 |
Claims  |
|
|
What we claim is:
1. A method of processing a silver halide color photographic material,
which comprises imagewise exposing a silver halide color photographic
material to light and then processing the silver halide color photographic
material with a color developing containing (i) an aromatic primary amine
color developing agent, (ii) a hydroxylamine compound represented by
formula (I):
##STR12##
wherein R.sup.1 and R.sup.2 each represent an unsubstituted or substituted
alkyl, alkenyl or aryl group and may optionally be joined together to form
a nitrogen-containing heterocyclic ring together with the associated
nitrogen atom, and (iii) at least one compound selected from the group
consisting of formulae (II-a), (II-b) and (II-c):
##STR13##
wherein R.sup.3, R.sup.4, R.sup.5 and R.sup.6, which may be the same or
different, each represent a hydrogen atom; an unsubstituted or substituted
alkyl, aryl or amino group; a hydroxyl group; an alkoxy group; an
alkylthio group; a carbamoyl group which may optionally be substituted; a
halogen atom; a cyano group; a carboxyl group; an alkoxycarbonyl group, or
a heterocyclic group; and R.sup.3 and R.sup.4 and R.sup.5 may optionally
form a 5 or 6-membered ring in combination, with the proviso that at least
one of R.sup.3 and R.sup.5 represents a hydroxyl group,
Z--S--M formula (II-c)
wherein M represents a hydrogen atom, cation or --S--Z, and Z represents a
heterocyclic group containing at least one nitrogen atom.
2. The method as claimed in claim 1, wherein the color developer is
substantially free of benzyl alcohol.
3. The method as claimed in claim 1, wherein the silver halide color
photographic material has at least one layer of a silver halide emulsion
containing silver halide grains which contain at least 60 mole % of silver
chloride.
4. The method as claimed in claim 1, wherein at least one of R.sup.1 and
R.sup.2 is a group having one or more further substitutents.
5. The method as claimed in claim 4, wherein the substituent or the groups
represented by each of R.sup.1 and R.sup.2 is a halogen atom, aryl group,
alkoxy group, aryloxy group, sulfonyl group, sulfonamido group, sulfamoyl
group, carbamoyl group, amido group, ureido group, alkoxycarbonylamino
group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl
group, cyano group, hydroxyl group, carboxyl group, sulfo group, nitro
group, amino group, alkylthio group, arylthio group, or heterocyclic
group.
6. The method as claimed in claim 4, wherein the substituent or R.sup.1 and
R.sup.2 is a hydroxyl group, alkoxy group, sulfonyl group, amido group
carboxyl group, cyano group, sulfo group, nitro group, or amino group.
7. The method as claimed in claim 1, wherein R.sup.1 and R.sup.2 have 1-10
carbon atoms.
8. The method as claimed in claim 1, wherein the nitrogen-containing
heterocyclic ring which is formed when R.sup.1 and R.sup.2 are joined
together is a piperidiyl group, pyrrolidinyl groupl, N-alkylpiperazyl
group, morpholinyl group, indolinyl group or benztriazolyl group.
9. The method as claimed in claim 1, wherein the hydroxylamine compound is
included in an amount of 0.1-20 g per liter of the color developer.
10. The method as claimed in claim 1, wherein the compounds of the general
formula (IIa), (IIb) and (IIc) are each included in an amount of 5 mg-3 g
per liter of the color developer.
11. The method as claimed in claim 1, wherein the color developer does not
contain hydroxylamine.
12. The method as claimed in claim 1, wherein the color developer has a pH
in the range of 9-11.
13. The method as claimed in claim 1, wherein the color developer further
comprises 0-5 g/l of sulfite as a preservative.
14. The method as claimed in claim 1, wherein the color developer is free
of benzyl alcohol.
15. The method as claimed in claim 5, wherein the substituents are selected
from the group consisting of fluorine, chlorine, bromine, phenyl,
p-chlorophenyl, methoxy, ethoxy, methoxyethoxy, phenoxy, methanesulfonyl,
p-toluenesulfonyl, methanesulfonamido, benzenesulfonamido,
diethylsulfamoyl, unsubstituted sulfamoyl, unsubstituted carbamoyl,
diethylcarbamoyl, acetamido, benzamido, methylureido, phenylureido,
methoxycarbonylamino, phenoxycarbonylamino, methoxycarbonyl,
phenoxycarbonyl, unsubstituted amino, diethylamino, methylthio,
phenylthio, morpholinyl and pyridyl.
16. The method as claimed in claim 1, wherein the compound of formula (I)
is a salt of an acid selected from the group consisting of hydrochloric
acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and acetic
acid.
17. The method as claimed in claim 1, wherein the compound of formula (I)
is present in an amount of 0.1 to 20 g per liter of the color developer.
18. The method as claimed in claim 1, wherein R.sup.3, R.sup.4, R.sup.5 and
R.sup.6 may be the same or different and represent a substituted or
unsubstituted alkyl group which has 1-20 carbon atoms in a cyclic or
branched form, an unsubstituted or substituted monocyclic or bicyclic aryl
group, an alkoxy group having 1-20 carbon atoms, an alkylthio group having
1-6 carbon atoms, a carbamoyl group which optionally has one or more
aliphatic or aromatic groups as a substituent, an alkoxycarbonyl group
having 2-20 carbon atoms, or a heterocyclic group containing a 5 or
6-membered ring having one or more hetero atoms selected from the group
consisting of nitrogen, oxygen, sulfur atoms and combinations thereof.
19. The method as claimed in claim 1, wherein unsubstituted alkyl groups
are selected from the group consisting of methyl, ethyl, n-propyl,
i-propyl, n-butyl, t-butyl, hexyl, cyclohexyl, cyclopentylmethyl, octyl,
dodecyl, tridecyl and heptadecyl; the substituted alkyl groups are
selected from the group consisting of monocyclic and bicyclic aryl groups,
heterocyclic groups, halogen atoms, carboxyl groups, alkoxycarbonyl groups
having 2-6 carbon atoms, alkoxy groups having not more than 20 carbon
atoms and hydroxyl groups.
20. The method as claimed in claim 1, wherein the substituted alkyl group
is selected from the group consisting of benzyl, phenethyl, chloromethyl,
2-chloroethyl, trifluoromethyl, carboxymethyl, 2-carboxyethyl,
2-(methoxycarbonyl)ethyl, ethoxycarbonylmethyl, 2-methoxyethyl,
hydroxymethyl and 2-hydroxyethyl; the unsubstituted aryl group is a phenyl
group or a naphthyl group; the substituted aryl group contains
substituents selected from the group consisting of alkyl group having 1-4
carbon atoms, halogen atoms, nitro groups, carboxyl groups, alkoxycarbonyl
groups having 2-6 carbon atoms, hydroxyl groups and alkoxy groups having
1-6 carbon atoms; the amino group represented by each of R.sup.3, R.sup.4,
R.sup.5 and R.sup.6 have a substituent selected from the group consisting
of alkyl groups and acyl groups.
21. The method as claimed in claim 1, wherein the carbamoyl group
represented by each of R.sup.3, R.sup.4, R.sup.5 and R.sup.6 contains as
substituent or substituents one or more alkyl groups having 1-20 carbon
atoms, monocyclic or bicyclic aryl groups; the alkoxycarbonyl group
represented by each of R.sup.3, R.sup.4, R.sup.5 and R.sup.6 is a
methoxycarbonyl group, ethoxycarbonyl group or a butoxycarbonyl group; the
heterocyclic group represented by each of R.sup.3, R.sup.4, R.sup.5 and
R.sup.6 is a monocyclic or a fused bicyclic or tricyclic ring; and a ring
formed by R.sup.3 and R.sup.4 or by R.sup.4 and R.sup.5 is a cyclopentane,
cyclohexane, cyclohexene, benzene, furan, pyrrolidine or a thiophene ring.
22. The method as claimed in claim 1, wherein R.sup.6 is a substituted
alkyl group represented by the following formula
##STR14##
wherein R.sup.3, R.sup.4 and R.sup.5 have the same meaning as defined
above and n represents 2 or 4.
23. The method as claimed in claim 1, wherein the heterocyclic group
represented by Z in formula (II-c) is a fused group selected from the
group consisting of imidazole, triazole, tetrazole, thiazole, oxazole,
selenazole, benzimidazole, benzoxazole, benzthiazole, thiadiazole,
oxadiazole, benzselenazole, pyrazole, pyrimidine, triazine, pyridine,
naphthothiazole, naphthoimidazole, naphthoxazole, azabenzimidazole, purine
and azaindenes.
24. The method as claimed in claim 1, wherein the heterocyclic groups are
substituted by substituents selected from the group consisting of alkyl
groups, alkenyl groups, aralkyl groups, aryl groups, heterocyclic groups,
halogen atoms, mercapto, cyano, carboxyl, sulfo, hydroxyl, carbamoyl,
sulfamoyl, amino groups, nitro groups, alkoxy groups, aryloxy groups,
acryl groups, acylamino groups, substituted amino groups, alkyl-thio
groups, aryl-thio groups, alkoxycarbonyl groups and aryloxycarbonyl
groups.
25. The method as claimed in claim 1, wherein the aromatic primary amine
color developing agent is a p-phenylenediamine derivative.
26. The method as claimed in claim 1, wherein the aromatic primary amine
color developing agent is present in an amount of about 0.1 g to about 20
g per liter of color developer.
27. The method as claimed in claim 1, wherein the compound represented by
formula (I) is selected from the group consisting of
##STR15##
28. The method as claimed in claim 1, wherein the compound represented by
formula (I) is selected from the group consisting of
##STR16##
29. The method as claimed in claim 1, wherein the compound represented by
formula (I) is
##STR17##
30. The method as claimed in claim 4, wherein R.sup.1 and R.sup.2 both have
a substituent.
31. The method as claimed in claim 6, wherein the substituent or R.sub.1
and R.sub.2 is an alkoxy group. |
|
 |
|
 |
Claims |
|
|
|
Description |
|
|
BACKGROUND OF THE INVENTION
(1) Field of the Invention
The invention relates to a method of processing a silver halide color
photographic material, and more particularly to a method of processing a
silver halide color photographic material in which the stability of a
color developer is improved so that the increased fogging problem in
continuous processing is lessened and the processing time is shortened.
(2) Description of the Prior Art
Reflecting the demand for a shorter customer waiting period and reduced
laboratory work, it has been desirable to shorten the processing time of
color photographic materials in recent years. As ways of shortening the
time of each processing step, it was a routine practice to raise the
temperature or increase the replenishing amount. Numerous other approaches
have also been proposed, including the use of intensified agitation and
the addition of various accelerators or promotors.
Of these, Japanese Patent Application (OPI) Nos. 95345/1983, 23242/1984,
19140/1985 and 70552/1986 disclose a method of processing a color
photographic material which contains an emulsion of silver chloride with a
view towards speeding up color development and/or reducing the
replenishing amount. When a photographic material utilizing an emulsion of
such a high chlorine content is processed, hydroxylamine, which has
conventionally been used as a preservative for color developers, cannot be
used because it induces silver development (black and white development)
and significantly lowers the dye density as described in Japanese Patent
Application (OPI) No. 19140/1985. For this reason, a
dihydroxybenzenecarboxylic acid was used in lieu of hydroxylamine in the
invention of the patent application. This approach, however, was still
unable to sufficiently stabilize a color developer.
Various preservatives and chelating agents have been investigated for many
years with a view towards improving the stability of color developers. As
exemplary preservatives may be mentioned the aromatic polyhydroxy
compounds described in Japanese Patent Application (OPI) Nos. 49828/1977,
160142/1984 and 47038/1981 and U.S. Pat. No. 3,746,544; the
hydroxycarbonyl compounds described in U.S. Pat. No. 3,615,503 and British
Pat. No. 1,306,176; the .alpha.-aminocarbonyl compounds described in
Japanese Patent Application (OPI) Nos. 143020/1977 and 89425/1978; the
alkanolamines described in Japanese Patent Application (OPI) No.
3532/1979; and the metal salts described in Japanese Patent Application
(OPI) Nos. 44148/1982 and 53749/1982. On the other hand, illustrative
examples of such chelating agents include the aminopolycarboxylic acids
described in Japanese Patent Publication Nos. 30496/1973 and 30232/1969;
the organophosphonic acids described in Japanese Patent Application (OPI)
No. 97347/1981, Japanese Patent Publication No. 39359/1981 and West German
Pat. No. 2,227,639; phosphonocarboxylic acids described, for example, in
Japanese Patent Application (OPI) Nos. 102726/1977, 42730/1978,
121127/1979, 126241/1980 and 65956/1980; and further, compounds described,
for example, in Japanese Patent Application (OPI) Nos. 195845/1983 and
203440/1983 and Japanese Patent Publication No. 40900/1978.
Use of the above-described various preservatives and chelating agents was,
however, unable to bring about sufficient effects for color developers
which did not contain hydroxylamine.
Furthermore, color photographic materials which contain a chlorobromide
emulsion having a high chlorine content tend to develop fogging upon color
development as disclosed in Japanese Patent Application (OPI) Nos.
95345/1983 and 232342/1984. The techniques disclosed in these patent
publications, however, failed to prevent fogging satisfactorily. Other
methods used to prevent development fogging have been to add, in
photographic materials or processing solutions, heterocyclic compounds
such as 1-phenyl-5-mercptotetrazoles (see, for example, Belgium Pat. No.
671,406, U.S. Pat. Nos. 3,295,976, 3,376,310, 3,615,616, 3,071,465,
3,420,664 and 2,403,927, and Japanese Patent Application (OPI) Nos.
37436/1975 and 95728/1983), benzotriazoles (see, for example, British Pat.
Nos. 919,061 and 768,438, U.S. Pat. Nos. 3,157,509 and 3,082,088, and
German Pat. No. 617,712), benzimidazoles (see, for example, U.S. Pat. Nos.
3,137,578, 3,148,066 and 3,511,663, British Pat. Nos. 271,475, 1,344,548,
3,148,066 and 3,511,663, and German Pat. Nos. 708,424, 635,769 and
2,205,539), and imidazoles (see, for example, U.S. Pat. Nos. 3,106,467,
3,420,670, 1,763,990 and 2,271,229). None of these heterocyclic compounds,
however, were able to achieve sufficient antifogging effects.
BRIEF SUMMARY OF THE INVENTION
An object of this invention is therefore to provide a processing method of
a silver halide color photographic material in which the stability of a
color developer can be improved to significantly lessen the increased
fogging problem of continuous processing.
Another object of this invention is to provide a processing method of a
silver halide color photographic material which can shorten the
development time and also prevent color density reduction.
A further object of this invention is to provide a processing method of a
silver halide color photographic material which does not use benzyl
alcohol and does not lower the color-forming property of the color
photographic material.
Other and further objects, features and advantages of the invention will be
detailed more fully in the following description.
DETAILED DESCRIPTION OF THE INVENTION
As a result of extensive research, the inventors have discovered that the
above-described objectives have been successfully realized by the
following:
A method of processing a silver halide color photographic material, which
comprises iamgewise exposing a silver halide color photographic material
to light and then processing the silver halide color photographic material
containing (i) an aromatic primary amine color developing agent, and (ii)
a hydroxylamine compound represented by the following general formula (I):
##STR1##
wherein R.sup.1 and R.sup.2 each represent an unsubstituted or substituted
alkyl, alkenyl or aryl group (hereinafter and in claims simply referred to
as alkyl, alkenyl or aryl group) and may optionally joined together to
form a heterocyclic ring with the associated nitrogen atom and at least
one compound selected from the group consisting of formulae (II-a), (II-b)
and (II-c) which are described hereinbelow.
In the present invention it is preferable that the color developer be
substantially free of benzyl alcohol from the viewpoint of prevention of
environmental contamination, convenience of preparation of the developer
solution and prevention of fogging. The term "substantially free" as used
in this specification and claims means that the content of benzyl alcohol
is not higher than 2 ml per liter of the color developer. It is more
preferable in the present invention that benzyl alcohol not be contained
at all. Fogging can be reduced further by making the color developer
substantially free of benzyl alcohol, as mentioned above.
In the present invention, the color developer contains at least one
compound selected from compounds represented respectively by the following
general formulae (II-a), (II-b) or (II-c): General formula (II-a)
##STR2##
wherein R.sup.3, R.sup.4, R.sup.5 and R.sup.6, which may be the same or
different, each represent a hydrogen atom; a substituted or unsubstituted
alkyl, aryl or amino group (hereinafter and in claims simply referred to
as alkyl, aryl or amino group); a hydroxyl group; an alkoxy group; an
alkylthio group; a carbamoyl group which may optionally be substituted; a
halogen atom; a cyano group; a carboxyl group; an alkoxycarbonyl group, or
a heterocyclic group; and R.sup.3 and R.sup.4 or R.sup.4 and R.sup.5 may
form a 5 or 6-membered ring in combination, with a proviso that at least
one of R.sup.3 and R.sup.5 represents a hydroxyl group.
Z--S--M
wherein M represents a hydrogen atom, cation or --S--Z (Z represents a
heterocyclic ring containing at least one nitrogen atom).
It is already disclosed in Japanese Patent Application (OPI) No.
232342/1984 to use the compounds of the general formula (IIc) used in the
present invention to prevent fogging. It was, however, used in the
presence of benzyl alcohol, and as such the antifogging effects were low.
In the present invention, a remarkable antifogging effect is exhibited in
a system which is substantially free of benzyl alcohol. This is by no
means expected from the description of Japanese Patent Application (OPI)
No. 232342/1984. Exclusion of benzyl alcohol generally resulted in a
reduction of the color-forming property. It is quite unpredictable that
the color-forming property is substantially unaffected by the omission of
benzyl alcohol in the presence of the compound of the general formula (I).
The compound of the general formula (I) will next be described in detail.
In the general formula (I), the alkyl and alkenyl groups represented by
each of R.sup.1 and R.sup.2 may be linear, branched or cyclic. As
exemplary substituents which these alkyl, alkenyl and aryl groups may
contain may be mentioned halogen atoms (e.g., F, Cl, Br), aryl groups
(e.g., phenyl, p-chlorophenyl), alkoxy groups (e.g., methoxy, ethoxy,
methoxyethoxy), aryloxy groups (e.g., phenoxy), sulfonyl groups (e.g.,
methanesulfonyl, p-toluenesulfonyl), sulfonamido groups (e.g.,
methanesulfonamido, benzenesulfonamido), sulfamoyl groups (e.g.,
diethylsulfamoyl, unsubstituted sulfamoyl), carbamoyl groups (e.g.,
unsubstituted carbamoyl, diethylcarbamoyl), amido groups (e.g., acetamido,
benzamido), ureido groups (e.g., methylureido, phenylureido),
alkoxycarbonylamino groups (e.g., methoxycarbonylamino),
aryloxycarbonylamino groups (e.g., phenoxycarbonylamino), alkoxycarbonyl
groups (e.g., methoxycarbonyl), aryloxycarbonyl groups (e.g.,
phenoxycarbonyl), cyano group, hydroxyl group, carboxyl group, sulfo
group, nitro group, amino groups (e.g., unsubstituted amino,
diethylamino), alkylthio groups (e.g., methylthio), arylthio groups (e.g.,
phenylthio), and heterocyclic groups (e.g., morpholinyl, pyridyl). Here,
R.sup.1 and R.sup.2 may be the same or different. In addition, the
substituents in R.sup.1 and R.sup.2 may also be the same or different.
R.sup.1 and R.sup.2 may preferably have carbon atoms of 1-10 with 1-5 being
especially preferred. As illustrative examples of the nitrogen-containing
heterocyclic ring which is formed when R.sup.1 and R.sup.2 are joined
together may be mentioned piperidyl groups, pyrrolidinyl groups,
N-alkylpiperazyl groups, morpholinyl groups, indolinyl groups and
benztriazolyl groups.
Preferable substituents on R.sup.1 and R.sup.2 are hydroxyl groups, alkoxy
groups, sulfonyl groups, amido groups, carboxyl groups, cyano groups,
sulfo groups, nitro groups and amino groups.
It is preferable in the present invention that at least one of R.sup.1 and
R.sup.2 be a group having one or more further substituents.
Hydroxylamines (I), in which R.sup.1 and R.sup.2 are both unsubstituted
alkyl groups, are not preferable due to their poor preserving ability and
offensive odor.
Specific examples of the compound represented by the general formula (I)
useful in the practice of this invention will be described below. It
should be borne in mind, however, that the scope of this invention is not
limited to the following compounds.
##STR3##
Compounds represented by the general formula (I) can be synthesized by
known processes described in the following publications.
U.S. Pat. No. 3,661,996;
U.S. Pat. No. 3,362,961;
U.S. Pat. No. 3,293,034;
Japanese Patent Publication No. 2794/1967;
U.S. Pat. No. 3,491,151;
U.S. Pat. No. 3,655,764;
U.S. Pat. No. 3,467,711;
U.S. Pat. No. 3,455,916;
U.S. Pat. No. 3,287,125; and
U.S. Pat. No. 3,287,124.
These compounds may be used in the form of salts with various acids such as
hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic
acid and acetic acid.
To a color developer, these compounds may each be added in an amount of
0.1-20 g, preferably 0.5-10 g, per liter of the color developer.
A description will next be made of the compounds of the general formulae
(IIa) and (IIb) which are also useful in this invention.
In these formulae, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 may be the same or
different and represent individually a hydrogen atom, a substituted or
unsubstituted alkyl group which has 1-20 carbon atoms in a cyclic or
branched form, an unsubstituted or substituted monocyclic or bicyclic aryl
group, an unsubstituted or substituted amino group, a hydroxyl group, an
alkoxy group having 1-20 carbon atoms, an alkylthio group having 1-6
carbon atoms, a carbamoyl group which may have one or more aliphatic or
aromatic groups as a substituent, a halogen atom, a cyano group, a
carboxyl group, an alkoxycarbonyl group having 2-20 carbon atoms, or a
heterocyclic group containing a 5 or 6-membered ring having one or more
hetero atoms such as nitrogen, oxygen and/or sulfur atoms. R.sup.3 and
R.sup.4 or R.sup.5 and R.sup.6 may, in combination, form a 5 or 6-membered
ring. At least one of R.sup.3 and R.sup.5, however, is a hydroxyl group.
Illustrative examples of the unsubstituted alkyl group may include methyl,
ethyl, n-propyl, i-propyl, n-butyl, t-butyl, hexyl, cyclohexyl,
cyclopentylmethyl, octyl, dodecyl, tridecyl and heptadecyl. As exemplary
substituents in the substituted alkyl group may be mentioned monocyclic
and bicyclic arylgroups, heterocyclic groups, halogen atoms, carboxyl
groups, alkoxycarbonyl groups having 2-6 carbon atoms, alkoxy groups
having not more than 20 carbon atoms and hydroxyl groups. Specific
examples of the substituted alkyl group may include benzyl, phenethyl,
chloromethyl, 2-chloroethyl, trifluoromethyl, carboxymethyl,
2-carboxyethyl, 2-(methoxycarbonyl)ethyl, ethoxycarbonylmethyl,
2-methoxyethyl, hydroxymethyl and 2-hydroxyethyl. Illustrative examples of
the unsubstituted aryl group may include phenyl and naphthyl. When an aryl
group is further substituted, exemplary substituents may be alkyl groups
having 1-4 carbon atoms, halogen atoms, nitro groups, carboxyl groups,
alkoxycarbonyl groups having 2-6 carbon atoms, hydroxyl groups and alkoxy
groups having 1-6 carbon atoms. Illustrative examples of the substituted
aryl group may include p-tolyl, m-tolyl, p-chlorophenyl, p-bromophenyl,
o-chlorophenyl, m-nitrophenyl, p-carboxyphenyl, o-carboxyphenyl,
o-(methoxycarbonyl)phenyl, o-hydroxyphenyl, p-methoxyphenyl and
m-ethoxyphenyl.
The amino group represented by each of R.sup.3, R.sup.4, R.sup.5 and
R.sup.6 may have a substituent. As exemplary substituents may be mentioned
alkyl groups (e.g., methyl, ethyl, butyl) and acyl groups (e.g., acetyl,
methylsulfonyl). As illustrative substituted amino groups may be mentioned
a dimethylamino group, diethylamino group, butylamino group and
acetylamino group.
As specific examples of the alkoxy group represented by each of R.sup.3,
R.sup.4, R.sup.5 and R.sup.6 may be mentioned a methoxy group, ethoxy
group, butoxy group and heptadecyloxy group.
The carbamoyl group represented by each of R.sup.3, R.sup.4, R.sup.5 and
R.sup.6 may contain as substituent or substituents one or more alkyl
groups having 1-20 carbon atoms, or monocyclic or bicyclic aryl groups. As
specific examples of the substituted carbamoyl group may be mentioned a
methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group and
phenylcarbamoyl group.
Specific examples of the alkoxycarbonyl group represented by each of
R.sup.3, R.sup.4, R.sup.5 and R.sup.6 may include a methoxycarbonyl group,
ethoxycarbonyl group and butoxycarbonyl group.
As specific examples of the halogen atom represented by each of R.sup.3,
R.sup.4, R.sup.5 and R.sup.6 may be mentioned a chlorine atom and bromine
atom.
The heterocyclic group represented by each of R.sup.3, R.sup.4, R.sup.5 and
R.sup.6 may be monocyclic or may contain a fused bicyclic or tricyclic
ring. Specific examples may include a furyl group, pyridyl group,
2-(3-methyl)benzothiazolyl group and 1-benzotriazolyl group.
Illustrative examples of the ring formed by R.sup.3 and R.sup.4 or by
R.sup.4 and R.sup.5 may include cyclopentane, cyclohexane, cyclohexene,
benzene, furan, pyrrolidine and thiophene.
When R.sup.6 represents a substituted alkyl group, a heterocyclic group may
be contained as a substituent. Substituted alkyl groups represented by the
following general formula are preferred:
##STR4##
wherein R.sup.3, R.sup.4 and R.sup.5 have the same meaning as defined
above and n stands for 2 or 4.
Specific examples of the compound represented by the general formula (IIa)
or (IIc) will be described below, though it should be borne in mind that
the present invention is not limited to them.
##STR5##
The compounds of the general formula (IIa) can be easily synthesized with
reference to Bulow and Haas, Berichte, 42, 4638 (1907) and ibid. 43, 375
(1910); Allen, et al., J. Org. Chem., 24, 796 (1959); De Cat and Dormael,
Bull. Soc. Chim. Belg., 60, 69 (1951); and Cook, et al., Rec. Trav. Chem.,
69, 343 (1950).
On the other hand, the compounds of the general formula (IIb) can be easily
synthesized with reference to Bower and Doyle, J. Chem. Soc., 1957, 727;
and Allen, et al., J. Org. Chem., 24, 787 (1959).
The compounds represented by the general formula (IIc) will next be
described in detail.
The heterocyclic group represented by Z in the above general formula (IIc)
may be a fused one. Specific examples may include imidazole, triazole,
tetrazole, thiazole, oxazole, selenazole, benzimidazole, benzoxazole,
benzthiazole, thiadiazole, oxadiazole, benzselenazole, pyrazole,
pyrimidine, triazine, pyridine, naphthothiazole, naphthoimidazole,
naphthoxazole, azabenzimidazole, purine and azaindenes (e.g.,
triazaindene, tetrazaindene, pentazaindene).
These heterocyclic groups and fused rings may be substituted by suitable
substituents. As exemplary substituents may be mentioned alkyl groups
(e.g., methyl, ethyl, hydroxyethyl, trifluoromethyl, sulfopropyl,
di-propylaminoethyl, adamantane), alkenyl groups (e.g., allyl), aralkyl
groups (e.g., benzyl, p-chlorophenethyl), aryl groups (e.g., phenyl,
naphthyl, p-carboxyphenyl, 3,5-di-carboxyphenyl, m-sulfophenyl,
p-acetamidophenyl, 3-capramidophenyl, p-sulfamoylphenyl, m-hydroxyphenyl,
p-nitrophenyl, 3,5-dichlorophenyl, 2-methoxyphenyl), heterocyclic groups
(e.g., pyridine groups, furan groups, thiophene groups), halogen atoms
(e.g., chlorine atom, bromine atom), mercapto, cyano, carboxyl, sulfo,
hydroxyl, carbamoyl, sulfamoyl, amino and nitro groups, alkoxy groups
(e.g., methoxy), aryloxy groups (e.g., phenoxy), acyl groups (e.g.,
acetyl), acylamino groups (e.g., acetylamino, capramido,
methylsulfonylamido), substituted amino groups (e.g., diethylamino,
hydroxyamino), alkyl- or aryl-thio groups (e.g., methylthio,
carboxyethylthio, sulfobutylthio), alkoxycarbonyl groups (e.g.,
methoxycarbonyl), and aryloxycarbonyl groups (e.g., phenoxycarbonyl).
The compounds represented by the general formula (I) can be synthesized
with reference to, for example, E. J. Birr, "Stabilization of Photographic
Silver Halide Emulsions" (Focal Press Inc., 1974); C. G. Barlow, et al.,
"Rep. Prog. Appln. Chem." 59, 159 (1974); and various literature cited in
"Research Disclosure", 17643 (1978).
Specific examples of the compound represented by the general formula (IIc)
useful in this invention will next be described. It should be borne in
mind, however, that the present invention is not limited to them.
##STR6##
The compounds of general formulae (IIa), (IIb) and (IIc) may each be added,
in an amount of 5 mg-3 g, preferably 10 mg-1 g, per liter of the color
developer.
Thee antifogging agents may each be dissolved out from a color photographic
material into a color developer in the course of its processing, such that
the amount of antifogging agent mentioned above may accumulate in the
color developer.
The color developer of this invention contains an aromatic primary amine as
a color developing agent. Preferable examples of the aromatic primary
amine are p-phenylenediamine derivatives. Typical examples will be given
below. It should be borne in mind, however, that the aromatic primary
amine is not necessarily limited to the following typical 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 also be used in the form of salts
such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The
developing agents of the aromatic primary amine type may each be used in
an amount of about 0.1 g-about 20 g, more preferably about 0.5-about 10 g,
per liter of developer.
It is preferable that the color developer employed in the present invention
not contain hydroxylamine. When hydroxylamine is contained, it is
preferable to lower its content as much as possible.
It is also preferable to contain, as a preservative, a sulfite such as
sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite,
sodium metasulfite or potassium metasulfite, or a carbonyl sulfite
addition product. The preservative may be added in an amount of 0 g-20
g/l, preferably 0 g-5 g/l. A smaller amount is preferable, provided that
the stability of the color developer is retained.
As other preservatives may be mentioned the hydroxyacetones described in
U.S. Pat. No. 3,615,503 and British Pat. No. 1,306,176; the
.alpha.-aminocarbonyl compounds described in Japanese patent application
(OPI) Nos. 14302/1977 and 89425/1978; the various metals described, for
example, in Japanese patent application (OPI) Nos. 44148/1982 and
53749/1982; the various saccharides described in Japanese patent
application (OPI) No. 102727/1977; the hydroxamic acids described in
Japanese patent application (OPI) No. 27638/1977; the
.alpha.,.alpha.'-dicarbonyl compounds described in Japanese patent
application (OPI) No. 160141/1984; the salicyclic acids described in
Japanese patent application (OPI) No. 180588/1984; the alkanolamines
described in Japanese patent application (OPI) No. 3532/1979; the
poly(alkyleneimines) described in Japanese patent application (OPI) Nos.
94349/1981; and the gluconic acid derivatives described in Japanese patent
application (OPI) No. 75647/1981. Two or more of these preservatives may
be used in combination as needed.
It is particularly preferable to add an alkanolamine (e.g., triethanol
amine, diethanolamine) and/or an aromatic polyhydroxyl compound.
The color developer useful in this invention preferably has a pH in the
range of 9-12, with a pH of 9-11.0 being more preferable. The color
developer may contain other compounds, known as developer components.
It is preferable to use a buffering agent to maintain the above pH.
As exemplary usable buffering agents may be mentioned carbonates,
phosphates, borates, tetraborates, hydroxybenzoates, glycine salt,
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. Carbonates, phosphates,
tetraborates and hydroxybenzoates have special merits; they have excellent
solubility and buffering effects in the pH range of 9.0 and higher; they
contribute no deleterious effects (e.g., fogging) to photographic
performance through their incorporation in color developers; and they are
economical. It is hence particularly preferable to use these buffering
agents.
As specific examples of these buffering agents may be mentioned sodium
carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
trisodium phosphate, tripotassium phosphate, bisodium phosphate,
bipotassium phosphate, sodium borate, potassium borate, sodium tetraborate
(borax), potassium tetraborate, | | |
