 |
Description  |
|
|
FIELD OF THE INVENTION
The present invention relates to a method of processing a silver halide
color photographic material and, more particularly, to a processing method
which ensures improvements in the stability and developability of a color
developer and marked reduction in the increase of fog in a running color
development process.
BACKGROUND OF THE INVENTION
Color developers containing color developing agents of the aromatic primary
amine type have been used from of old for formation of color images and at
present have a primary role in the color photographic image-forming
process. However, the color developers described above are exceedingly
prone to air oxidation and oxidation due to the presence of. It is
well-known that when color images are formed using oxidized developing
solutions, an increase in fog density and changes in photographic speed
and gradation are caused, which interfere with achieving the intended
photographic characteristics.
Therefore, various means for enhancing preservability of color developers
have so far been investigated. The most general means among them is the
combined use of hydroxylamine and sulfite ion. However, this method has
the drawback that the hydroxylamine produces ammonia by decomposition
which causes fog and the sulfite ion competes against the developing agent
to impair developability. Accordingly, it is hard to say that both of them
are preferred as a compound capable of enhancing the preservability of a
color developer (or a preservative).
In particular, sulfite ion, though it has been used from of old as an agent
capable of increasing the preservability of various color developing
agents or preventing the decomposition of hydroxylamines, drastically
impairs developability and lowers color density of the developed image to
a considerable extent, especially when it is used in a system free of
benzyl alcohol. Benzyl alcohol is harmful from the standpoint of
environmental pollution and preparation of developers.
Alkanolamines described in Japanese Patent Application (OPI) No. 3532/79
(the term "OPI" as used herein means an "unexamined published
application") and polyethylene imines described in Japanese Patent
Application (OPI) No. 94349/81 have been proposed as a substitute for
sulfites. However, these compounds cannot produce sufficient effects.
In addition, various kinds of preservatives and chelating agents have been
examined for the purpose of improving the stability of color developers.
As examples of preservatives, aromatic polyhydroxy compounds described in
Japanese Patent Application (OPI) Nos. 49828/77, 160142/84 and 47038/81,
U.S. Pat. No. 3,746,544, and so on, hydroxycarbonyl compounds described in
U.S. Pat. No. 3,615,503 and British Pat. No. 1,306,176,
.alpha.-aminocarbonyl compounds described in Japanese Patent Application
(OPI) Nos. 143020/77 and 89425/78, metal salts described in Japanese
Patent Application (OPI) Nos. 44148/82 and 53749/82, hydroxamic acids
described in Japanese Patent Application (OPI) Nos. 27638/77, and so on,
may be mentioned.
As examples of chelating agents, on the other hand, mention may be made of
aminopolycarboxylic acids described in Japanese Patent Publication Nos.
30496/73 and 30232/69, organic phosphonic acids described in Japanese
Patent Application (OPI) No. 97347/81, Japanese Patent Publication No.
39359/81 and West German Pat. No. 2,227,639, phosphonocarboxylic acids
described in Japanese Patent Application (OPI) Nos. 102726/77, 42730/78,
121127/79, 126241/80 and 65956/80, and so on, and other compounds
described in Japanese Patent Application (OPI) Nos. 195845/83 and
203440/83, Japanese Patent Publication No. 40900/78, and so on.
However, sufficient preservability cannot be obtained with any of the
preservatives and chelating agents described above and, what is worse,
some of them exert undesirable effects upon photographic characteristics.
For the foregoing reasons, satisfactory results have not yet been achieved
and the advent of excellent preservatives, especially those capable of
taking the place of sulfites, have been desired.
Further, it is described in Japanese Patent Application (OPI) Nos. 95345/83
and 232342/84 that a color photographic material comprising a silver
chlorobromide emulsion with a high chloride content tends to generate fog
at the time of color development. When an emulsion of the above-described
kind is used, a preservative which has low solubility in the emulsion and
more excellent preservability is essential to a color developer. Any
preservative which will suffice for the above-described needs also has not
been found until now.
SUMMARY OF THE INVENTION
Therefore, one object of the present invention is to provide a method of
processing a silver halide color photographic material in which the color
developer used is excellent in stability and the increase in fog density
in the running color development process is reduced to a considerable
extent.
Another object of the present invention is to provide a method of
processing a silver halide color photographic material in which excellent
developability can be acquired, not withstanding the fact that the color
developer is substantially free of benzyl alchol.
The above-described objects of the present invention have been attained
with a method of processing a silver halide color photographic material in
which the development processing is performed using a developer containing
an aromatic primary amine color developing agent and at least one compound
represented by the formula:
##STR2##
wherein X is a trivalent group necessary to complete a condensed ring; and
R.sup.1 and R.sup.2 may be the same as or different from each other and
R.sup.1 and R.sup.2 each represents an alkylene group, an arylene group,
an alkenylene group, or an aralkylene group.
DETAILED DESCRIPTION OF THE INVENTION
In formula (I), groups preferred as X are trivalent groups containing not
more than 20 carbon atoms, preferably not more than 10 carbon atoms, and
more preferably not more than 6 carbon atoms. X may further containing
other atoms like nitrogen, oxygen, sulfur or so on.
X preferably represents a trivalent group containing not more than 6 carbon
atoms, which may further contain a nitrogen atom or an oxygen atom.
Each of the groups represented by R.sup.1 and R.sup.2 in formula (I) may be
substituted by other groups, for example, by a hydroxy group, an alkoxy
group, etc. The number of carbon atoms contained in R.sup.1 and R.sup.2,
respectively, is preferably 10 or less, more preferably 6 or less, and
particularly preferably 3 or less. R.sup.1 and R.sup.2 each preferably
represents an alkylene group or an arylene group, and particularly
preferably represents an alkylene group.
The compound of formula (I) may be a bis or tris body formed by connecting
to each other through X.
Specific examples of groups represented by X in formula (I) include
##STR3##
so on.
Specific examples of groups represented by R.sup.1 abnd R.sup.2 in formula
(I) include a methylene group, an ethylene group, a propylene group, a
butylene group, a pentylene group, a 1,2-cyclohexylene group, a
1-methylethylene group, a 1,2-dimethylethylene group, a 1-carbocxyethylene
group, a 1,2-phenylene group, a 1,2-vinylene group, a 1,3-propenylene
group, and so on. These groups each may further be substituted with an
alkyl group, a halogen atom, a carboxyl group, a sulfo group, a hydroxyl
group, an alkoxy group, an alkylthio group, an amino group, an amido
group, an acyl group, a carbamoyl group, a sulfamoyl group, a heterocyclyl
group, and so on.
Of the compounds represented by formula (I), particularly preferred ones
are represented by formulae (I-a) and (I-b).
##STR4##
In the above formula, X.sup.1 represents
##STR5##
R.sup.1 and R.sup.2 may be the same or different and each have the same
meanings, respectively, as R.sup.1 and R.sup.2 in formula (I). R.sup.3
represents one of the groups represented by R.sup.1 and R.sup.2, or
##STR6##
In formula (I-a), a preferred X.sup.1 is
##STR7##
The number of carbon atoms contained in the groups represented by each of
R.sup.1, R.sup.2 and R.sup.3, respectively, is preferably 6 or less, more
preferably 3 or less, and particularly preferably 2. Groups preferred as
R.sup.1, R.sup.2 and R.sup.3 respectively are an alkylene group and an
arylene group, and the most preferred one is an alkylene group.
##STR8##
In the above formula, R.sup.1 and R.sup.2 may be the same or different and
each have the same meanings, respectively, as R.sup.1 and R.sup.2 in
formula (I).
The number of carbon atoms in groups represented by R.sup.1 and R.sup.2,
respectively, is preferably 8 or less, more preferably 6 or less in the
formula (I-b). Among groups represented by R.sup.1 and R.sup.2, favored
ones are an alkylene group and an arylene group, and the most favored one
is an alkylene group.
The compounds represented by formula (I-a) are preferable to those
represented by formula (I-b).
Specific examples of the compounds of the present invention, which are
represented by the foregoing formula (I), are illustrated below. However,
the invention should not be constured as being limited to the following
compounds.
##STR9##
Many of the compounds represented by formula (I) in the present invention
are easily available as commercial products.
Each of the compounds represented by formula (I) is added in an amount of
preferably 0.1 to 50 g, particularly 0.2 to 20 g, per liter of color
developer.
A color developer which can be used in the present invention is described
below.
The color developer to be used in the present invention contains a known
color developing agent of the aromatic primary amine type.
Aromatic primary amines preferred as a color developing agent are
p-phenylene diamine derivatives, and typical examples of the derivatives
are cited below. However, the invention should not be contrued as being
limited to the following examples.
D-1 N,N-diethyl-p-phenylenediamine.
D-2 4-[N-ethyle-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 may used in their salt form, such as
sulfate, hydrochloride, sulfite, p-toluene-sulfonate, etc, salts. A color
developing agent of the aromatic primary amine type is used in a quantity
of preferably about 0.1 g to about 20 g, more preferably about 0.5 g to
about 10 g, per liter of developing solution.
It is particularly preferred to use the color developing agent of D-4 in
the presence of the compound of formula (I) in respect that increase in
fog is checked and more desirable photographic characteristics are
obtained.
In addition, the compounds of the present invention can fully achieve their
preservability when used in combination with a compound capable of
directly stabilizing a color developing agent in the system using an
aromatic primary amine as the color developing agent. In general,
water-soluble antioxidants are known as the compounds capable of directly
stabilizing developing agents, with specific examples including
hydroxylamines and other compounds described hereinafter.
As the compound which can be used together with the compounds of the
present invention in the color developer, hydroxylamines are preferred. In
particular, those represented by the formula
##STR10##
are favored over others,
In formula (II), R.sup.21, and R.sup.22 each represents a hydrogen atom, or
an unsubstituted or substituted alkyl, alkenyl or aryl group.
Of groups represented by R.sup.21 and R.sup.22, an alkyl group and an
alkenyl group are preferred. When at least one of R.sup.21 and R.sup.22 is
a substituted alkyl or alkenyl group, the compound can produce a more
desirable effect. Also, R.sup.21 and R.sup.22 may combine with each other
to form a nitrogen atom-containing hetero ring.
Alkyl and alkenyl groups may assume any form, such as a straight chain, a
branched chain or a cyclic group, and they may be substituted by a halogen
atom, an aryl group (e.g., phenyl, p-chlorophenyl, etc.), an alkoxy group
(e.g., methoxy, ethoxy, methoxyethoxy, etc.), an aryloxy group (e.g.,
phenoxy, etc.), a sulfonyl group (e.g., methanesulfonyl,
p-toluenesulfonyl, etc.), a sulfonamido group (e.g., methanesulfonamido,
benzenesulfonamido, etc.), a sulfamoyl group (e.g., diethylsulfamoyl,
unsubstituted sulfamoyl, etc.), a carbamoyl group (e.g., unsubstituted
carbamoyl, diethylcarbamoyl, etc.), an amido group (e.g., acetamido,
benzamido, etc.), a ureido group (e.g., methylureido, phenylureido, etc.),
an alkoxycarbonylamino group (e.g., methoxycarbonyl amino, etc.), an
aryloxycarbonylamino group (e.g., phenoxycarbonylamino, etc.), a cyano
group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, an
amino group (e.g., unsubstituted amino, diethylamino, etc.), an alkylthio
group (e.g., methylthio, etc.), an arylthio group (e.g., phenylthio,
etc.), or a heterocyclyl group (e.g., morpholyl, pyridyl, etc.), or so on
The groups represented by R.sup.21 and R.sup.22 may be the same or
different and the substituent groups thereof may be the same or different.
The number of carbon atoms contained in the groups represented by R.sup.21
and R.sup.22 is preferably 1 to 10, particularly preferably 1 to 5.
Suitable examples of nitrogen-containing heterocyclyl groups formed by
combining R.sup.21 and R.sup.22 include a piperidyl group, a pyrrolidyl
group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, a
benzotriazolyl group, and so on.
Preferred substituent groups of R.sup.21 and R.sup.22 include a hydroxy
group, an alkoxy group, a sulfonyl group, an amido group, a carboxy group,
a cyano group, a sulfo group, a nitro group, and an amino group.
Specific examples of the compound represented by formula (II) which can be
used in the present invention are illustrated below. However, the
invention should not be construed as being limited to the following
compounds.
##STR11##
Other specific examples of the compound represented by formula (II) and
methods for synthesizing the compounds of formula (II) are shown in U.S.
Pat. Nos. 3,661,996, 3,362,961 and 3,293,034, Japanese Patent Publication
No. 2794/67, and U.S. Pat. Nos. 3,491,151, 3,655,764, 3,467,711,
3,455,916, 3,287,125 and 3,287,124.
Those compounds may form salts together with various kinds of acids, such
as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic
acid, acetic acid and so on.
As examples of "compounds capable of directly stabilizing color developing
agents", other than hydroxylamines, which are preferably used in
combination with the compounds of the present invention, mention may be
made of hydrazines, hydrazides, phenols, sugars, hydroxamic acids,
.alpha.-aminoketones, .alpha.-hydroxyketones, and so on.
Details of these compounds are illustrated below.
The hydroxamic acids are preferably represented by the formula
##STR12##
In formula (III), 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
carboxy group, a hydroxyamino group, or a hydroxyaminocarbonyl group.
These groups each may have a substituent group, such as a halogen atom, an
aryl group, an alkyl group, an alkoxy group, an aryloxy group, a hydroxy
group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, a sulfo
group, an amido group, an ureido group, a cyano group, a
hydroxyaminocarbonyl group, a carboxy group, a nitro group, an amino
group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio
group. an arylthio group, a heterocyclic group (e.g., pyridyl, morpholino,
etc.), or so on
Preferred examples of groups represented by A.sup.31 include substituted or
unsubstituted alkyl, aryl, amino, alkoxy and aryloxy groups. Particularly
favorable ones are substituted or unsubstituted amino, alkoxy and aryloxy
groups. The number of carbon atoms contained in such groups may range from
1 to 10.
X.sup.31 represents
##STR13##
--SO.sub.2 --, or --SO--. A preferred group represented by X.sup.31 is
##STR14##
R.sup.31 represents a hydrogen atom, an alkyl group, or an aryl group.
Further, R.sup.31 may combine with A.sup.31 to form a cyclic structure.
These groups each may have a substituent group. Suitable examples of such
substituent groups include the same as those cited with regard to
A.sup.31. A hydrogen atom is particularly preferred as R.sup.31.
Y.sup.31 represents a hydrogen atom, or a group capable of being converted
to a hydrogen atom by hydrolysis.
As specific examples of such groups to be converted to a hydrogen atom by
hydrolysis, mention may be made of the following.
(1) Those protected by an ester linkage or an urethane linkage, wherein
Y.sup.31 represents
##STR15##
Suitable examples of groups represented by R.sup.32 include alkyl, aryl
and amino groups.
(2) Those protected by an imidomethyl blocking group described in U.S. Pat.
No. 4,363,865, wherein Y.sup.31 represents
##STR16##
In the blocking group, J represents
##STR17##
and Z represents plural atoms necessary to complete a hetero ring having
at least one 5- to 6-membered ring.
Specific examples of hydroxamic acids are illustrated below. However, the
invention should not be construed as being limited to the following
examples.
##STR18##
Other specific examples of hydroxamic acids include those described in
Japanese Patent Application No. 18559/86 incorporated herein by reference,
and such acids are available on a basis of the description therein.
The hydrazines and hydrazides are preferably represented by the formula
##STR19##
In formula (IV), R.sup.41, R.sup.42 and R.sup.43 each represents a hydrogen
atom, an alkyl group (containing 1 to 20 carbon atoms, with examples
including a methyl group, an ethyl group, a sulfopropyl group, a
carboxybutyl group, a hydroxyethyl group, and the like), an aryl group
(containing 6 to 20 carbon atoms, with examples including a phenyl group,
a 2,5-dimethoxyphenyl group, a 4-hydroxyphenyl group, a 2-carboxyphenyl
group and the like), or heterocyclic group (containing 1 to 20 carbon
atoms, with examples including a pyridine-4-yl group and so on).
R.sup.44 represents a hydroxy group, a hydroxyamino group, an alkyl group
(containing 1 to 20 carbon atoms, with examples including a methyl group,
an ethyl group, a sulfopropyl group, a carboxybutyl group, a hydroxyethyl
group, a cyclohexyl group, a benzyl group and so on), an aryl group
(containing 6 to 20 carbon atoms, with examples including a phenyl group,
a 2,5-dimethoxyphenyl group, a 4-hydroxyphenyl group, a 2-carboxyphenyl
group and so on), a heterocyclic group (containing 1 to 20 carbon atoms,
with examples including a pyridin-4-yl group and so on), an alkoxy group
(containing 1 to 20 carbon atoms, with examples including a methoxy group,
an ethoxy group, a methoxyethoxy group, a benzyloxy group, a cyclohexyloxy
group and so on), an aryloxy group (containing 6 to 20 carbon atoms, with
examples including a phenoxy group, a p-methoxyphenoxy group and so on), a
carbamoyl group (containing 1 to 20 carbon atoms, with examples including
an unsubstituted carbamoyl group, an N,N-diethylcarbamoyl group, a
hydrazinocarbonyl group and so on), or an amino group (containing 0 to 20
carbon atoms, with examples including an unsubstituted amino group, an
N-phenylamino group, a hydrazino and so on).
X.sup.41 represents a divalent group selected from the group consisting of
--CO--, --SO.sub.2 -- and
##STR20##
n represents 0 or 1. When n is 0, R.sup.44 represents an alkyl group, an
aryl group or a heterocyclic group alone, or it may combine with R.sup.43
to form a hetero ring. These groups R.sup.43 and R.sup.44 each may be
substituted.
In formula (IV), R.sup.41, R.sup.42 and R.sup.43 preferably are each
selected from a hydrogen atom or an alkyl group. In particular, R.sup.41
and R.sup.42 are each most preferably a hydrogen atom.
In formula (IV), R.sup.44 is preferably an alkyl group, an aryl group, an
alkoxy group, a carbamoyl group or an amino group.
X.sup.41 is preferably --CO-- or --SO.sub.2 --, and --CO-- is particularly
favored.
Specific examples of compounds of formula (IV) which may be used in the
present invention are set forth below. However, the present invention
should not be construed as being limited to the following examples.
##STR21##
Other typical examples of such compounds include those described in
Japanese Patent Application No. 170756/86, incorporated herein by
reference, and they are available on the basis of the description therein.
Preferred phenols are represented by the formula.
##STR22##
In the formula (V), 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 aryloxycarbonyl 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, suitable examples of groups by which
it may be substituted include one or more halogen atoms, alkyl groups,
aryl groups, hydroxyl groups, alkoxy groups, aryloxy groups, carboxyl
groups, sulfo groups, carbamoyl groups, sulfamoyl groups, amido groups,
sulfonamido groups, ureido groups, alkylthio groups, arylthio groups,
nitro groups, cyano groups, amino groups, formyl groups, acyl groups,
sulfonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups,
alkoxysulfonyl groups, aryloxysulfonyl groups, and heterocyclic groups
(e.g., morpholyl, pyridyl, etc., groups).
When R.sup.51 is substituted by two or more of the above-mentioned
substituent groups, the two or more substituent groups may be the same or
different.
When two or more R.sup.51 are present, they may be the same or different.
When --OR.sup.52 and --R.sup.51 are adjacent to each other, they may
combine with each other to form a ring. The ring formed may be a 5- or
6-membered, saturated or unsaturated ring, and may be comprised of atoms
selected from carbon, hydrogen, halogen, oxygen, nitrogen, sulfur and
other atoms.
In addition, when R.sup.51 or its substituent group represents carboxyl or
sulfo group, the group may assume the form of an alkali metal salt (e.g.,
Na, K or like salt), and amino groups also may form salts together with
various acids, e.g., hydrochloric acid. R.sup.52 represents a hydrogen
atom or a hydrolyzable group. The term hydrolyzable group refers to a
group capable of being replaced with a hydrogen atom by hydrolysis. As an
example of such a group, mention may be made of
##STR23##
(wherein R.sup.53 represents an alkyl group, an aryl group, or an amino
group). More specifically, R.sup.52 is a means for protecting the phenolic
--OH group and forms an ester of urethane linkage. As another example of
the protecting means, mention may be made of imidomethyl blocking groups
described in U.S. Pat. No. 4,363,865. That is, R.sup.52 represents
##STR24##
(wherein R.sup.54 represents
##STR25##
and R.sup.55 represents the atoms necessary to complete a hetero ring
having at least 5- or 6-members).
m and n each represents an integer of 1 to 5.
In the foregoing formula (V), preferred groups as R.sup.51 include an alkyl
group, a 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, and a cyano
group. Of these groups, the alkoxy, alkylthio, amino and nitro groups are
particularly favored over the others.
Each R.sup.51 group is preferably located in positions ortho or para to the
--OR.sup.52 group.
In addition, the number of carbon atoms contained in R.sup.51 is preferably
from 1 to 10, and particularly preferably from 1 to 6.
Preferred groups as R.sup.52 include a hydrogen atom and hydrolyzable
groups containing 1 to 5 carbon atoms. When not less than two
(--OR.sup.52) groups are present, they are preferably located in positions
ortho or para to each other.
Specific examples of the phenols of formula (V) are illustrated below.
However, the invention should not be construed as being limited to these
compounds.
##STR26##
Other specific compounds are described in Japanese Patent Application Nos.
188742/86 and 203253/86, incorporated herein by reference and available on
the basis of the descriptions therein.
.alpha.-hydroxyketones and .alpha.-aminoketones are preferably those
represented by the formula:
##STR27##
In the above formula, R.sup.61 represents a hydrogen atom, an alkyl group
(containing 1 to 20 carbon atoms, e.g., a methyl group, an ethyl group, a
hydroxymethyl group, a methoxyethyl group, a cyclohexyl group, etc.), an
aryl group (containing 6 to 20 carbon atoms, e.g., a phenyl group, a
2-hydroxyphenyl group, etc.), an alkoxy group (containing 1 to 20 carbon
atoms, e.g., a methoxy group, an ethoxy group, a methoxyethoxy group,
etc.), an aryloxy group (containing 6 to 20 carbon atoms, e.g., a phenoxy
group, a 4-methoxyphenoxy group, etc.), or an amino group (containing 0 to
20 carbon atoms, e.g., an unsubstituted amino group, an N,N-diethylamino
group, an N-phenylamino group, etc.).
R.sup.62 represents a hydrogen atom, an alkyl group (containing 1 to 20
carbon atoms, e.g., a methyl group, an ethyl group, a hydroxymethyl group,
etc.), or an aryl group containing from 6 to 20 carbon atoms, e.g., a
phenyl group, a 2-hydroxyphenyl group, etc.).
R.sup.61 and R.sup.62 may combine to form a carbon ring or a hetero ring.
X.sup.61 represents a hydroxyl group or an amino group (containing 0 to 20
carbon atoms, e.g., an unsubstituted amino group, an N,N-diethylamino
group, a morpholino group, etc.).
In the foregoing formula (VI), preferred groups as R.sup.61 include a
hydrogen atom, an alkyl group, an aryl group and an alkoxy group, while
preferred groups as R.sup.62 include a hydrogen atom and an alkyl group.
Specific examples of the .alpha.-hydroxyketones and .alpha.-aminoketones of
formula (VI) are illustrated below. However, the present invention should
not be construed as being limited to these compounds.
##STR28##
Other specific compounds are described in Japanese Patent Application No.
188741/86, incorporated herein by reference and available on the basis of
the description therein.
"Saccharides" are described in detail below.
Saccharides (which may also be called carbohydrates) consist of
monosaccharides and polysaccharides. Many have the formula C.sub.n
H.sub.2n O.sub.m. In general, aldehydes or ketones or polyhydric alcohols
(which are called aldoses and ketoses), reduced derivatives thereof,
oxidized derivatives thereof, dehydrated derivatives thereof, amino
sugars, thio sugars are collectively called monosaccharides. The term
polysaccharides refers to the products obtained by condensing two or more
of the above-described monosaccharide through dehydration.
Of these saccharides, aldoses having a reductive aldehyde group and
derivatives thereof are preferred over the others. In particular, the
corresponding monosaccharides of such aldoses are favored.
Specific examples of saccharides which can be used are illustrated below.
However, the invention should not be construed as being limited to these
compounds. (Optical isomers of the exemplified saccharides can also be
used.)
##STR29##
The above cited compounds are easily available as commercial products.
The compounds represented by the formulae (II) to (VII), respectively, are
added to a color developer in an amount of preferably from 0.01 to 20 g/l
and more preferably from 0.5 to 10 g/l.
In addition, a sulfite, such as sodium sulfite, potassium sulfite, sodium
bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite,
etc., or a carbonyl/sulfurous acid adduct can be added to a color
developer as other preservatives, if desired. An addition amount thereof
is preferably 0 to 20 g/l, more preferably 0 to 5 g/l, and a more
desirable result can be obtained using the minimum addition amount
necessary to preserve the color developer.
Further, various kinds of metals described in Japanese Patent Application
(OPI) Nos. 44148/82 and 53749/82, various kinds of saccharides described
in Japanese Patent Application (OPI) No. 102727/77,
.alpha.,.alpha.'-dicarbonyl compounds described in Japanese Patent
Application (OPI) No. 160141/84, salicylic acids described in Japanese
Patent Application (OPI) No. 180588/84, gluconic acid derivatives
described in Japanese Patent Application (OPI) No. 75647/81, and so on may
be optionally added to a color developer as preservatives. Two or more of
these preservatives may be used together, if desired. In particular,
addition of aromatic polyhydroxy compounds is preferred.
A color developer which can be used in the present invention is adjusted
preferably to pH 9-12, more preferably to pH 9-11.0, and can contain other
known developer components.
In order to maintain the above-described pH, various buffers may be used.
Suitable examples of buffers which can be used include carbonates,
phosphates, borates, tetraborates, hydroxybenzoates, glycine salts,
N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts,
3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrates,
2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts,
trishydroxyaminomethane salts, lysine salts, and so on.
Of these buffers, carbonates, phosphates, tetraborates, and
hydroxybenzoates are particularly favored over the others as they
generally have excellent solubility and buffering ability in the high pH
region beyond 9.0, have no adverse effect on photographic properties, such
as fogging etc., when added to a color developer, and are available at low
prices.
Specific examples of the foregoing preferred 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-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium
5-sulfosalicylate), and so on. However, the invention should not be
construed as being limited to the above-mentioned compounds.
Such a buffer as described above is added to the color developer in a
concentration of preferably 0.1 mol/l or more, and particularly preferably
from 0.1 to 0.4 mol/l of color developer.
Furthermore, various kinds of chelating agents can be used in the color
developer for the purpose of preventing calcium and magnesium ions from
precipitating or for increasing the stability of the color developer.
Preferred chelating agents are organic acid compounds, with examples
including aminopolycarboxylic acids described in Japanese Patent
Publication Nos. 30496/69, organic phosphonic acids described in Japanese
Patent Application (OPI) No. 97347/81, Japanese Patent Publication No.
39359/81 and West German Pat. No. 2,227,639, phosphonocarboxylic acids
described in Japanese Patent Application (OPI) Nos. 102726/77, 42730/78,
121127/79, 126241/80 and 659506/80, and so on, and the compounds described
in Japanese Patent Application (OPI) Nos. 195845/83 and 203440/83,
Japanese Patent Application No. 40900/78, and so on.
Specific examples of these chelating agents are set forth below. However,
the invention should not be construed as being limited to these
exemplified compounds.
Representative of such chelating agents are nitrilotriacetic acid,
diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid,
N,N,N-trimethylenephosphonic acid,
ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid,
transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic
acid, glycol ether diminetetraacetic acid, ethylenediamine
o-hydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid,
1-hydroxyethylidene-1,1-diphosphonic acid, and
N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid.
Two or more of these chelating agents may be used together, if desired.
These chelating agents are added in amounts large enough to block metal
ions in the color developer, for example from 0.1 to 10 g/l.
Any development accelerator can be added to the color developer, if needed.
From the standpoint of preventing pollution, facility in preparation and
prevention of fog generation, however, it is to be desired that the color
developer of the present invention should not contain benzyl alcohol in
any substantial amount. The expression, "no benzyl alcohol in any
substantial amount" as used herein means benzyl alcohol contained in a
concentration of 2 ml/l or less and, preferably, benzyl alcohol is
completely absent.
The foregoing compounds to be used in the present invention have a
remarkable effect even on the stability of the color developer not
containing benzyl alcohol in any substantial amount.
As other development accelerators, thioether compounds described in
Japanese Patent Publication Nos. 16088/62, 5987/62, 7826/63, 12380/69 and
9019/70, U.S. Pat. No. 3,813,247, and so on, p-phenylenediamine compounds
described in Japanese Patent Application (OPI) Nos. 49829/77 and 15554/75,
and so on, 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, and so on,
amine 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, 2,597,926 and 3,582,346, and so on, 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, and so on,
1-phenyl-3-pyrazolidones, imidazoles or the like can be added, if needed.
In the present invention, an arbitrary antifoggants can be added, if
needed.
As typical examples of antifoggants which can be used, mention may be made
of alkali metal halides, such as sodium chloride, potassium bromide and
potassium iodide, and organic antifoggants including nitrogen-containing
heterocyclic compounds, such as benzotriazole, 6-nitrobenzimidazole,
5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
5-chloro-benzotriazole, 2-thiazolyl-benzimidazole,
2-thiazoylmethyl-benzimidazole, indazole, hydroxyazaindolidine and
adenine.
The color developer which can be used in the present invention preferably
contains a brightening agent. Preferred brightening agents are
4,4'-diamino-2,2'-disulfostilbene compounds. The brightening agent may be
added in an amount of from 0 to 5 g/l, and particularly preferably from
0.1 to 4 g/l.
In addition, various kinds of surface active agents, such as alkylsulfonic
acids, arylphosphonic acids, aliphatic carboxylic acids, aromatic
caboxylic acid and the like, may be added to the color developer, if
desired.
The processing temperature of the color developer of the present invention
ranges from 20.degree. to 50.degree. C., preferably from 30.degree. to
40.degree. C. and the processing time ranges from 20 seconds to 5 minutes,
preferably from 30 seconds to 2 minutes. It is preferred to use a
replenisher in a smaller amount. Specifically, the amount ranges from 20
to 600 ml, preferably from B 50 to 300 ml, and more preferably from 100 to
200 ml, per square meter of the light-sensitive material processed.
A bleaching bath, a bleach-fix bath, and a fixer, which can be employed in
the present invention, are described below.
Any bleaching agent can be used in a bleaching bath or a bleach-fix bath to
be employed in the present invention. In particular, Fe(III) complex salts
of organic acids, such as aminopolycarboxylic acids (e.g.,
ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
etc.), organic phosphonic acid (e.g., aminopolyphosphonic acids,
phosphonocarboxylic acids, etc.), and other organic acids (e.g., citric
acid, tartaric acid, malic acid, etc.); persulfates; hydrogen peroxide;
and so on are favored.
Of these bleaching agents, Fe(III) complex salts of organic acids are
especially preferred over others from the standpoint of speeding up the
development process and preventing environmental pollution.
As specific examples of aminopolycarboxylic acids, aminopolyphosphonic
acid, organic phosphonic acids, and salts thereof, which are useful for
the formation of organic complex salts of Fe(III), mention may be made of
ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid,
nitrilotriacetic acie, cyclohexanediaminetetraacetic acid,
methyliminodiacetic acid, iminodiacetic acid, glycol ether
diaminetetraacetic acid, and so on.
These compounds may take the form of a sodium, potassium, lithium or
ammonium salt. Of the foregoing compounds, Fe(III) complex salts of
ethylenediaminetetraacetic acid, diethylenetriaminepentaaectic acid,
cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid and
methyliminodiacetic acid are favored over the o | | |
