly, the
use of such buffers is especially preferred.
Specific examples of these buffers include sodium carbonate, potassium
carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate,
tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium
borate, potassium borate, sodium tetraborate (borax), potassium
tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium
o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium
5-sulfosalicyalte), potassium 5-sulfo-2-hydroxybenzoate (potassium
5-sulfosalicylate), etc. However, these compounds are not intended to
restrict the scope of the present invention.
The amount of the said buffer to be added to the color developer is
preferably 0.1 mol/liter or more, and is especially preferably from 0.1
mol/liter to 0.4 mol/liter.
In addition, the color developer can further contain various kinds of
chelating agents as a flocculation (precipitation)-preventing agent with
respect to calcium or magnesium, or for the purpose of improving the
stability of the color developer.
As the chelating agent, organic acid compounds are preferred, and for
example, there may be mentioned the aminopolycarboxylic acids described in
Japanese Patent Publication Nos. 30496/73 and 30232/69, etc.; the organic
phosphonic acids described in Japanese Patent Application No. 97347/81,
Japanese Patent Publication No. 39359/81, West German Pat. No. 2,227,639,
etc.; the phosphonocarboxylic acids described in Japanese Patent
Application (OPI) Nos. 102726/77, 42730/78, 121127/79, 126241/80 and
659506/80, etc.; and the compounds described in Japanese Patent
Application Nos. 195845/83 and 203440/83, Japanese Patent Publication No.
40900/78, etc.
Specific examples of the compounds, which, however, are not limitative,
include nitrilo-triacetic acid; diethylenetriamine-pentaacetic acid;
ethylenediamine-tetraacetic acid; N,N,N-trimethylene-phosphonic acid;
ethylenediamine-N,N,N',N'-tetramethylene-phosphonic acid;
trans-cyclohexane-diamine-tetraacetic acid; 1,2-diaminopropanetetraacetic
acid; glycolether-diamine-tetraacetic acid;
ethylenediamine-orthohydroxyphenylacetic acid;
2-phosphonobutane-1,2,4-tricarboxylic acid;
1-hydroxyethylidene-1,1-diphosphonic acid;
N,N'-bis(2-hydroxybenzyl)-ethylenediamine-N,N'-diacetic acid.
These chelating agents can be used in the form of a mixture of two or more
kinds thereof.
The amount of the chelating agent to be added to the color developer may be
a sufficient amount for blocking the metal ions in the developer. For
example, the amount may preferably be from about 0.1 g to 10 g, per liter
of the developer.
The color developer may contain an optional development accelerator, if
desired. However, it is preferred that the color developer of the present
invention does not substantially contain benzyl alcohol, in view of the
prevention of environmental pollution, the ease of the preparation of the
developer solution, and the prevention of fog. The terminology "does not
substantially contain benzyl alcohol" means that the content of the benzyl
alcohol in the developer is 2 ml/liter or less, or preferably the
developer contains no benzyl alcohol.
The above-mentioned compounds of the present invention are extremely
effective for improving the stability of even the color developer which
does not substantially contain benzyl alcohol.
As the other development accelerators which can be added to the color
developer for use in the present invention, there may be mentioned, for
example, the thioether series compounds described in Japanese Patent
Publication Nos. 16088/62, 5987/62, 7826/63, 12380/79 and 9019/70, U.S.
Pat. No. 3,813,247, etc.; the p-phenylenediamine series compounds
described in Japanese Patent Application (OPI) Nos. 49829/77 and 15554/75,
etc.; the quaternary ammonium salts described in Japanese Patent
Application (OPI) No. 137726/75, Japanese Patent Publication No. 30074/69,
Japanese Patent Application (OPI) Nos. 156826/81 and 43429/77, etc.; the
amine series compounds described in U.S. Pat. Nos. 2,494,903, 3,128,182,
4,230,796 and 3,253,919, Japanese Patent Publication No. 11431/66, U.S.
Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, etc.; the polyalkylene
oxides described in Japanese Patent Publication Nos. 16088/62 and
25201/67, U.S. Pat. No. 3,128,183, Japanese Patent Publication Nos.
11431/66 and 23883/67, U.S. Pat. No. 3,532,501, etc.; as well as
1-phenyl-3-pyrazolidones, imidazoles, etc. These can be added to the
developer, if desired.
In the practice of the present invention, any optional anti-foggant can be
added to the color developer, if desired. As the anti-foggant can be used
alkali metal halides such as sodium chloride, potassium bromide or
potassium iodide as well as organic anti-foggants. Specific examples of
the organic anti-foggants are nitrogen-containing heterocyclic compounds,
including, for example, benzotriazole, 6-nitrobenzimidazole,
5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
5-chlorobenzotriazole, 2-thiazolyl-benzimidazole,
2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolidine, adenine,
etc.
The color developer for use in the present invention preferably contains a
brightening agent. As the brightening agent are preferred
4,4'-diamino-2,2'-disulfostilbene series compounds. The amount of the
brightening agent to be added to the color developer is up to 5 g/liter,
and preferably from 0.1 to 4 g/liter.
In addition, various kinds of surfactants may be added to the color
developer, if desired, including alkylsulfonic acids, arylsulfonic acids,
aliphatic carboxylic acids, aromatic carboxylic acids. etc.
The processing temperature of the color developer of the present invention
is from 20.degree. to 50.degree. C., and preferably from 30.degree. to
40.degree. C. The processing time is from 20 seconds to 5 minutes, and
preferably from 30 seconds to 2 minutes. The amount of the replenisher is
preferred to be smaller and is, for example, from 20 to 600 ml, preferably
from 50 to 300 ml, and more preferably from 100 to 200 ml, per m.sup.2 of
the photographic light-sensitive material as being processed.
Next, the bleaching solution, bleach-fixing solution, and fixing solution
for use in the present invention are explained hereunder.
Any and every bleaching agent can be used in the bleaching solution or
bleach-fixing solution for use in the present invention. More
particularly, organic complex salts of iron(III) (for example, complex
salts with aminopolycarboxylic acids such as ethylenediaminetetraacetic
acid, diethylenetriaminepentaacetic acid, etc., aminopolyphosphonic acids,
phosphonocarboxylic acids or o | | |
