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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 the step of developing a silver halide color photographic
material with a developer containing an aromatic primary amine color
developing agent and at least one compound represented by the following
general formulae (Ia) and (Ib):
##STR53##
the material being image-wise exposed, wherein R.sup.1, R.sup.2, R.sup.3
and R.sup.4, which may be the same or different, each represents a
hydrogen atom or an unsubstituted alkyl group; R.sup.5, R.sup.6 and
R.sup.7, which may be the same or different, each represents an
unsubstituted alkylene group; X.sup.1 and X.sup.2, which may be the same
or different, each represents
##STR54##
--O--, --S--, --CO--, --SO.sub.2 or --SO--, or a combination thereof, and
R.sup.8 represents a hydrogen atom or an unsubstituted alkyl group; and m
and n, which may be the same or different, each is 0, 1, 2 or 3; and
##STR55##
wherein R.sup.13 represents a substituted alkylene group; and R.sup.9,
R.sup.10, R.sup.11 and R.sup.12, which may be the same or different, each
represents a hydrogen atom, a substituted or unsubstituted alkyl group or
a substituted or unsubstituted aryl group wherein said developer further
comprises at least one compound capable of directly stabilizing a
developing agent, which is selected from the group consisting of a
hydroxylamine, a hydrazine, a hydrazide, a hydroxamic acid and an
.alpha.-hydroxyketone, and wherein said hydroxylamine is represented by
the following general formula (II):
##STR56##
wherein R.sup.21 and R.sup.22, which may be the same or different, each
represents a hydrogen atom, a substituted or unsubstituted alkyl group, a
substituted or unsubstituted alkenyl group or a substituted or
unsubstituted aryl group, provided R.sup.21 and R.sup.22 do not represent
a hydrogen atom at the same time; and provided that R.sup.21 and R.sup.22
may be linked to form a heterocyclic ring including the nitrogen atom of
general formula (II).
2. The method as claimed in claim 1, wherein said unsubstituted alkyl group
represented by R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.8 each
contains 1 to 10 carbon atoms; the unsubstituted alkylene groups
represented by R.sup.5, R.sup.6 and R.sup.7 each contains 1 to 6 carbon
atoms; X.sup.1 and X.sup.2 each represents
##STR57##
--O--, or --S--; m and n each represents 0 or 1; R.sup.13 represents an
alkylene group substituted with at least one substituent selected from the
group consisting of a hydroxyl group, an alkoxy group, an aryloxy group,
an amino group, a sulfo group, a phosphonic acid group, a sulfonyl group,
a ureido group, an acyl group, an alkylthio group, an arylthio group, a
carbamoyl group, a sulfamoyl group, an acylamino group, a sulfonamido
group, a halogen, a cyano group, and a nitro group; and said substituted
alkyl group and substituted aryl group represented by R.sup.9, R.sup.10,
R.sup.11 and R.sup.12 each is substituted with at least one substituent
selected from the group consisting of a hydroxyl group, an alkoxy group,
an aryloxy group, a carboxyl group, an amino group, a sulfo group, a
phosphonic acid group, a sulfonyl group, a ureido group, an acyl group, an
alkylthio group, an arylthio group, a carbamoyl group, a sulfamoyl group,
an acylamino group, a sulfonamido group, a halogen atom, a cyano group and
a nitro group.
3. The method as claimed in claim 2, wherein said unsubstituted alkyl group
represented by R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.8 contains
from 1 to 6 carbon atoms; X.sup.1 and X.sup.2 each represents
##STR58##
R.sup.13 represents an alkylene group substituted with a substituent
selected from the group consisting of a hydroxyl group, an alkoxy group,
an amino group, a sulfo group, and a ureido group; R.sup.9, R.sup.10,
R.sup.11 and R.sup.12 each represents a hydrogen atom, an unsubstituted
alkyl group, or an alkyl group substituted with a substituent selected
from the group consisting of a hydroxyl group, an alkoxy group, a carboxyl
group, and a sulfo group; and the total number of carbon atoms contained
in R.sup.9, R.sup.10, R.sup.11, R.sup.12 and R.sup.13 is at most 30.
4. The method as claimed in claim 3, wherein the total number of carbon
atoms contained in R.sup.9, R.sup.10, R.sup.11, R.sup.12 and R.sup.13 is
at most 20.
5. The method as claimed in claim 1, wherein said aromatic primary amine
color developing agent comprises a p-phenylenediamine, or a salt thereof
selected from a sulfate, a hydrochloride, a sulfite and a p-toluene
sulfonate.
6. The method as claimed in claim 1, wherein the total amount of said
compound represented by general formulae (Ia) and (Ib) present in said
developer is from about 0.05 to 30 g per liter of said developer, and the
amount of said aromatic primary amine developing agent is from about 0.01
to about 30 g per liter of said developer.
7. The method as claimed in claim 1, wherein said developer further
comprises at least one compound capable of directly stabilizing a
developing agent, which is selected from the group consisting of a
hydroxylamine, a hydrazine, a hydrazide, a hydroxamic acid and an
.alpha.-hydroxyketone.
8. The method as claimed in claim 1, wherein R.sup.21 and R.sup.22 each
represents a substituted or unsubstituted alkyl group or a substituted or
unsubstituted alkenyl group.
9. The method as claimed in claim 8, wherein at least one of R.sup.21 and
R.sup.22 represents a substituted alkyl group or a substituted alkenyl
group, wherein the substituent is selected from the group consisting of a
halogen atom, an aryl group, an alkoxy group, an aryloxy group, a sulfonyl
group, a sulfonamido group, a sulfamoyl group, a carbamoyl group, an amido
group, a ureido group, an alkoxycarbonylamino group, an
aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl
group, a cyano group, a hydroxyl group, a carboxyl group, a sulfo group, a
nitro group, an amino group, an alkylthio group, an arylthio group, and a
heterocyclic group.
10. The method as claimed in claim 9, wherein each of R.sup.21 and R.sup.22
contains from 1 to 10 carbon atoms, and said substituent is selected from
the group consisting of a hydroxyl group, an alkoxy group, a sulfonyl
group, an amido group, a carboxyl group, a cyano group, a sulfo group, a
nitro group and an amino group.
11. The method as claimed in claim 10, wherein the amount of said compound
represented by formula (II) is from about 0.01 to 30 g per liter of said
developer.
12. The method as claimed in claim 1, wherein said developer is
substantially free from benzyl alcohol.
13. The method as claimed in claim 1, wherein said developer is
substantially free from p-aminophenol type developing agent.
14. The method as claimed in claim 1, wherein said developing step is
conducted at a temperature of from about 20.degree. to 50.degree. C. for a
time of from about 20 seconds to 5 minutes.
15. The method as claimed in claim 1, wherein said silver halide color
photographic material comprises a support having thereon at least one
silver halide light-sensitive emulsion layer, wherein said silver halide
comprises at least about 60 mol % of silver chloride.
16. The method as claimed in claim 1, wherein said silver halide color
photographic material comprises a support having thereon at least one
silver halide light-sensitive emulsion layer, wherein said silver halide
is silver bromide or silver chlorobromide comprising at least about 50 mol
% of silver bromide.
17. The method as claimed in claim 1, wherein said silver halide color
photographic material comprises at least one cyan coupler represented by
the following general formulae (C-I) and (C-II):
##STR59##
wherein R.sup.31 represents an alkyl group, a cycloalkyl group, an aryl
amino group, an amino group or heterocyclic ring group; R.sup.32
represents an alkyl group or an aryl group; R.sup.33 represents a hydrogen
atom, a halogen atom, an alkyl group or an alkoxy group; provided that
R.sup.33 may be linked with R.sup.32 to form a ring; and Z.sub.1
represents a hydrogen atom, a halogen atom or a coupling-off group capable
of being cleaved by a reaction of said coupler with the oxidation product
of an aromatic primary amine color developing agent; and
##STR60##
wherein R.sup.34 represents an alkyl group, acycloalkyl group, an aryl
group or a heterocyclic group; R.sup.35 represents an alkyl group having
at least 2 carbon atoms; R.sup.36 represents a hydrogen atom, a halogen
atom or an alkyl group; and Z.sup.2 represents a hydrogen atom, a halogen
atom or a coupling-off group capable of being cleaved by a reaction of
said coupler with the oxidation product of an aromatic primary amine color
developing agent.
18. A color developer composition comprising an aromatic primary amine
color developing agent and at least one compound represented by the
following general formulae (Ia) and (Ib):
##STR61##
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4, which may be the same or
different, each represents a hydrogen atom or an unsubstituted alkyl
group; R.sup.5, R.sup.6 and R.sup.7, which may be the same or different,
each represents an unsubstituted alkylene group; X.sup.1 and X.sup.2,
which may be the same or different, each represents
##STR62##
--O--, --S--, --CO--, --SO.sub.2 or --SO--, or a combination thereof, and
R.sup.8 represents a hydrogen atom or an unsubstituted alkyl group; and m
and n, which may be the same or different, each is 0, 1, 2 or 3; and
##STR63##
wherein R.sup.13 represents a substituted alkylene group; and R.sup.9,
R.sup.10, R.sup.11 and R.sup.12, which may be the same or different, each
represents a hydrogen atom, a substituted or unsubstituted alkyl group or
a substituted or unsubstituted aryl group wherein said developer further
comprises at least one compound capable of directly stabilizing a
developing agent, which is selected from the group consisting of a
hydroxylamine, a hydrazine, a hydrazide, a hydroxamic acid and an
.alpha.-hydroxyketone, and wherein said hydroxylamine is represented by
the following general formula (II):
##STR64##
wherein R.sup.21 and R.sup.22 which may be the same or different, each
represents a hydrogen atom, a substituted or unsubstituted alkyl group, a
substituted or unsubstituted alkenyl group or a substituted or
unsubstituted aryl group, provided R.sup.21 and R.sup.22 do not represent
a hydrogen atom at the same time; and provided that R.sup.21 and R.sup.22
may be linked to form a heterocyclic ring including the nitrogen atom of
general formula (II).
19. A color developing composition comprising an aromatic primary amine
color developing agent and at least one compound represented by the
following general formula (Ia):
##STR65##
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4, which may be the same or
different, each represents a hydrogen atom or an unsubstituted alkyl
group; R.sup.5, R.sup.6 and R.sup.7, which may be the same or different,
each represents an unsubstituted alkylene group; X.sup.1 and X.sup.2,
which may be the same or different, each represents
##STR66##
--O--, --S--, --CO--, --SO.sub.2 or --SO--, or a combination thereof, and
R.sup.8 represents a hydrogen atom or an unsubstituted alkyl group; and m
and n, which may be the same or different, each is 0, 1, 2 or 3 wherein
said developer further comprises at least one compound capable of directly
stabilizing a developing agent, which is selected from the group
consisting of a hydroxylamine, a hydrazine, a hydrazide, a hydroxamic acid
and an .alpha.- hydroxyketone, and wherein said hydroxylamine is
represented by the following general formula (II):
##STR67##
wherein R.sup.21 and R.sup.22, which may be the same or different, each
represents a hydrogen atom, a substituted or unsubstituted alkyl group, a
substituted or unsubstituted alkenyl group or a substituted or
unsubstituted aryl group; provided R.sup.21 and R.sup.22 do not represent
a hydrogen atom at the same time; provided that R.sup.21 and R.sup.22 may
be linked to form a heterocyclic ring including the nitrogen atom of
general formula (II).
20. A color developing composition comprising an aromatic primary amine
color developing agent and at least one compound represented by the
following formula (Ib):
##STR68##
wherein R.sup.13 represents a substituted alkylene group; and R.sup.9,
R.sup.10, R.sup.11 and R.sup.12, which may be the same or different, each
represents a hydrogen atom, a substituted or unsubstituted alkyl group or
a substituted or unsubstituted aryl group wherein said developer further
comprises at least one compound capable of directly stabilizing a
developing agent, which is selected from the group consisting of a
hydroxylamine, a hydrazine, hydrazide, a hydroxamic acid and an
.alpha.-hydroxyketone, and wherein said hydroxylamine is represented by
the following general formula (II):
##STR69##
wherein R.sup.21 and R.sup.22, which may be the same or different, each
represents a hydrogen atom, a substituted or unsubstituted alkyl group, a
substituted or unsubstituted alkenyl group or a substituted or
unsubstituted aryl group; provided R.sup.21 an R.sup.22 do not represent a
hydrogen atom at the same time; and provided that R.sup.21 and R.sup.22
may be linked to form a heterocyclic ring including the nitrogen atom of
general formula (II).
21. The color developing composition as claimed in claim 18, wherein said
unsubstituted alkyl group represented by R.sup.1, R.sup.2, R.sup.3,
R.sup.4 and R.sup.8 each contains 1 to 10 carbon atoms; the unsubstituted
alkylene groups represented by R.sup.5, R.sup.6 and R.sup.7 each contains
1 to 6 carbon atoms; X.sup.1 and X.sup.2 each represents
##STR70##
--O--, or --S--; m and n each represents 0 or 1; R.sup.13 represents an
alkylene group substituted with at least one substituent selected from the
group consisting of a hydroxyl group, an alkoxy group, an aryloxy group,
an amino group, a sulfo group, a phosphonic acid group, a sulfonyl group,
a ureido group, an acyl group, an alkylthio group, an arylthio group, a
carbamoyl group, a sulfamoyl group, an acylamino group, a sulfonamido
group, a halogen, a cyano group, and a nitro group; and said substituted
alkyl group and substituted aryl group represented by R.sup.9, R.sup.10,
R.sup.11 and R.sup.12 each is substituted with at least one substituent
selected from the group consisting of a hydroxyl group, an alkoxy group,
an aryloxy group, a carboxyl group, an amino group, a sulfo group, a
phosphonic acid group, a sulfonyl group, a ureido group, an acyl group, an
alkylthio group, an arylthio group, a carbamoyl group, a sulfamoyl group,
an acylamino group, a sulfonamido group, a halogen atom, a cyano group and
a nitro group.
22. The color developing composition as claimed in claim 21, wherein said
unsubstituted alkyl group represented by R.sup.1, R.sup.2, R.sup.3,
R.sup.4 and R.sup.8 each contains from 1 to 6 carbon atoms; X.sup.1 and
X.sup.2 each represents
##STR71##
R.sup.13 represents an alkylene group substituted with a substituent
selected from the group consisting of a hydroxyl group, an alkoxy group,
an amino group, a sulfo group, and a ureido group; R.sup.9, R.sup.10,
R.sup.11 and R.sup.12 each represents a hydrogen atom, an unsubstituted
alkyl group, or an alkyl group substituted with a substituent selected
from the group consisting of a hydroxyl group, an alkoxy group, a carboxyl
group, and a sulfo group; and the total number of carbon atoms contained
in R.sup.9, R.sup.10, R.sup.11, R.sup.12 and R.sup.13 is at most 30.
23. The color developing composition as claimed in claim 21, wherein the
total number of carbon atoms contained in R.sup.9, R.sup.10, R.sup.11,
R.sup.12 and R.sup.13 is at most 20.
24. The color developing composition as claimed in claim 18, wherein said
aromatic primary amine color developing agent comprises a
p-phenylenediamine, or a salt thereof selected from a sulfate, a
hydrochloride, a sulfite and a p-toluene sulfonate.
25. The color developing composition as claimed in claim 18, wherein said
developer is substantially free from p-aminophenol type developing agent.
26. The color developing composition as claimed in claim 18, wherein the
amount of said compound represented by general formula (Ia) or (Ib)
present in said developer is from about 0.05 to 30 g per liter of said
developer, and the amount of said aromatic primary amine developing agent
is from about 0.01 to about l30 g per liter of said developer. |
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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 silver halide
color photographic materials, particularly a method for processing silver
halide color photographic materials using a color developing solution with
improved stability and color formation properties that remarkably limits
the increase in fogging in continuous processing.
BACKGROUND OF THE INVENTION
Color photographic developing solutions containing aromatic primary amine
color developing agents have long been conventionally used in the
formation of color images, and now have a major role in the color
photographic image formation process. However, it is well known that
conventional color developing solutions are easily oxidized by air or
metals, and that if the developing solutions thus oxidized are used to
form a color image, fogging increases, sensitivity or gradation changes,
and therefore photographic characteristics are adversely affected.
Therefore, various measures to improve the preservability of color
developing solutions have been studied, and use of a combination of
hydroxylamine and a sulfite ion is the most general current practice.
However, when hydroxylamine decomposes, ammonia is released, which causes
fogging, and a sulfite ion acts as a competing compound against developing
agents, for example, to disadvantageously reduce their color formation
capability, so that neither is a preferred preservative.
Particularly, although a sulfite ion has been used as a compound to improve
the preservability of various developing agents or to prevent
decomposition of hydroxylamine, it greatly impedes color development, and
when it is used in a system without benzyl alcohol (which is
disadvantageous from the point of view of environmental pollution and
preparation of a developing solution), the developed color density is
significantly lowered.
Alkanolamines described in Japanese patent application (OPI) No. 3532/79
(corresponding to U.S. Pat. No. 4,170,478) (the term "OPI" as used herein
refers to a "published unexamined Japanese patent application") and
polyethyleneimines described in Japanese Patent Application (OPI) No.
94349/81 (corresponding to U.S. Pat. No. 4,252,892) are suggested as
compounds that can be substituted for sulfites, but these compounds remain
unsatisfactory.
Conventionally, to improve the stability of color developing solutions,
various preservatives and chelating agents have been studied. For example,
preservatives include aromatic polyhydroxy compounds described in Japanese
patent application (OPI) Nos. 49828/77, 160142/84 and 47038/81
(corresponding to U.S. Pat. No. 4,264,716) and U.S. Pat. No. 3,746,544;
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 (corresponding to U.S. Pat. No.
4,155,764) and 89425/78; metal salts described in Japanese Patent
Application (OPI) Nos. 44148/82 (corresponding to U.S. Pat. No. 4,330,616)
and 53749/82; and hydroxamic acids described in Japanese patent
application (OPI) No. 27638/77 (corresponding to U.S. Pat. No. 4,055,426).
Chelating agents include aminopolycarboxylic acids described in Japanese
Patent Publication Nos. 030496/73 and 30232/69 (corresponding to U.S. Pat.
No. 3,462,269); organic phosphonic acids described in Japanese Patent
Application (OPI) No. 97347/81, Japanese Patent Publication No. 39359/81
(corresponding to U.S. Pat. No. 3,794,591) and West German Patent
2,227,639; phosphonocarboxylic acids described, for example, in Japanese
Patent Application (OPI) Nos. 102726/77 (corresponding to U.S. Pat. No.
4,083,723), 42730/78, 121127/79, 126241/80 and 65956/80 and compounds
described, for example, in Japanese patent application (OPI) Nos.
195845/83 (corresponding to U.S. Pat. No. 4,482,626) and 203440/83 and
Japanese Patent Publication No. 40900/78.
However, even if these techniques are used, preservative performance is
inadequate, or photographic characteristics are adversely affected, so
that satisfactory results have not yet been attained, and excellent
preservatives that can be substituted for sulfites are still keenly
sought.
In the case of color photographic materials containing a silver
chlorobromide emulsion with a high chlorine content, fogging is liable to
occur during color development as described in Japanese patent application
(OPI) Nos. 95345/83 and 232342/84. When such an emulsion is used, it is
essential to use a preservative that dissolves the emulsion to a reduced
extent and has better preservability, and satisfactory preservatives from
this viewpoint have not been found.
SUMMARY OF THE INVENTION
Therefore, an object of the invention is to provide a method for processing
a silver halide color photographic material using a color developing
solution that is excellent in stability and that remarkably limits
increase in fogging in continuous processing.
Still further, an object of the present invention is to provide a method
for processing silver halide color photographic materials that is
excellent in color formation property even by processing the silver halide
color photographic materials with a color developing solution
substantially free from benzyl alcohol.
It has now been discovered that these and other objects of the invention
are attained by a method for processing a silver halide color photographic
material including the step of developing a silver halide color
photographic material with a developing solution containing an aromatic
primary amine color developing agent and at least one compound represented
by the following general formulae (Ia) and (Ib):
##STR4##
wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4, which may be the same or
different, each represents a hydrogen atom or an unsubstituted alkyl
group; R.sup.5, R.sup.6 and R.sup.7, which may be the same or different,
each represents an unsubstituted alkylene group; X.sup.1 and X.sup.2,
which may be the same or different, each represents
##STR5##
--O--, --S--, --CO--, --SO.sub.2 -- --SO--, or a combination thereof and
R.sup.8 represents a hydrogen atom or an unsubstituted alkyl group; and m
and n, which may be the same or different, each is 0, 1, 2 or 3; and
##STR6##
wherein R.sup.13 represents a substituted alkylene group; and R.sup.9,
R.sup.10, R.sup.11 and R.sup.12, which may be the same or different, each
represents a hydrogen atom, a substituted or unsubstituted alkyl group or
a substituted or unsubstituted aryl group.
DETAILED DESCRIPTION OF THE INVENTION
The compounds represented by general formula (I) are now described in
detail.
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 and each represents a hydrogen atom
or an unsubstituted alkyl group; R.sup.5, R.sup.6 and R.sup.7 each
represents an unsubstituted alkylene group; X.sup.1 and X.sup.2 each
represents
##STR7##
--O--, --S--, --CO--, --SO.sub.2 --, --SO-- or a linking group made up of
a combination of these, in which R.sup.8 represents a hydrogen atom or an
unsubstituted alkyl group; and m and n each is 0, 1, 2 or 3, with 0 or 1
being preferred for both.
The unsubstituted alkyl groups represented by R.sup.1, R.sup.2, R.sup.3,
R.sup.4 and R.sup.8 may be linear, branched or cyclic, and contain 1 to 10
carbon atoms, preferably 1 to 6 carbon atoms. Specific examples of the
unsubstituted alkyl groups include a methyl group, an ethyl group, an
n-propyl group, an isopropyl group, an n-butyl group, an n-hexyl group, a
t-amyl group and a cyclohexyl group.
The unsubstituted alkylene groups represented by R.sup.5, R.sup.6 and
R.sup.7 may be linear or branched, and contain 1 to 6 carbon atoms.
Specific examples include a methylene group, a dimethylene group, a
trimethylene group, a dimethyldimethylene group, a tetramethylene group
and a heptamethylene group.
The linking groups represented by X.sup.1 and X.sup.2 are preferably
##STR8##
--O-- and --S--, particularly preferably
##STR9##
R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.8 may be the same or different
and R.sup.5, R.sup.6 and R.sup.7 may be the same or different.
The compounds represented by general formula (Ib) are now described in more
detail.
In general formula (Ib), R.sup.13 represents a linear or branched alkylene
group having 1 to 30 carbon atoms and being substituted by at least one of
a hydroxyl group, an alkoxy group having 1 to 30 carbon atoms, an aryloxy
group having 6 to 30 carbon atoms, an amino group, a sulfo group, a
phosphonic acid group, a sulfonyl group, a ureido group, an acyl group
having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon
atoms, an arylthio group having 6 to 30 carbon atoms, a carbamoyl group, a
sulfamoyl group, an acylamino group having 1 to 30 carbon atoms, a
sulfonamido group having 1 to 30 carbon atoms, a halogen atom, a cyano
group and a nitro group. Examples of the alkylene groups represented by
R.sup.13 are a 2-hydroxytrimethylene group and a 1-methoxypentamethylene
group. R.sup.9, R.sup.10, R.sup.11 and R.sup.12 may be the same or
different, and each represents a hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or
unsubstituted aryl group having 6 to 30 carbon atoms. Preferably the
substituents of the substituted alkyl group or the substituted aryl group
are a hydroxyl group, an alkoxy group having 1 to 30 carbon atoms, an
aryloxy group having 6 to 30 carbon atoms, a carbamoyl group having 1 to
30 carbon atoms, an amino group, a sulfo group, a phosphonic acid group, a
sulfonyl group, a ureido group, an acyl group having 1 to 30 carbon atoms,
an alkylthio group having 1 to 30 carbon atoms, an arylthio group having 6
to 30 carbon atoms, a carbamoyl group, a sulfamoyl group, an acylamino
group having 1 to 30 carbon atoms, a sulfonamido group, a halogen atom, a
cyano group and a nitro group. Two or more kinds of or two or more
substituents may be present on the alkyl group or the aryl group. Of the
functional groups in these substituents, the carboxyl group, the
phosphonic acid group and the sulfo group may form a salt with an alkali
metal (e.g., sodium and potassium), or may form a salt of positive
elements (e.g., NH.sub.4.sup.+, CA.sup.++, etc.), and an amino group may
form a salt with an acid such as a hydrochloric acid, a sulfuric acid, a
nitric acid, a phosphoric acid, an oxalic acid, an acetic acid, etc.
In general formula (Ib), preferably R.sup.13 represents a
hydroxy-substituted alkylene group, an alkoxy-substituted alkylene group,
an amino-substituted alkylene group, a sulfo-substituted alkylene group
and a ureido-substituted alkylene group. Preferably, R.sup.9, R.sup.10,
R.sup.11 and R.sup.12 each represents a hydrogen atom, an unsubstituted
alkyl group (e.g., a methyl group, an ethyl group and an isopropyl group),
a hydroxy-substituted alkyl group, an alkoxy-substituted alkyl group, a
carboxy-substituted alkyl group or a sulfo-substituted alkyl group.
Generally, it is preferred that the sum of the carbon numbers of R.sup.13,
R.sup.9, R.sup.10, R.sup.11 and R.sup.12 in general formula (Ib) be 30 or
below, and more preferably 20 or below, and most preferably 10 or below.
Specific examples of the compounds represented by general formulae (Ia) and
(Ib) are given below, but the present invention is not to be construed as
being limited to these compounds.
##STR10##
Although the compounds represented by general formulae (Ia) and (Ib) are
commercially available, the amine compounds represented by general formula
(Ia) can be synthesized by generally known reactions, for example, by a
reaction of a primary amine or a secondary amine with an alkyl halide or
an alkyl sulfonate, as described in J. Am. Chem. Soc., 68, 895 (1946); S.
Caspe, J. Am. Chem. Soc., 54, 4457 (1932); E. R. Alexander, J. Am. Chem.
Soc., 70, 2592 (1948); P. Kovacic in Friedel and Related Reactions, Vol.
3, Part 2, Chapt. 44, edited by G. A. Olah (John Wiley, 1964); F. Minisci,
Synthesis, 1974, 1. Also, the compounds represented by general formula
(Ib) can be synthesized easily according to methods described in Organic
Synthesis I, 102, 154, 328, 558; III, 370, 800.
The total amount of the compounds represented by general formula (Ia) or
(Ib) to be added to a color developing solution is preferably about 0.05
to 30 g per liter, more preferably about 0.1 to 15 g, and most preferably
0.5 to 10 g, per liter.
The color developing solution used in the present invention is now
described in greater detail.
The color developing solution used in the present invention contains a
known aromatic primary amine color developing agent. Preferred examples of
aromatic primary amine color developing agents are p-phenylenediamine
derivatives. Typical examples are given below, but the present invention
is not limited to these specific examples:
D- 1: N,N-Diethyl-p-phenylenediamine
D- 2: 2-Amino-5-diethylaminotoluene
D- 3: 2-Amino-5-(N-ethyl-N-laurylamino)toluene
D- 4: 4-[N-Ethyl-N-(.beta.- hydroxyethyl)amino]aniline
D- 5: 2-Methyl-4-[N-ethyl-N-(.beta.-hydroxyethyl)amino]aniline
D- 6: N-Ethyl-N-(.beta.-methanesulfonamidoethyl)-3-methyl-4-aminoaniline
D- 7: N-(2-Amino-5-diethylaminophenylethyl)methanesulfonamide
D- 8: N,N-Dimethyl-p-phenylenediamine
D- 9: 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline
D-10: 4-Amino-3-methyl-N-ethyl-N-.beta.-ethoxyethylaniline
D-11: 4-Amino-3-methyl-N-ethyl-N-.beta.-butoxyethylaniline
These p-phenylenediamine derivatives may be in the form of salts such as
sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of
the aromatic primary amine developing agent used is preferably about 0.1 g
to about 20 g, more preferably about 0.5 g to about 10 g, per liter of a
developing solution.
Particularly, the use of a color developing agent of D-5, D-6 and D-9 in
combination with a compound of general formula (Ia) or (Ib) is preferred
to limit the increase in fogging and provide good photographic
characteristics.
In the color developing solution, it is preferred that p-aminophenol
developing agent is not substantially contained. Practically,
p-aminophenol developing agent is preferably contained in an amount of
less than 1 g, more preferably less than 0.1 g, per liter of the color
developing solution in view of stability of the developing solution.
Further, it is preferred that the color developing solution substantially
contains no couplers, such as color couplers.
In a system wherein an aromatic primary amine color developing agent is
used, the compounds of the present invention are remarkably effective
preservatives when the compounds are used in combination with a compound
capable of directly stabilizing the developing agent. Compounds capable of
directly stabilizing a developing agent include generally known
water-soluble antioxidants, such as hydroxylamines.
Preferred compounds that can be optionally added to the color developing
solution used in the present invention are hydroxylamines, and
particularly preferred compounds are represented by the following general
formula (II):
##STR11##
wherein R.sup.21 and R.sup.22, which may be the same or different, each
represents a hydrogen atom, a substituted or unsubstituted alkyl group, a
substituted or unsubstituted alkenyl group or a substituted or
unsubstituted aryl group.
Preferably, R.sup.21 and R.sup.22 each represents an alkyl group or an
alkenyl group, and it is more preferable that at least one of them have a
substituent. R.sup.21 and R.sup.22 may be linked to form a heterocyclic
ring including the nitrogen atom of general formula (II).
The alkyl group and the alkenyl group represented by R.sup.21 and R.sup.22
may be linear, branched or cyclic, and the substituents for these groups
include a halogen atom (e.g., F, Cl and Br), an aryl group (e.g., a phenyl
group and a p-chlorophenyl group), an alkoxy group (e.g., a methoxy group,
an ethoxy group and a methoxyethoxy group), an aryloxy group (e.g., a
phenoxy group), a sulfonyl group (e.g., a methanesulfonyl group and a
p-toluenesulfonyl group), a sulfonamido group (e.g., a methanesulfonamido
group and a benzenesulfonamido group), a sulfamoyl group (e.g., a
diethylsulfamoyl group and an unsubstituted sulfamoyl group), a carbamoyl
group (e.g., an unsubstituted carbamoyl group and a diethylcarbamoyl
group), an amido group (e.g., an acetamido group and a benzamido group), a
ureido group (e.g., a methylureido group and a phenylureido group), an
alkoxycarbonylamino group (e.g., a methoxycarbonylamino group), an
aryloxycarbonylamino group (e.g., a phenoxycarbonylamino group), an
alkoxycarbonyl group (e.g., a methoxycarbonyl group), an aryloxycarbonyl
group (e.g., a phenoxycarbonyl group), a cyano group, a hydroxyl group, a
carboxyl group, a sulfo group, a nitro group, an amino group (e.g., an
unsubstituted amino group and a diethylamino group), an alkylthio group
(e.g., a methylthio group), an arylthio group (e.g., a phenylthio group)
and a heterocyclic ring group (e.g., a morpholino group and a pyridyl
group).
The substituent for the aryl group includes the same groups as those for
the above-described alkyl group and the alkenyl group.
R.sup.21 and R.sup.22 may be the same or different, and the substituents
for R.sup.21 and R.sup.22 may be the same or different.
Preferably, the carbon number of each of R.sup.21 and R.sup.22 is from 1 to
10, more preferably from 1 to 5. Nitrogen-containing heterocyclic rings
that may be formed by R.sup.21 and R.sup.22 include a piperidyl group, a
pyrrolidyl group, an N-alkylpiperadyl group, a morpholyl group, an
indolinyl group and a benzotriazole group.
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, a nitro group and an amino group.
Specific examples of compounds represented by general formula (II) used in
the present invention are given below, but the present invention is not to
be construed as being limited thereto.
##STR12##
Compounds represented by general formula (II) can be synthesized by known
processes as described 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.
These compounds may form salts with acids such as hydrochloric acid,
sulfuric acid, nitric acid, phosphoric acid, oxalic acid and acetic acid.
In addition to hydroxylamines, other "compounds capable of directly
stabilizing a developing agent", preferred compounds that can be used in
combination with the present compounds include, for example, hydrazines
and hydrazides as described in Japanese patent application Nos. 170756/86,
171682/86, 173468/86, etc., hydroxamic acids as described in Japanese
patent application No. 186559/86, .beta.- hydroxyketones and
.beta.-aminoketones as described in Japanese patent application No.
188741/86, phenols as described in Japanese patent application Nos.
188742/86 and 203253/86, and saccharoses as described in Japanese patent
application No. 180616/86. In addition to the above compounds, monoamines
as described in Japanese patent application Nos. 147823/86, 166674/86,
165621/86, 164515/86, 170789/86, 168159/86, etc., diamines as described in
Japanese patent application Nos. 173595/86, 164515/86, 186560/86, etc.,
polyamines as described in Japanese patent application Nos. 165621/86,
169789/86, etc., polyamines as described in Japanese Patent Application
No. 188619/86, nitroxy radicals as described in Japanese patent
application No. 197760/86, alcohols as described in Japanese patent
application Nos. 186561/86 and 197419/86, oximes as described in Japanese
Patent Application No. 198987/86, tertiary amines as described in Japanese
patent application No. 265149/86 and condensed cyclic amines as described
in Japanese Patent Application No. 24374/87 (such as
1,4-diazabicyclo[2,2,2]octane, etc.) are preferably used together with the
compounds of the present invention.
The amount of these compounds to be added to a color developing solution is
preferably about 0.01 g to 30 g, more preferably about 0.1 g to 20 g, and
most preferably about 0.5 to 10 g, per liter of the color developing
solution.
Other preservatives may be added, if desired, for example, sulfites such as
sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfate,
sodium metasulfite and potassium metasulfite, or carbonyl sulfite adducts.
The amount of these to be added to a color developing solution is 0 g to
about 20 g/liter, preferably 0 g to about 5 g/liter, and it is preferable
to use the smallest amount necessary to provide stability to a color
developing solution.
Examples of such other preservatives are hydroxyacetones described in U.S.
Pat. No. 3,615,503 and British Patent No. 1,306,176; .beta.-aminocarbonyl
compounds described in Japanese patent application (OPI) Nos. 143020/77
and 89425/78; metals described in Japanese Patent Application (OPI) Nos.
44148/82 and 53749/82; sugars described in Japanese patent application
(OPI) No. 102727/77; .beta.,.beta.'-dicarbonyl compounds described in
Japanese patent application (OPI) No. 160141/84; salicylic acids described
in Japanese patent application (OPI) No. 180588/84; and gluconic acid
derivatives described in Japanese patent application (OPI) No. 75647/81;
and two or more of these can be used in combination, if desired. Of these
compounds, aromatic polyhydroxy compounds are preferred.
Preferably, the pH of the color developing solution used in the present
invention is about 9 to 12, more preferably about 9 to 11.0, and other
known compounds that are components of developing solutions can be added
to the color developing solution.
To maintain the pH, preferably, various buffers are used. Buffers 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 and lysine salts. In particular, carbo | | |
