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Claims  |
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What is claimed is:
1. A process for processing a DIR coupler-containing silver halide color
photographic material for photographing use in a continuous manner with
replenishment of a developing solution, in which said DIR coupler is a
coupler which has in a coupling active site a group that functions as a
development inhibitor or a development inhibitor precursor upon being
eliminated from the coupling active site by color development processing
and that will be decomposed to a compound exerting substantially no
influences on photographic properties after flowing into a color
developing solution, said development inhibitor having a half-value period
of 4 hours or shorter at a pH of 10.0, and in which process the developing
solution is replenished in an amount of 700 ml or less per m.sup.2 of
light-sensitive material developed; wherein the DIR coupler is represented
by the following general formula (I'):
A[(L.sub.1).sub.a --Z--(L.sub.2 --Y).sub.b --].sub.m (I')
wherein:
A represents a coupler component;
Z represents a fundamental portion of a compound which shows
development-inhibiting action, and is bound to the coupling site of a
coupler directly (a=0) or through a linking group, L.sub.1 (a=1);
Y represents a substituent bond to Z through a linking group L.sub.2 to
allow the development-inhibiting effect of Z to emerge, with the linking
group represented by L.sub.2 containing a chemical bond to be cleaved in a
developer;
a represents 0 or 1, and b represents 1 or 2, provided that when b
represents 2, two (--L.sub.2 Y)s may be the same or different; and
m represents 1 or 2.
2. A process for processing a DIR coupler-containing silver halide color
photographic material for photographing use in a continuous manner with
replenishment of a developing solution, in which said DIR coupler is a
coupler which in a coupling active site a group that functions as a
development inhibitor or a precursor thereof upon being eliminated from
the coupling active site by color development processing and that will be
decomposed to a compound exerting substantially no influences on
photographic properties after flowing into a color developing solution,
said development inhibitor having a half-value period of 4 hours or
shorter at a pH of 10.0, and which process is conducted in the presence of
a compound or compounds represented by the following general formula (I)
and/or (II):
##STR27##
wherein: A represents an n-valent aliphatic, aromatic or heterocyclic
linking group (provided that, when n=1, A represents a mere aliphatic,
aromatic or heterocyclic group);
X.sub.1 represents
##STR28##
R.sup.1 and R.sup.2 each represents a substituted or unsubstituted lower
alkyl group;
R.sup.3 represents a lower alkylene group containing 1 to 5 carbon atoms;
R.sup.4 represents a lower alkyl group; or
R.sup.1 and R.sup.2, R.sup.1 and A, R.sup.1 and R.sup.3, R.sup.2 and A, or
R.sup.2 and R.sup.3 may be connected to each other to form a ring;
Y represents an anion;
l represents 0 or 1;
m represents 0 or 1;
n represents 1, 2 or 3;
p represents 0 or 1; and
q represents 0, 1, 2 or 3;
##STR29##
wherein: r represents an integer of 1 to 3:
R.sub.11 and R.sub.12 each represents a hydrogen atom, a lower alkyl group
containing 1 to 5 carbon atoms, or an acyl group containing 1 to 3 carbon
atoms (provided that R.sub.11 and R.sub.12 do not represent a hydrogen
atom at the same time); or
R.sub.11 and R.sub.12 may be taken together to form a ring;
and wherein the DIR coupler is represented by the following general formula
(I'):
A[(L.sub.1).sub.a --Z--(L.sub.2 --Y).sub.b --].sub.m (I')
wherein:
A represents a coupler component;
Z represents a fundamental portion of a compound which shows
development-inhibiting action, and is bound to the coupling site of a
coupler directly (a=0) or through a linking group, L.sub.1 (a=1);
Y represents a substituent bound to Z through a linking group L.sub.2 to
allow the development-inhibiting effect of Z to emerge, with the linking
group represented by L.sub.2 containing a chemical bond to be cleaved in a
developer;
a represents 0 or 1, and b represents 1 or 2, provided that when b
represents 2, two (--L.sub.2 Y)s may be the same or different; and
m represents 1 or 2.
3. A process for processing a DIR coupler-containing silver halide color
photographic material for photographing use in a continuous manner with
replenishment of a developing solution, in which said DIR coupler is a
coupler which has in a coupling active site a group that functions as a
development inhibitor or a precursor thereof upon being eliminated from
the coupling active site by color development processing and that will be
decomposed to a compound exerting substantially no influences on
photographic properties after flowing into a color developing solution,
said development inhibitor having a half-value period of 4 hours or
shorter at a pH of 10.0, and in which process the light-sensitive material
is processed, after the color development, in a bleaching solution having
a pH of 5.7 or less; and wherein the DIR coupler is represented by the
following general formula (I'):
A[(L.sub.1).sub.a --Z--(L.sub.2 --Y).sub.b --].sub.m (I')
wherein:
A represents a coupler component;
Z represents a fundamental portion of a compound which shows
development-inhibiting action, and is bound to the coupling site of a
coupler directly (a=0) or through a linking group, L.sub.1 (a=1);
Y represents a substituent bond to Z through a linking group L.sub.2 to
allow the development-inhibiting effect of Z to emerge, with the linking
group represented by L.sub.2 containing a chemical bond to be cleaved in a
developer;
a represents 0 or 1, and b represents 1 or 2, provided that when b
represents 2, two (--L.sub.2 Y)s may be the same or different; and
m represents 1 or 2.
4. The process for processing a silver halide photographic material as
described in claim 2, wherein the photographic material is processed, in a
silver-removing step, in a bath having a bleach-fixing ability or in a
bleaching bath and a subsequent bath having a bleach-fixing ability.
5. The process for processing a silver halide photographic material as
described in claim 2, wherein a bleaching bath having a pH of 5.7 or less
is provided in a silver-removing step.
6. The process for processing a silver halide photographic material as
described in claim 1, which is conducted in the presence of at least one
of the compounds represented by the general formula (I) and/or (II):
##STR30##
wherein: A represents an n-valent aliphatic, aromatic or heterocyclic
linking group (provided that, when n=1, A represents a mere aliphatic,
aromatic or heterocyclic group);
X represents
##STR31##
R.sup.1 and R.sup.2 each represents a substituted or unsubstituted lower
alkyl group;
R.sup.3 represents a lower alkylene group containing 1 to 5 carbon atoms;
R.sup.4 represents a lower alkyl group; or
R.sup.1 and R.sup.2, R.sup.1 and A, R.sup.1 and R.sup.3, R.sup.2 and A, or
R.sup.2 and R.sup.3 may be connected to each other to form a ring;
Y represents an anion;
l represents 0 or 1;
m represents 0 or 1;
n represents 1, 2 or 3;
p represents 0 or 1; and
q represents 0, 1, 2 or 3,
##STR32##
wherein: r represents an integer of 1 to 3;
R.sub.11 and R.sub.12 each represents a hydrogen atom, a lower alkyl group
containing 1 to 5 carbon atoms, or an acyl group containing 1 to 3 carbon
atoms (provided that R.sub.11 and R.sub.12 do not represent a hydrogen
atom at the same time); or
R.sub.11 and R.sub.12 may be taken together to form a ring.
7. The process for processing a silver halide photographic material as
described in claim 6, wherein the photographic material is processed, in
the silver-removing step, in a bath having a bleach-fixing ability or in a
bleaching bath and a subsequent bath having a bleach-fixing ability.
8. The process for processing a silver halide photographic material as
described in claim 7, wherein said bleaching solution has a pH of 5.7 or
less.
9. A process as in claims 1, 2, or 3 wherein Z in formula (I') represents a
divalent N-containing heterocyclic group or a N-containing heterocyclic
thiogroup.
10. A process as in claims 1, 2, or 3 wherein Z in formula (I') represents
a thiogroup selected from the group consisting of tetraazylthio group, a
benzylthiozylthio group, benzimidazolylthio group, a triazolylthiolyl
group, and an imidazoylythio group.
11. The process as in claims 1, 2 or 3 wherein the DIR coupler is
represented by the following general formula (II'), (III'), (IV'), (V'),
(VI'), (VII'), (VIII'), (IX'), (X'), (XI'), (XII'):
##STR33##
wherein: A represents a coupler component;
Y represents a substituent bound to a fundamental portion of a compound
which shows development-inhibiting action through a linking group L.sub.2
to allow the development-inhibiting effect of a compound which shows
development-inhibiting action to emerge, with the linking group
represented by L.sub.2 containing a chemical bond to be cleaved in a
developer;
a represents 0 or 1, and b represents 1 or 2, provided that when b
represents 2, two (--L.sub.2 Y)s may be the same or different; and
m represents 1 or 2.
12. A process as in claim 1, wherein said half-value period is not longer
than 2 hours.
13. A process as in claim 1, wherein said half-value period is not longer
than 1 hours.
14. A process as in claim 1, wherein said L.sub.2 in the general formula
(I') is selected from the following groups together with the substitution
positions of Z and Y:
##STR34##
wherein d represents an integer of 0 to 10, W.sub.1 is a hydrogen atom, a
halogen atom, an alkyl group containing 1 to 10 carbon atoms, an
alkanamido group containing 1 to 10 carbon atoms, an alkoxycarbonyl group
containing 2 to 10 carbon atoms, an aryloxycarbonyl group, an
alkanesulfonamido group containing 7 to 10 carbon atoms, an aryl group
containing 6 to 10 carbon atoms, a carbamoyl group, an N-alkylcarbamoyl
group containing 1 to 10 carbon atoms, a nitro group, a cyano group, an
arylsulfonamido group containing 6 to 10 carbon atoms, a sulfamoyl group,
or an imido group, W.sub.2 represents a hydrogen atom, an alkyl group
containing 1 to 6 carbon atoms, an aryl group containing 6 to 10 carbon
atoms, or an alkenyl group containing 2 to 10 carbon atoms, W.sub.3
represents a hydrogen atom, a halogen atom, a nitro group, an alkoxy group
containing 1 to 6 carbon atoms, or an alkyl group containing 1 to 6 carbon
atoms, and P represents an integer of 0 to 6.
15. A process as in claim 1, wherein the amount of the developing solution
to be replenished is not more than 600 ml per m.sup.2 of the
light-sensitive material developed.
16. A process as in claim 1, wherein the amount of the developing solution
to be replenished is not more than 500 ml per m.sup.2 of the
light-sensitive material developed. |
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Claims |
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Description |
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FIELD OF THE INVENTION
The present invention relates to a process for processing silver halide
photographic materials for photographing use and, more particularly, to a
process for processing photographic materials which enables reduction in
the amount of replenishing developer.
In addition, it pertains to a novel light-sensitive material and a process
for processing it, which enables shortening of the time of the
silver-removing step.
BACKGROUND OF THE INVENTION
In general, color photographic images can be formed by color-developing an
imagewise exposed light-sensitive material in a color developer containing
an aromatic primary amine developing agent such as p-phenylenediamine,
then subjecting it to the processing of bleaching, fixing, washing with
water, and stabilizing. A bleach-fixing processing is also known, in which
bleaching and fixing are conducted at the same time for accelerating the
ordinary processing.
In recent years, it has been regarded important to keep the environment
clean, and to save and recover water and silver in automatic processing
color photographic materials in a continuous manner, and method for
preventing environmental pollution, methods for effectively recovery
silver, methods for reducing the amount of washing water, methods for
re-using washing water, and the like have been eagerly demanded.
In view of simplifying photographic processing, too, it has been strongly
desired to reduce the amount of replenishing developer in a replenishing
type development processing step.
In continuous development processing, the replenishing amount of a
developer used somewhat varies depending upon the kind of light-sensitive
materials to be processed, but is usually about 1300 to 1100 ml per
m.sup.2 of processed silver halide color photographic materials for
photographing use.
From the above-described standpoint, it has been desired to reduce the
amount of replenishing developer. However, reduction in amount of
replenishing developer leads to deterioration of photographic properties,
and hence it is generally extremely difficult.
On the other hand, in order to fill the demand for maintaining a clean
environment, various processes have been tried for reproducing color
developer in color development processing steps.
For example, there are illustrated those described in J. Appl. Phot. Eng.,
5, 208 (1979), Gekkan Labo, 15, 113 (1979), SMPTE, J., 88, 165 (1979), J.
Appl. Phot. Eng., 5, 32 (1979), SMPTE, J. 88, 168 (1979), Japanese Patent
Application (OPI) Nos. 143018/77, 1462336/77, 149331/78, 9629/79, J. Appl.
Phot. Eng., 5, 216 (1979), etc.
In general, reduction in the amount of replenishing developer results in a
relative increase in the amount of substance dissolved into the developer
from silver halide photographic materials (for example, halide ions
produced by decomposition of silver halide), causing the problem of
reduction in sensitivity.
As a countermeasure for this problem of reduction in sensitivity, it has
been attempted to raise the processing temperature to reduce the amount of
replenishing developer without reduction in sensitivity. For example,
there is a color paper-processing agent made by Hunt Co. (processing agent
CP-LR) (specially described in Photographic Bulletin, No. 49 (published by
Hunt Co.), p. 6, in the item of "Color Print Chemistries"), and processes
are described in "Preliminary Text for the Meeting of the Photographic
Society of Japan, A-7", "Reduction in the amount of replenisher in color
paper processing" (1980), etc. Additionally, the former processing agent
enables reduction in the amount of replenishing color developer 1/2 to
2/3.
However, since these are agents for processing color papers, they cannot be
applied as such to color photographic materials for photographing use in
view of the problems with respect to photographic properties such as
sensitivity, gradation, color reproduction, etc.
In processing color negative-working films, the aforesaid processing agent
made by Hunt Co. (described in Photographic Bulletin, No. 55 published by
Hunt Co.) has a formulation of replenishing in an amount as low as 754 ml
per m.sup.2. However, it is still insufficient with respect to processing
stability.
This may be attributed to the fact that, as a problem peculiar to color
photographic materials for photographing use, a development inhibitor
released after a coupling reaction from a DIR (development
inhibitor-releasing) type coupler which is often used for improving
interlayer effect and sharpness dissolves into and accumulates in the
developer.
It is, therefore, a primary object of the present invention to provide a
process for processing silver halide color photographic materials for
photographing use without causing the problem with photographic properties
such as desensitization in the case of reducing the amount of replenishing
developer.
On the other hand, fundamental steps of color light-sensitive materials are
generally a developing step and a silver-removing step. In the
color-developing step, exposed silver halide is reduced with a
color-developing agent to produce silver and, at the same time, the
oxidized color-developing agent in turn reacts with a color former
(coupler) to give a dye image. In the subsequent silver-removing step,
silver having been produced in the color-developing step is oxidized by
the action of an oxidant (called bleaching agent), then dissolved with a
silver ion-chelating agent usually called a fixing agent. After this
silver-removing step, only a dye image is formed in the color
light-sensitive material.
The above-described silver-removing step is conducted in two manners: one
being conducted using two baths of a bleaching agent-containing bleaching
bath and a fixing agent-containing bath; and the other being conducted
using a mono-bath of a bleach-fixing bath containing both a bleaching
agent and a fixing agent.
In addition to the above-described fundamental steps, actual development
processing involves various auxiliary steps such as a hardening bath, a
stopping bath, an image-stabilizing bath, a water-washing bath, etc., for
the purpose of keeping the photographic and physical quality of the image,
or for impoving preservability of the image.
In general, red pressiate, dichromates, ferric chloride, ferric
aminopolycarboxylate complex salts, persulfates, etc., are known as the
bleaching agents.
However, red prussiate and dichromates involve the environmental pollution
problem with respect to cyan compounds and hexavalent chromium, and
require special processing equipment. Ferric chloride involves the problem
of production of ferric hydroxide in the subsequent water-washing step and
the problem of forming stains, thus involving various difficulties in
practical use. Persulfates have the defect that they possess such a weak
bleaching effect that they require a seriously long bleaching time. As to
this defect, it has been proposed to enhance the bleaching effect by using
together a bleaching accelerator. However, persulfates themselves are
regulated by the law of the prevention and extinction of fire which
provides persulfates and dangerous substances, and require various
measures for storage, thus being generally difficult to use.
Ferric aminopolycarboxylate complex salts (particularly ferric
ethylenediaminetetraacetate complex salts or ferric
diethylenetriaminepentaacetate complex salts) are at present most widely
used as bleaching agents since they cause less environmental problems and
can be stored with no trouble which is different from persulfates.
However, the bleaching power of the ferric aminopolycarboxylate complex
salts is not necessarily sufficient. When they are used as bleaching
agents, the desired purpose can be attained to some extent in the case of
bleaching or bleach-fixing low speed silver halide color light-sensitive
materials primarily containing a silver chlorobromide emulsion, but there
results insufficient removal of silver, or a long bleaching time is
required in the case of bleaching or bleach-fixing high speed
color-sensitized color light-sensitized materials primarily containing a
silver chlorobromoiodide or silver bromoiodide emulsion, particularly
color reversal light-sensitive materials and color negative
light-sensitive materials for photographing using high silver content
emulsions.
For example, in bleach-fixing color negative-working light-sensitive
materials for photographing use using a bleaching solution containing
ferric aminopolycarboxylate complex salt, bleaching must be conducted for
at least four minutes and, in order to keep the bleaching powder,
complicated control such as control of pH of the bleaching solution and
controlled aeration are required. In fact, such control still often fails
to prevent bleaching failure.
Further, in order to remove silver, a processing using a fixing solution
for at least 3 minutes is required subsequent to the bleaching processing.
It has been eagerly desired to shorten the long time required for the
silver-removing processing.
On the other hand, as a means for accelerating the silver-removing step, a
bleach-fixing solution containing a ferric aminopolycarboxylate complex
salt and a thiosulfate as described in German Pat. No. 866,605 is known.
However, when allowed to be copresent with the thiosulfate having a
reducing power, the ferric aminopolycarboxylate originally having a weak
oxidizing (bleaching) powder undergoes such a serious reduction of
bleaching power that it is extremely difficult to fully remove silver from
a high-speed, high-silver content color light-sensitive material for
photographing use, thus such means cannot be put into practice. Of course,
various attempts have so far been made to remove the above-described
effects of the bleach-fixing solution. For example, there is a technique
of adding an iodide or bromide as described in British Pat. No. 926,569
and Japanese Patent Publication No. 11854/78 and a technique of
incorporating a ferric aminopolycarboxylate complex salt in a high
concentration with the aid of triethanolamine as described in Japanese
Patent Application (OPI) Nos. 192953/82 and 95834/73 (the term "OPI" as
used herein means an "unexamined published patent application") and U.S.
Pat. No. 4,552,834. However, these techniques provide still insufficient
effects, and cannot be practically employed with sufficient effects.
In addition to the problem of insufficient silver-removing power, the
bleach-fixing solution involves a serious problem of spoiling color
reproduction by reducing a cyan dye once formed by the color developement
to a leuco dye. This problem is known to be solved by raising the pH of
the bleach-fixing solution as is described in U.S. Pat. No. 3,773,510.
However, a raised pH further weakens the bleaching power, and thus cannot
be employed. U.S. Pat. No. 3,189,452 discloses a process of oxidizing,
after the processing in the bleach-fixing solution, the leuco dye to the
former cyan dye by using a bleaching solution containing red prussiate.
However, the use of red prussiate involves the problem of environmental
pollution as has been described hereinbefore and, even when bleaching is
further conducted after the bleach-fixing processing, the amount of
remaining silver is scarcely decreased.
As another technique for raising the bleaching power of ferric
aminopolycarboxylate complex salt, it has been proposed to add various
bleaching accelerators to a bleaching bath, a bleach-fixing bath, or a
pre-bath thereof.
As the bleaching accelerators, there are illustrated, for example, various
mercapto compounds as described in U.S. Pat. No. 3,893,858, British Pat.
No. 1,138,842, and Japanese Patent Application (OPI) No. 141623/78,
disulfide bond-containing compounds described in Japanese Patent
Application (OPI) No. 98630/78, thiazolidine derivatives as described in
Japanese Patent Publication No. 9854/78, isothiourea derivatives as
described in Japanese Patent Application (OPI) No. 94927/78, thiourea
derivatives as described in Japanese Patent Publication Nos. 8506/70 and
26586/74, thioamide compounds as described in Japanese Patent Application
(OPI) No. 42349/74, dithiocarbamic acid salts as described in Japanese
Patent Application (OPI) No. 26506/80, etc.
Some of these accelerators show a bleaching-acclerating effect to some
extent, but the effect is not necessarily sufficient. Thus, they fail to
meet the requirement for shortening the processing time.
SUMMARY OF THE INVENTION
As a result of intensive investigations for attaining the above-described
objects, the inventors have found that it is important to control the
hydrolysis rate of a development inhibitor released and dissolved from a
DIR coupler into a color developer, thus having completed the present
invention.
(1) A process for processing a DIR coupler-containing silver halide color
photographic material for photographing use in a continuous manner with
replenishment of a developer, in which said DIR coupler is a coupler which
has in a coupling active site a group that functions as a development
inhibitor or a precursor thereof upon being eliminated from the coupling
active site by color development processing and that will be decomposed to
a compound exerting substantially no influence on photographic properties
after flowing into a color developer, said development inhibitor having a
half-value period of 4 hours or shorter at a pH of 10.0, and in which
process the developer is replenished in an amount of 700 ml or less per
m.sup.2 of light-sensitive materials developed.
(2) A process for processing a DIR coupler-containing silver halide color
photographic material for photographing use in a continuous manner with
replenishment of a developer, in which said DIR coupler is a coupler which
has in a coupling active site a group that functions as a development
inhibitor or a precursor thereof upon being eliminated from the coupling
active site by color development processing and that will be decomposed to
a compound exerting substantially no influences on photographic properties
after flowing into a color developer, said development inhibitor having a
half-value period of 4 hours or shorter at a pH of 10.0, and which process
is conducted in the presence of a compound or compounds represented by the
following general formula (I) and/or (II):
##STR1##
In the above general formula (I), A represents an n-valent aliphatic,
aromatic or heterocyclic linking group (provided that when n=1, A
represents a mere aliphatic, aromatic or heterocyclic group).
As the aliphatic linking group represented by A, there are illustrated
alkylene groups containing 3 to 12 carbon atoms (e.g., a trimethylene
group, a hexamethylene group, a cyclohexylene group, etc.).
As the aromatic linking group, there are illustrated 5- or 6-membered
arylene groups containing 6 to 18 carbon atoms (e.g., a phenylene group, a
naphthylene group, etc.).
As the heterocyclic linking group, there are illustrated heterocyclic
groups containing one or more hetero atoms (e.g., a thienyl group, a furyl
group, a thiazinyl group, a pyridyl group, a piperidyl group, etc.).
Usually, one aliphatic, aromatic or heterocyclic group is present, but two
or more of them may be linked to each other directly or through a divalent
linking group (e.g.,
##STR2##
or a linking group formed by these linking groups, with R.sup.5
representing a lower alkyl group having 1 to 10 carbon atoms).
These aliphatic, aromatic, and heterocyclic groups may have substituents.
Examples of such substituents include an alkoxy group having 1 to 10
carbon atoms, a halogen atoms, an alkyl group having 1 to 10 carbon atoms,
a hydroxyl group, a carboxy group, a sulfo group, a sulfonamido group, a
sulfamoyl group, etc. X represents
##STR3##
(wherein R.sup.4 represents a lower alkyl group having 1 to 6 carbon atoms
such as a methyl group, an ethyl group, etc.).
R.sup.1 and R.sup.2 each represents a substituted or unsubstituted lower
alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl
group, a propyl group, an isopropyl group, a pentyl group, etc.). As the
substituents thereof, a hydroxy group, a lower alkoxy group having 1 to 6
carbon atoms (e.g., a methoxy group, a methoxyethoxy group, a
hydroxyethoxy group, etc.), an amino group (e.g., an unsubstituted amino
group, a dimethylamino group, an N-hydroxyethyl-N-methylamino group, etc.)
are preferable. Where two or more substituents exist, they may be the same
or different.
R.sup.3 represents a lower alkylene group containing 1 to 5 carbon atoms
(e.g., a methylene group, an ethylene group, a trimethylene group, a
methylmethylene group, etc.).
Y represents an anion (a halide ion such as chloride ion or bromide ion, a
nitrate ion, a sulfate ion, a p-toluenesulfonate ion, an oxalate ion,
etc.).
R.sup.1 and R.sup.2 may be taken together through a carbon atom or a hetero
atom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom, etc.) to form
a 5- or 6-membered hetero ring (e.g., a pyrrolidine ring, a piperidine
ring, a morpholine ring, a triazine ring, an imidazoline ring, etc.).
R.sup.1 (or R.sup.2) and A may be taken together through a carbon atom or a
hetero atom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom, etc.)
to form a 5- or 6-membered hetero ring (e.g., a hydroxyquionline ring, a
hydroxyindole ring, an isoindoline ring, etc.). Further, R.sup.1 (or
R.sup.2) and R.sup.3 may be taken together through a carbon atom or a
hetero atom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom, etc.)
to form a 5- or 6-membered hetero ring (e.g., a piperidine ring, a
pyrrolidine ring, a morpholine ring, etc.).
l represents 0 or 1, m represents 0 or 1, n represents 1, 2 or 3, p
represents 0 or 1, and q represents 0, 1, 2 or 3.
Specific compounds within the scope of the present invention are
illustrated below which, however, do not limit the present invention in
any way.
##STR4##
Compounds of the general formula (I) can be synthesized by the well known
processes described in the following literature: U.S. Pat. No. 4,552,834,
Japanese Patent Publication No. 12056/79, and Japanese Patent Application
(OPI) No. 192953/82.
##STR5##
In the above general formula (II), R.sub.11 and R.sub.12, which may be the
same or different, each represents a hydrogen atom, a substituted or
unsubstituted lower alkyl group (preferably containing 1 to 5 carbon
atoms; particularly a methyl group, an ethyl group or a propyl group) or
an acyl group containing preferably 1 to 3 carbon atoms (e.g., an acetyl
group, a propionyl group, etc.), and r represents an integer of 1 to 3.
R.sub.11 and R.sub.12 may be taken together through a carbon atom or a
hetero atom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom, etc.)
to form a 5- or 6-membered hetero ring (e.g., a piperidine ring, a
pyrrolidine ring, a morpholine ring, etc.).
As R.sub.11 and R.sub.12, substituted or unsubstituted lower alkyl groups
are particularly preferable.
Examples of the substituents R.sub.11 and R.sub.12 include a hydroxyl
group, a carboxy group, a sulfo group, an amino group, etc.
Specific examples of the compounds represented by the general formula (II)
are illustrated below which, however, do npot limit the present invention
in any way.
##STR6##
Compounds of the general formula (II) can be synthesized by the method
described in Japanese Patent Application (OPI) No. 95630/78.
(3) A process for processing a DIR coupler-containing silver halide color
photographic material for photographing use in a continuous manner with
replenishment of a developer, in which said DIR coupler is a coupler which
has in a coupling active site a group that functions as a development
inhibitor or a precursor thereof upon eliminated from the coupling active
site by color development processing and that will be decomposed of a
compound exerting substantially no influences on photographic properties
after flowing into a color developer, said development inhibitor having a
half-value period of 4 hours or shorter at a pH of 10.0, and in which
process the light-sensitive material is processed, after the color
development, in a bleaching solution having a pH of 5.7 or less.
(4) The process for processing a silver halide photographic material as
described in (2) above, wherein the photographic material is processes, in
a silver-removing step, in a bath having a bleach-fixing ability or in a
bleaching bath and a subsequent bath having a bleach-fixing ability.
(5) The process for processig a silver halide photographic material as
described in (2) above, wherein a bleaching bath having a pH of 5.7 or
less is provided in a silver-removing step.
(6) The process for processing a silver halide photographic material as
described in (1) above, which is conducted in the presence of at least one
of the compounds represented by the general formula (I) and/or (II) as
described above.
(7) The process for preparing a silver halide photographic material as
described in (6) above, wherein said photographic material is processed,
in the silver-removing step, in a bath having a bleach-fixing ability or
in a bleaching bath and a subsequent bath having a bleach-fixing ability.
(8) The process for processing a silver halide photographic material as
described in (7) above, wherein said bleaching solution has a pH of 5.7 or
less.
The objects of the present invention can be attained by the above-described
processes.
DETAILED DESCRIPTION OF THE INVENTION
With the recent increase in demand for high quality of light-sensitive
materials, DIR couplers have become more important, and the amounts
thereof to be added to light-sensitive materials have been increases.
On the other hand, the detrimental influence of development inhibitors
releases from DIR couplers has been overlooked as a cause of deteriorating
silver-removing properties accompanying shortening of the processing time.
The inventors have found that development inhibitors released from DIR
couplers are the main cause of deterioration of silver-removing properties
encountered when silver-removing steps are shortened.
As a result of further investigation, the inventors have found that
silver-removing properties can be greatly improved by using a silver
removal-accelerating agent together with the DIR coupler and decreasing
the pH of the bleaching solution, thus having completed the present
invention.
The present invention enables attainment of the objects of reducing the
amount of reducing the amount of replenishing developer and shortening the
time for the silver-removing steps, which have been required for
photographic processing.
The DIR couplers to be used in the present invention are couplers which
have, in a coupling-active site, a group that comes a
development-inhibiting compound (a development inhibitor or a precursor
thereof) when released from the active site of the coupler by color
development reaction and that will be decomposed, after flowing into a
color developer, to a compound which exerts substantially no photographic
influences. In addition, the development inhibitor must have a definite
decomposition rate constant. That is, the development inhibitor must have
a half-value period of not longer than 4 hours, preferably not longer than
2 hours, more preferably not longer than 1 hour.
The half-value period of the development inhibitor or a precursor thereof
is measured according to the following method. That is, a sample
development inhibitor is added to a developer of the following formulation
in a concentration of 1.times.10.sup.-4 mol/liter and, after keeping the
solution at 38.degree. C., the concentration of the remaining development
inhibitor is measured by liquid chromatography.
Diethylenetriaminepentaacetic acid 0.8 g
1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 g
Sodium sulfite 4.0 g
Potassium carbonate 30.0 g
Potassium bromide 1.4 g
Potassium iodide 1.3 mg
Hydroxylamine sulfate 2.4 g
4-(N-Ethyl-N-.beta.-hydroxyethylamino)-2-methylaniline sulfate 4.5 g
Water to make 1 liter
pH 10.0
The half-value period greatly varies depending upon pH of the developer
used. therefore, the amount of remaining development inhibitor can be
controlled by controlling the pH of a developer upon development
processing.
The equilibrium concentration (x) of the development inhibitor in a running
state in the case of using the DIR coupler having the above-described
hydrolysis elimination group can be represented by the following
differential equation:
dx=[a-(v+kV)x]dt
k: decomposition rate constant
V: volume of developing tank
a: amount of dissolved development inhibitor
v: replenishing amount
t: time
To solve this equation, let dx/dt=0, X=a/(v+kV). Thus, equilibrium
concentration of the development inhibitor, x, depends upon the amount of
dissolved development inhibitor, a, and the decomposition rate constant,
k.
As the hydrolysis type DIR couplers to be used in the present invention,
any of those which have a half-value period of the above-described length
may be used. More particularly, there are illustrated hydrolysis type DIR
couplers represented by the following general formula (I'):
A--(L.sub.1).sub.a --Z--(L.sub.2 --Y).sub.b --].sub.m
wherein:
A represents a coupler component;
Z represents a fundamental portion of a compound which shows
development-inhibiting action, and is bound to the coupling site of a
coupler directly (a--0) or through a linking group, L.sub.1 (a=1);
Y represents a substituent bond to Z through a linking group L.sub.2 to
allow the development-inhibiting effect of Z to | | |
