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Claims  |
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What is claimed is:
1. A method for processing a silver halide color photographic material
which comprises, after color development of an imagewise exposed silver
halide color photographic material, processing the developed silver halide
color photographic material by subjecting the developed silver halide
color photographic material to a desilvering step, said desilvering step
having a processing time of 1 to 4 minutes, said desilvering step
including processing the developed silver halide color photographic
material with a bleaching solution having a pH of from 5.3 to 2, wherein
the silver halide color photographic material contains at least one DIR
coupler having at its coupling active position a group which forms a
development inhibitor or precursor thereof when released from the coupling
active position of the coupler upon a coupling reaction with an oxidation
product of an aromatic primary amine color developing agent which is
formed upon a color development reaction, and further decomposes into a
compound having substantially no effect on photographic properties once
discharged into a color developing solution wherein the half-life period
of the development inhibitor or precursor thereof at pH 10.0 is not more
than 4 hours, and wherein the bleaching solution contains, as a bleaching
agent, a ferric complex salt of 1,3-diaminopropanetetraacetic acid.
2. A method for processing a silver halide color photographic material as
in claim 1, wherein said bleaching solution contains, as bleaching agents,
a ferric complex salt of 1,3-diaminopropanetetraacetic acid and at least
one ferric complex salt of a compound selected from the group consisting
of Compounds (A) in a molar ratio of the latter to the former being not
more than 3:
Compounds (A)
A-1:Ethylenediaminetetraaceetic acid
A-2:Dithylenetriaminepentaacetic acid
A-3:Cyclohexanediaminetetraacetic acid
A-4:1,2-Propylenediaminetetraacetic acid.
3. A method for processing a silver halide color photographic material as
in claim 2, wherein said molar ratio is 0.2 to 2.0.
4. A method for processing a silver halide color photographic material as
in claim 1, wherein the half-life period of the development inhibitor or
precursor thereof at pH of 10.0 is 2 hours or less.
5. A method for processing a silver halide color photographic material as
in claim 4, wherein the half-life period of the development inhibitor or
precursor thereof at a pH of 10.0 is 1 hour or less.
6. A method for processing a silver halide color photographic material as
in claim 1, wherein the DIR coupler is represented by the general formula
(I)
A--(L.sub.1).sub.a --Z--L.sub.2 --Y.sub.b ].sub.m (I)
wherein A represents a coupler residue; Z represents a fundamental portion
of a compound having a development inhibiting function which is connected
directly (when a is 0) or through a linking group L.sub.1 (when a is 1) to
the coupling position of the coupler; Y represents a substituent connected
to Z through linking group L.sub.2 to allow the development-inhibiting
function of Z to emerge; L.sub.1 represents a linking group; L.sub.2
represents a linking group including a chemical bond which is cleaved in a
developing solution; a represents the integer 0 or 1; b represents the
integer 1 or 2, and when b represents 2, the two --L.sub.2 --Y groups may
be the same or different; and m represents the integer 1 or 2.
7. A method for processing a silver halide color photographic material as
claimed in claim 6, wherein the coupler residue represented by A is a
coupler residue derived from a yellow color image forming coupler, a
magenta color image forming coupler, a cyan color image forming coupler,
or a non-color image forming coupler.
8. A method for processing a silver halide color photographic material as
in claim 6, wherein the fundamental portion represented by Z is a divalent
nitrogen-containing heterocyclic group or a nitrogen-containing
heterocyclic thio group.
9. A method for processing a silver halide color photographic material as
in claim 8, wherein the nitrogen-containing heterocyclic thio group is a
tetrazolylthio group, a benzothiazolylthio group, a benzimidazolylthio
group, a triazolylthio group, or an imidazolylthio group.
10. A method for processing a silver halide color photographic material as
claimed in claim 6, wherein the DIR coupler is represented by one of the
following general formulae:
##STR26##
wherein A, L.sub.1, a, L.sub.2, Y, b and m each has the same meaning as
defined for the general formula (I); and X represents a hydrogen atom, a
halogen atom, an alkyl group, an alkenyl group, an alkanamido group, an
alkenamido group, an alkoxy group, a sulfonamido group, or an aryl group.
11. A method for processing a silver halide color photographic material as
in claim 6, wherein the substituent represented by Y is an alkyl group, an
alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group.
12. A method for processing a silver halide color photographic material as
in claim 6, wherein the DIR coupler is represented by one of the following
general formulae:
##STR27##
wherein R.sub.21 represents a hydrogen atom, a halogen atom, an alkyl
group, an alkenyl group, an aralkyl group, an alkoxy group, an
alkoxycarbonyl group, an anilino group, an acylamino, a ureido group, a
cyano group, a nitro group, a sulfonamido group, a sulfamoyl group, a
carbamoyl group, an aryl group, a carboxy group, a sulfo group, a
cycloalkyl group, an alkanesulfonyl group, an arylsulfonyl group, or an
acyl group; R.sub.22 represents a hydrogen atom, an alkyl group, an
alkenyl group, an aralkyl group, a cycloalkyl group or an aryl group; c
represents an integer from 0 to 2; b and l each represent the integer 1 or
2, and when l represents the integer 2, two R.sub.21 groups may be bonded
to each other to form a condensed ring.
13. A method for processing a silver halide color photographic material as
in claim 6, wherein the moiety forming the linking group represented by
L.sub.2 is --COO--, --NHCOO--, --SO.sub.2 O--, --OCH.sub.2 CH.sub.2
SO.sub.2 --,
##STR28##
or
##STR29##
14. A method for processing a silver halide color photographic material as
in claim 6, wherein the linking group represented by L.sub.2 and the
bonding thereof to Z and Y is represented by one of the following general
formulae:
##STR30##
wherein d represents an integer from 0 to 10; W.sub.1 represents a
hydrogen atom, a halogen atom, an alkyl group having from 1 to 10 carbon
atoms, an alkanamido group having from 1 to 10 carbon atoms, an alkoxy
group having from 1 to 10 carbon atoms, an alkoxycarbonyl group having
from 2 to 10 carbon atoms, an aryloxycarbonyl group having from 6 to 22
carbon atoms, an alkanesulfonamido group having from 1 to 10 carbon atoms,
an aryl group having from 6 to 22 carbon atoms, a carbamoyl group, an
N-alkylcarbamoyl group having from 1 to 10 carbon atoms, a nitro group, a
cyano group, an arylsulfonamido group having from 6 to 10 carbon atoms, a
sulfamoyl group or an imido group; W.sub.2 represents a hydrogen atom, an
alkyl group having from 1 to 6 carbon atoms, an aryl group having from 6
to 22 carbon atoms or an alkenyl group having from 2 to 10 carbon atoms;
W3 represents a hydrogen atom, a halogen atom, a nitro group, an alkoxy
group having from 1 to 6 carbon atoms or an alkyl group having from 1 to 6
carbon atoms; and p represents an integer of from 0 to 6.
15. A method for processing a silver halide color photographic material as
in claim 6, wherein the DIR coupler is represented by the following
general formula (II), (III), (IV), (V), (VI), (VII), or (VIII)
##STR31##
wherein A, L.sub.2, and Y each has the same meaning as defined for the
general formula (I); A.sub.1 represents a coupler residue as defined for A
in the general formula (I), excluding cyan color image forming coupler
residues; A.sub.2 represents a cyan color image forming coupler residue of
the coupler residues as defined for A in the general formula (I); X
represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl
group, an alkanamido group, an alkenamido group, an alkoxy group, a
sulfonamido group, or an aryl group; R.sub.21 represents a hydrogen atom,
a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an
alkoxy group, an alkoxycarbonyl group, an anilino group, an acylamino
group, a ureido group, a cyano group, a nitro group, a sulfonamido group,
a sulfamoyl group, a carbamoyl group, an aryl group, a carboxy group, a
sulfo group, a cycloalkyl group, an alkanesulfonyl group, an arylsulfonyl
group or an acyl group; R.sub.22 represents a hydrogen atom, an alkyl
group, an alkenyl group, an aralkyl group, a cycloalkyl group or an aryl
group; l represents the integer of 1 to 4 and when l represents the
integer Of 2 or more, the R.sub.21 grOups may be bonded to each other to
form a condensed ring.
16. A method for processing silver halide color photographic material as in
claim 2, wherein the bleaching solution further contains an
aminopolycarboxylic acid.
17. A method for processing a silver halide color photographic material as
in claim 2, wherein the bleaching solution further contains a bleach
accelerating agent.
18. A method for processing a silver halide color photographic material as
in claim 17, wherein the bleach accelerating agent is a compound
represented by the following general formula (IA), (IIA), (IIIA), (IVA),
(VA) or (VIA):
R.sup.1A --S--M.sup.1A (IA)
wherein M.sup.1A represents a hydrogen atom, an alkali metal atom or an
ammonium: and R.sup.1A represents an alkyl group, an alkylene group, an
aryl group or a heterocyclic group,
R.sup.1A --S--S--R.sup.6A (IIA)
wherein R.sup.1A is same as R.sup.1A defined in the general formula (IA);
R.sup.6 A has the same meaning as R.sup.1A defined in the general formula
(IA); and R.sup.1A and R.sup.6A may be the same or different,
##STR32##
wherein R.sup.10A and R.sup.11A, which may be the same or different, each
represents a hydrogen atom, a substituted or unsubstituted alkyl group, a
substituted or unsubstituted phenyl group or a substituted or
unsubstituted heterocyclic group; R.sup.12A represents a hydrogen atom or
a substituted or unsubstituted lower alkyl group; and R.sup.13A represents
a hydrogen atom an alkyl group or a carbonyl group,
##STR33##
wherein R.sup.14A, R.sup.15A and R.sup.16A, which may be the same or
different, each represents a hydrogen atom or a lower alkyl group or
R.sup.14A and R.sup.15A or R.sup.16A may be bonded to each other to form a
ring; X.sup.1A represents a substituted or unsubstituted amino group, a
sulfo group, a hydroxy group, a carboxy group or a hydrogen atom; and kB
represents an integer from 1 to 5,
##STR34##
wherein A.sup.1A represents an n-valent aliphatic linking group, an
n-valent aromatic linking group or an n-valent heterocyclic linking group
(when n is 1, A.sup.1A represents an aliphatic group, an aromatic group or
a heterocyclic group); X.sup.2A represents --O--, --S--or
##STR35##
wherein R.sup.21A represents a lower alkyl group; R.sup.17A and R.sup.18A,
which may be the same or different, each represents a substituted or
unsubstituted lower alkyl group, or R.sup.17A and R.sup.18A may be
connected with each other through a carbon atom or a hetero atom to form a
5-membered or 6-membered heterocyclic ring; R.sup.19A represents a lower
alkylene group having from 1 to 5 carbon atoms; Z.sup.2A represents an
anion; R.sup.17A or R.sup.18A and A.sup.1A may be connected with each
other through a carbon atom or a hetero atom to form a 5-membered or
6-membered heterocyclic ring; R.sup.17A or R.sup.18A and R.sup.19A may be
connected with each other through a carbon atom or a hetero atom to form a
5-membered or 6-membered heterocyclic ring; lA represents 0 or 1; mA
represents 0 or 1; nA represents 1, 2 or 3; pA represents 0 or 1; and qA
represents 0, 1, 2 or 3,
##STR36##
wherein X.sup.1A and kB are same as X.sup.1A and kB defined in general
formula (IVA) respectively; M.sup.2A represents a hydrogen atom, an alkali
metal atom, ammonium or
##STR37##
R.sup.22A represents a hydrogen atom or a substituted or unsubstituted
lower alkyl group.
19. A method for processing a silver halide color photographic material as
in claim 18, wherein the bleach accelerating agent is a compound
represented by the following general formulae (IA-1), (IA-2), (IA-3) or
(IA-4):
##STR38##
wherein R.sup.2A, R.sup.3A and R.sup.4A, which may be the same or
different, each represents a hydrogen atom, a substituted or unsubstituted
lower alkyl group or an acyl group, or R.sup.2A and R.sup.3A may be bonded
to each other to form a ring; kA represents an integer from 1 to 3;
Z.sup.1A represents an anion; hA represents the integer 0 or 1; and iA
represents the integer 0 or 1,
##STR39##
wherein R.sup.5A represents a hydrogen atom, an amino group, a substituted
or unsubstituted lower alkyl group, an amino group substituted with an
alkyl group or a substituted or unsubstituted alkylthio group.
20. A method for processing a silver halide color photographic material as
in claim 18, wherein the bleach accelerating agent is a compound
represented by the following general formula (IIA-1):
##STR40##
wherein R.sup.7A, R.sup.8A and R.sup.9A each has the same meaning as
R.sup.2A, R.sup.3A and R.sup.4A defined in the general formula (IA-1); hA,
kA and Z.sup.1A are same as hA, kA and Z.sup.1A defined in the general
formula (IA-1) respectively; and iB represents the integer 0, 1 or 2.
21. A method for processing a silver halide color photographic material as
in claim 1, wherein the bleaching solution has a pH of 2.0 to 5.0.
22. A method for processing a silver halide color photographic material as
in claim 1, wherein the processing time for the desilvering step is 1.5 to
3 minutes.
23. A method for processing a silver halide color photographic material as
in claim 2, wherein compound (A) is A-1. |
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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 an exposed silver
halide color photographic material (hereinafter referred simply to as a
color light-sensitive material) which comprises developing, bleaching, and
fixing (hereinafter referred simply to as a processing method), and more
particularly, to an improved processing method which accelerates the
bleaching function, thus shortening the processing time while conducting
sufficient bleaching, thus providing a color photographic image of good
image quality.
BACKGROUND OF THE INVENTION
The fundamental steps of processing color light-sensitive materials
generally include a color developing step and a silver removing step.
Thus, an exposed silver halide color photographic material is introduced
into a color developing step, where silver halide is reduced with a color
developing agent to produce silver and the oxidized color developing agent
in turn reacts with a color former (a color coupler) in situ to form a dye
intermediate (a leuco dye). Subsequently, the color photographic material
having the silver and the dye intermediate imagewise distributed therein
is introduced into a silver removing step, where the silver produced in
the preceding step is oxidized with an oxidizing agent (usually called a
bleaching agent) and dissolved away with a silver ion complexing agent
usually called a fixing agent, and at the same time, the dye intermediate
in the color photographic material is oxidized with the oxidizing agent to
provide a dye image. As a result, only the dye image is formed in the
processed photographic material. In addition to the above described two
fundamental steps of color development and silver removal, actual
development processing involves auxiliary steps for maintaining the
photographic and physical quality of the resulting image or for improving
the preservability of the image. For example, these auxiliary steps may
include a hardening bath for preventing a light-sensitive layer from being
excessively softened during photographic processing, a stopping bath for
effectively stopping the developing reaction, an image stabilizing bath
for stabilizing the image, and a layer removing bath for removing the
backing layer on the support.
The above described silver removal step may be conducted in two ways: the
first uses two steps individually employing a bleaching bath and a fixing
bath; and the second is more simple and is conducted in one step employing
a bleach-fixing bath containing both a bleaching agent and a fixing agent
to accelerate processing and reduce labor.
In recent years, bleach processing using a ferric ion complex salt (e.g.,
aminopolycarboxylic acid ferric ion complex salt, particularly iron (III)
ethylenediaminetetraacetate complex salt) as a major bleaching component
has mainly been employed in the processing of color photographic
light-sensitive materials in view of the acceleration and simplification
of the bleaching provided thereby and environmental factors.
However, ferric ion complex salts have a comparatively low oxidizing power
and, therefore, have insufficient bleaching power. A bleaching or
bleach-fixing solution containing such a complex salt as a bleaching agent
can attain some desirable objects when bleaching or bleach-fixing a low
speed silver halide color photographic light-sensitive material
containing, e.g., a silver chlorobromide emulsion as a major component.
However, such a solution provides insufficient silver removal due to
insufficient bleaching power or requires an unacceptably long time to
bleach when processing a high speed, spectrally sensitized silver halide
color photographicmaterial containing a silver chlorobromoiodide emulsion
or a silver iodobromide emulsion as a major component. This is
particularly true for color reversal light-sensitive materials or color
negative light-sensitive materials for photographing which comprise an
emulsion containing larger amounts of silver.
In color light-sensitive materials, sensitizing dyes are generally employed
for the purpose of spectral sensitization. In particular, when a silver
halide emulsion containing a large amount of silver or tabular grains
having a high aspect ratio is employed in order to achieve high
sensitivity, a problem occurs in that sensitizing dyes adsorbed on the
surfaces of silver halide grains interfere with the bleaching of silver
formed by development of the silver halide.
Bleaching agents other than ferric ion complex salts include persulfates.
Persulfates are usually used in a bleaching solution together with a
chloride. However, this persulfate-containing bleaching solution has less
bleaching ability than ferric ion complex salts, thus requiring a
substantially longer period of time for bleaching.
Bleaching agents which do not cause environmental pollution or corrode
vessels and apparatus typically have weak bleaching power. Hence, it is
desirable to enhance the bleaching power of a bleaching solution or a
bleach-fixing solution containing a bleaching agent having a weak
bleaching power, particularly when the bleaching agent comprises a ferric
ion complex salt or a persulfate.
In order to accelerate bleaching, processing methods wherein two or more
kinds of aminopolycarboxylic acid ferric complex salts are employed in
combination are described, e.g., in Research Disclosure No. 24033 (April
1984), and in JP-A-60-230653 (the term "JP-A" as used herein means an
"unexamined published Japanese patent application"). However, these
methods are also inadequate for obtaining a satisfactorily high bleach
accelerating effect.
Recently, the importance of using DIR couplers increases, as higher image
quality light-sensitive materials are desired. Also, the amount of DIR
couplers being added to light-sensitive materials has increased.
On the other hand, it is known that development inhibitors released from
DIR couplers adversely affect desilvering and cause insufficient silver
removal when the processing time is shortened. In order to solve this
problem, a method is described in JP-A-62-148951 wherein the desilvering
property is improved by using a DIR coupler which releases a development
inhibitor which further decomposes into a compound having substantially no
effect on photographic properties once entered into a color developing
solution. However, improvement in the desilvering property using the above
described method is inadequate, and furthermore causes the cyan density,
particularly the high density portion thereof to decrease due to inferior
coloring resulted from insufficient oxidation of the dye intermediates in
the processed photographic material during the bleaching step.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to provide a processing
method for desilveration which provides good quality photographic images
without the occurrence of inferior coloring.
Another object of the present invention is to provide a processing method
which is both rapid and has an excellent desilvering property.
Other objects of the present invention will become apparent from the
following description and examples.
As a result of extensive investigations to solve the above described
problems, it has been found that the inferior coloring described above is
prevented by processing color light-sensitive materials containing a
hydrolyzable type DIR coupler with a processing solution containing a
specific bleaching agent thus accomplishing the present invention.
More specifically, the objects of the present invention are accomplished by
a method for processing a silver halide color photographic material which
comprises, after color development of an imagewise exposed silver halide
color photographic material, processing the developed silver halide color
photographic material with a processing solution and having a bleaching
ability, wherein the silver halide color photographic light-sensitive
material contains at least one DIR coupler having at its coupling active
position a group which forms a development inhibitor or precursor thereof
when released from the coupling active position of the coupler upon a
coupling reaction with an oxidation product of an aromatic primary amine
color developing agent which is formed upon a color development reaction,
and further decomposes into a compound having substantially no effect on
photographic properties once discharged into a color developing solution
wherein the half-life period of the development inhibitor or precursor
thereof at pH 10.0 is not more than 4 hours, and wherein the processing
solution having a bleaching ability contains, as bleaching agents, a
ferric complex salt of 1,3-diaminopropanetetraacetic acid and has a pH of
from 5.8 to 1.5.
DETAILED DESCRIPTION OF THE INVENTION
The DIR coupler for use in the present invention is a coupler having at its
coupling active position a group which forms a compound having a
development inhibiting function (i.e., a development inhibitor) or
precursor thereof when released from the coupling active position of the
coupler upon a coupling reaction with the oxidized color developing agent
and which decomposes into a compound having substantially no effect on
photographic properties (i.e., no development-inhibiting effect) after
being discharged into a color developing solution. The development
inhibitor or precursor thereof is to have a certain decomposition rate
coefficient. More specifically, a half-life period of the development
inhibitor or precursor thereof at pH 10.0 is 4 hours or less, preferably 2
hours or less, and more preferably 1 hour or less.
The half-life period of the development inhibitor or precursor thereof in
the present invention is readily measured in the following manner. A
development inhibitor or precursor thereof to be measured is added to a
developing solution having the composition shown below in an amount of
1.times.10.sup.-4 mol/liter. The solution is maintained at 38.degree. C.
and the concentration of the remaining development inhibitor or precursor
thereof is determined by liquid chromatography at periodic intervals to
give the half-life period of the development inhibitor or precursor
thereof. The half-life period is the time required for the initial
inhibitor concentration to decrease by one-half.
Composition of Developing Solution
______________________________________
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)-
4.5 g
2-methylaniline sulfate
Water to make 1.0 l
pH 10.0
______________________________________
The half-life period of the development inhibitor or precursor thereof
varies depending on the pH of a developing solution used. More
specifically, as the pH increases, the half-life period decreases.
Therefore, the remaining amount of development inhibitor is controlled by
means of adjusting the pH of the developing solution used at development
processing.
The equilibrium concentration (x) of a development inhibitor in the
developing solution during continuous processing in case of using the
above-described DIR coupler having a hydrolyzable releasing group can be
represented by the following differential equation:
dx=[a-(v+kV)x]dt
wherein k represents the decomposition rate coefficient; V represents the
capacity of the developing tank; a represents the discharge amount of the
development inhibitor from the photographic material into a developing
solution; and v represents the amount of replenishment.
In the equation, when dx/dt is 0, x is a/(v+kV). Accordingly it can be seen
that the equilibrium concentration (x) of development inhibitor depends on
the discharge amount of the development inhibitor (a) and the
decomposition rate coefficient (k).
Any hydrolyzable type DIR coupler which satisfies the half life period
condition described above can be employed in the present invention. More
specifically, hydrolyzable type DIR couplers represented by the following
general formula (I) can be used.
A--(L.sub.1).sub.a --Z--L.sub.2 --Y).sub.b ].sub.m (I)
wherein A represents a coupler residue; Z represents a fundamental portion
of a compound having a development-inhibiting function which is connected
directly (when a is 0) or through linking group L.sub.1 (when a is 1) with
the coupling position of the coupler; Y represents a substituent connected
with Z through linking group L.sub.2 to allow the development-inhibiting
function of Z to emerge; L.sub.1 represents a linking group; L2 represents
a linking group including a chemical bond which is cleaved in a developing
solution; a represents the integer of 0 or 1; b represents the integer of
1 or 2, when b represents 2, the two --L.sub.2 --Y groups may be the same
or different; and m represents the integer of 1 or 2.
The compound represented by the general formula (I) may release either
.sup..crclbar. Z--L.sub.2 --Y).sub.b or L.sup..crclbar..sub.1 --Z--L.sub.2
--Y).sub.b after the coupling reaction with an oxidation product of a
color developing agent. The latter changes immediately into .sup..crclbar.
Z--L.sub.2 --Y).sub.b by releasing L.sub.1. The moiety .sup..crclbar.
Z--L.sub.2 --Y).sub.b diffuses in the light-sensitive layer while exerting
the development inhibiting function and a part thereof enters into the
color developing solution. The .sup..crclbar. Z--L.sub.2 --Y).sub.b having
entered into the color developing solution rapidly decomposes at the
chemical bonds of L.sub.2 ; that is, the connection between Z and Y is
cleaved, whereby a compound which has no development-inhibiting function
and which has a water-soluble group in Z remains in the color developing
solution, and the development-inhibiting function is thus terminated.
As a result, compounds having a development inhibiting function are not
accumulated in a processing solution, and thus it becomes possible not
only to repeatedly reuse the processing solution, but also to incorporate
a sufficient amount of DIR couplers into the light-sensitive material.
Hydrolyzable type DIR couplers represented by the general formula (I) are
described in more detail below.
Preferred examples of yellow color image forming coupler residues
represented by A include those of pivaloyl acetanilide type, benzoyl
acetanilide type, malonic diester type, malondiamide type,
dibenzoylmethane type, benzothiazolyl acetamide type, malonic ester
monoamide type, benzothiazolyl acetate type, benzoxazolyl acetamide type,
benzoxazolyl acetate type, benzimidazolyl acetamide type and
benzimidazolyl acetate type; the coupler residues derived from hetero
ring-substituted acetamides or hetero ring-substituted acetates as
described in U.S. Pat. No. 3,841,880; the coupler residues derived from
the acyl acetamides as described in U.S. Pat. No. 3,770,446, British
Patent 1,459,171, West German Patent Application (OLS) No. 2,503,099,
JP-A-50-l39738 and Research Disclosure, No. 15737; and the hetero ring
type coupler residues as described in U.S. Pat. No. 4,046,574, etc.
Preferred examples of magenta color image forming coupler residues
represented by A include those of 5-oxo-2-pyrazoline type,
pyrazolo[1,5-a]benzimidazole type and cyanoacetophenone type; and coupler
residues having a pyrazolotriazole nucleus, etc.
Preferred examples of cyan color image forming coupler residues represented
by A include those having a phenol nucleus or an .alpha.-naphthol nucleus.
Further, DIR couplers are also employed which release a development
inhibitor upon coupling with an oxidation product of a developing agent
but do not form a dye. Suitable examples of such coupler residues
represented by A include the coupler residues as described in U.S. Pat.
Nos. 4,052,213, 4,088,491, 3,632,345, 3,958,993, and 3,961,959, etc.
The fundamental portion of a development inhibitor represented by Z
includes a divalent nitrogen-containing heterocyclic group or
nitrogen-containing thio group. Suitable examples of heterocyclic thio
groups include a tetrazolylthio group, a benzothiazolylthio group, a
benzimidazolylthio group, a triazolylthio group, and an imidazolylthio
group, etc. Suitable examples of Z are set forth below, including showing
the positions of substitution of the A--L.sub.1 --.sub.a group and the
--L.sub.2 --Y).sub.b group.
##STR1##
In the above formulae, the substituent represented by X is included in a
portion represented by Z in the general formula (I), and represents a
hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms
(e.g., methyl, ethyl, propyl, isopropyl, pentyl), an alkenyl group having
2 to 10 carbon atoms (e.g., vinyl, allyl), an alkanamindo group having 1
to 10 carbon atoms (e.g., methanamido, ethanamido), an alkenamido group
having 2 to 10 carbon atoms (e.g., ethanamido), an alkoxy group having 1
to 10 carbon atoms (e.g., methoxy, ethoxy, propoxy), a sulfonamido group
having 1 to 10 carbon atoms (e.g., methanesulfonamido, ethanesulfonamido)
or an aryl group having 6 to 10 carbon atoms (e.g., phenyl).
Examples of the group represented by Y in the general formula (I) include
an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl,
isopropyl, pentyl), a cycloalkyl group having 3 to 10 carbon atoms (e.g.,
cyclopentyl, cyclohexyl), an alkenyl group having 2 to 10 carbon atoms
(e.g., vinyl, allyl), a cycloalkenyl group having 3 to 10 carbon atoms
(e.g., cyclopentenyl, cyclohexenyl), an aryl group having 6 to 10 carbon
atoms (e.g., phenyl), an aralkyl group having 7 to 10 carbon atoms (e.g.,
benzyl, phenethyl), or a 5-or 6-membered heterocyclic group containing an
oxygen atom, a nitrogen atom or a sulfur atom as a hetero atom (e.g.,
phridyl).
Suitable examples of the linking group represented by L.sub.1 in the
general formula (I) are set forth below, together with the groups A-- and
--Z--(L.sub.2 --Y).sub.b.
A--OCH.sub.2 --Z--(L.sub.2 --Y).sub.b ].sub.m
(a linking group as described in U.S. Pat. No. 4,146,396)
##STR2##
(a linking group as described in West German Patent Application (OLS) No.
2,626,315)
##STR3##
(a linking group as described in West German Patent Application (OLS) No.
2,855,697; c represents an integer from 0 to 2)
##STR4##
In the above formulae, R.sub.21 represents a hydrogen atom, a halogen atom,
an alkyl group having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl,
isopropyl, pentyl), an alkenyl group having 2 to 6 carbon atoms (e.g.,
vinyl, allyl), an aralkyl group having 7 to 10 carbon atoms (e.g., benzyl,
phenethyl), an alkoxy group having 1 to 6 carbon atoms (e.g., methoxy,
ethoxy, pentyloxy), an alkoxycarbonyl group having 2 to 7 carbon atoms
(e.g., methylcarbonyl, ethylcarbonyl), an anilino group, an acylamino
group having 1 to 6 carbon atoms (e.g., acetylamino), a ureido group
having up to 6 carbon atoms (e.g., ureido, methylureido), a cyano group, a
nitro group, a sulfonamido group having up to 6 carbon atoms (e.g.,
sulfonamido, methanesulfonamido, ethansulfonamido), a sulfamoyl group up
to 6 carbon atoms (e.g, sulfamoyl, methylsulfamoyl), a carbamoyl group
having 1 to 6 carbon atoms (e.g., carbamoyl, methylcarbamoyl), an aryl
group having 6 to 10 carbon atoms (e.g., phenyl), a carboxy group, a sulfo
group, a cycloalkyl group having 3 to 6 carbon atoms (e.g., cyclopentyl,
cyclohexyl), an alkanesulfonyl group having 1 to 6 carbon atoms (e.g.,
methanesulfonyl), an arylsulfonyl group having 6 to 10 carbon atoms (e.g.,
phenylsulfonyl) or an acyl group having 1 to 6 carbon atoms (e.g.,
acetyl),
R.sub.22 represents a hydrogen atom, an alkyl group having 1 to 6 carbon
atoms (e.g., methyl, ethyl), an alkenyl group having 2 to 7 carbon atoms
(e.g., vinyl, allyl), an aralkyl group having 7 to 10 carbon atoms (e.g.,
benzyl, phenetyl), a cycloalkyl group having 3 to 6 carbon atoms (e.g.,
cyclopentyl, cyclohexyl) or an aryl group having 6 to 10 carbon atoms
(e.g., phenyl), and
b and l each represents 1 or 2 and, when l represents 2, R.sub.21 's may be
bound to each other to form a fused ring.
With these DIR couplers (i.e., cases wherein a represents 1 in the general
formula (I)), a releasing group released upon the reaction with an
oxidation product of a developing agent decomposes immediately and leases
a development inhibitor [H--Z--(L.sub.2 --Y).sub.b ]. These re couplers
have the same effect in accordance with the present invention as DIR
couplers which do not contain the group represented by L.sub.1 (i.e.,
cases wherein "a" represents 0 in the general formula (I)).
The linking group represented by L.sub.2 in the general formula (I)
includes a chemical bond which is cleaved in a developing solution.
Suitable examples of such chemical bonds include those described in the
table below. These chemical bonds are cleaved with a nucleophilic reagent
such as a hydroxy ion or a hydroxylamine, etc., which is a component of
the color developing solution of the present invention. The desired effect
of the present invention is thereby attained.
TABLE
______________________________________
Chemical Bond Cleavage Reaction of Chemical
Included in L.sub.2
Bond (Reaction with .sup..crclbar. OH)
______________________________________
COO COOH + HO
##STR5## NH.sub.2 + HO + CO.sub.2
SO.sub.2 O SO.sub.3 H + HO
OCH.sub.2 CH.sub.2 SO.sub.2
OH + CH.sub.2CHSO.sub.2
##STR6## OH + HO + CO.sub.2
##STR7## NH.sub.2 + HO + 2CO.sub.2
______________________________________
The divalent linking group shown in the above table is linked to Z directly
or through an alkylene group having 1 to 6 carbon atoms (e.g., ethylene)
and/or a phenylene group, whereas it is linked directly to Y. In the case
of the divalent linking group being linked to Z through an alkylene group
or a phenylene group, the divalent alkylene or phenylene group may contain
an ether bond, an amido bond, a carbonyl bond, a thioether bond, a sulfon
group, a sulfonamido bond, and a urea bond.
Preferred examples of the linking group represented by L.sub.2 and the
bonding thereof to Z and Y are set forth below.
##STR8##
In the above described formulae, d represents an integer from 0 to 10,
preferably from 0 to 5; W.sub.1 represents a hydrogen atom, a halogen
atom, an alkyl group having from 1 to 10, preferably from 1 to 5 carbon
atoms, an alkanamido group having from 1 to 10, preferably from 1 to 5
carbon atoms, an alkoxy group having from 1 to 10, preferably from 1 to 5
carbon atoms, an alkoxycarbonyl group having from 2 to 10, preferably
from 2 to 5 carbon atoms, an aryloxycarbonyl group having from 6 to 22,
preferably from 6 to 10 carbon atoms, an alkanesulfonamido group having
from 1 to 10, preferably from 1 to 5 carbon atoms, an aryl group having
from 6 to 22, preferably from 6 to 10 carbon atoms, a carbamoyl group, an
N-alkylcarbamoyl group having from 1 to 10, preferably from 1 to 5 carbon
atoms, a nitro group, a cyano group, an arylsulfonamido group having from
6 to 10 carbon atoms, a sulfamoyl group or an imido group; W.sub.2
represents a hydrogen atom, an alkyl group having from 1 to 6 carbon
atoms, an aryl group having from 6 to 22, preferably from 6 to 10 carbon
atoms or an alkenyl group having from 2 to 10, preferably from 2 to 5
carbon atoms; W.sub.3 represents a hydrogen atom, a halogen atom, a nitro
group, an alkoxy group having from 1 to 6 carbon atoms or an alkyl group
having from 1 to 6 carbon atoms; and p represents an integer from 0 to 6.
The alkyl group or the alkenyl group represented by X or Y specifically
represents a straight chain, branched chain or cyclic alkyl group or
alkenyl group having from 1 to 10, preferably from 1 to 5 carbon atoms
(e.g., methyl, ethyl, propenyl, etc.), and preferably has a substituent.
Examples of the substituents include a halogen atom, a nitro group, an
alkoxy group having from 1 to 4 carbon atoms, an aryloxy group having from
6 to 10 carbon atoms, an alkanesulfonyl group having from 1 to 4 carbon
atoms, an arylsulfonyl group having from 6 to 10 carbon atoms, an
alkanamido group having from 1 to 5 carbon atoms, an anilino group, a
benzamido group, a carbamoyl group, a carbamoyl group substituted with an
alkyl group having from 1 to 6 carbon atoms, a carbamoyl group substituted
with an aryl group having from 6 to 10 carbon atoms, an alkylsulfonamido
group having from 1 to 4 carbon atoms, an arylsulfonamido group having
from 6 to 10 carbon atoms, an alkylthio group having from 1 to 4 carbon
atoms, an arylthio group having from 6 to 10 carbon atoms, a phthalimido
group, a succinimido group, an imidazolyl group, a 1,2,4-triazolyl group,
a pyrazolyl group, a benzotriazolyl group, a furyl group, a benzothiazolyl
group, an alkylamino group having from 1 to 4 carbon atoms, an alkanoyl
group having from 1 to 4 carbon atoms, a benzoyl group, an alkanoyloxy
group having from 1 to 4 carbon atoms, a benzoyloxy group, a
perfluoroalkyl group having from 1 to 4 carbon atoms, a cyano group, a
tetrazolyl group, a hydroxy group, a carboxy group, a mercapto group, a
sulfo group, an amino group, an alkylsulfamoyl group having from 1 to 4
carbon atoms, an arylsulfamoyl group having from 6 to 10 carbon atoms, a
morpholino group, an aryl group having from 6 to 10 carbon atoms, a
pyrrolidinyl group, a ureido group, a urethane group, a carbonyl group
substituted with an alkoxy group having from 1 to 6 carbon atoms, a
carbonyl group substituted with an aryloxy group having from 6 to 10
carbon atoms, an imidazolidinyl group or an alkylidenamino group having
from 1 to 6 carbon atoms, etc. Specific examples of the substituent
include chlorine atom, methoxy, methylsulfonyl, phenylsulfonyl,
methanamido, isopropylcarbamoyl, etc.
The alkanamido group or the alkenamido group represented by X specifically
represents a straight chain, branched chain or cyclic alkanamido or
alkenamido group having from 1 to 10, and preferably from 1 to 5 carbon
atoms which may be substituted. Examples of the substituents are selected
from the substituents as defined for the above described alkyl group or
alkenyl group, etc. Specific examples of the alkanamido or alkenamido
group represented by X include methanamido, propenamido, etc.
The alkoxy group represented by X specifically represents a straight chain,
branched chain or cyclic alkoxy group having from 1 to 10, and preferably
from 1 to 5 carbon atoms which may be substituted. Examples of the
substituents are selected from the substituents as defined for the above
described alkyl group or alkenyl group, etc. Specific examples of the
alkoxy group represented by X include ethoxy.
The aryl group represented by X or Y specifically represents a phenyl group
or a naphthyl group which may be substituted. Examples of the substituents
are selected from the substituents as defined for the above described
alkyl group or alkenyl group and an alkyl group having from 1 to 4 carbon
atoms (e.g., methyl, ethyl) and the like.
The heterocyclic group represented by Y include a diazolyl group (e.g.,
2-imidazolyl, or 4-pyrazolyl), a triazolyl group (e.g.,
1,2,4-triazol-3-yl), a thiazolyl group (e.g., 2-benzothiazolyl), an
oxazolyl group (e.g., 1,3-oxazol-2-yl), a pyrrolyl group, a pyridyl group,
a diazinyl group (e.g., 1,4-diazin-2-yl), a triazinyl group (e.g.,
1,2,4-triazin-5-yl), a furyl group, a diazolinyl group (e.g.,
imidazolin-2-yl), a pyrrolinyl group, or a thienyl group, etc.
Of the couplers represented by the general formula (I), preferred couplers
are those represented by the general formula (II), (III), (IV), (V), (VI),
(VII) or (VIII) shown below. These couplers are preferred since the
development inhibiting function of the development inhibitor released
therefrom is particularly str | | |
