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Description  |
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FIELD OF THE INVENTION
This invention concerns silver halide color photographic materials and the
processing characteristics thereof, and mover precisely it concerns
photosensitive materials and methods of processing which provide excellent
sharpness and a shorter bleaching time.
BACKGROUND OF THE INVENTION
Technological progress has been made with the latest color photographic
materials and processing methods with a view to improving picture quality
and to simplifying and speeding up processing as in the case of
mini-laboratories.
In connection with the improvement of picture quality, the importance of
the so-called DIR couplers as disclosed in U.S. Pat. Nos. 3,227,554,
3,701,783, 3,615,506, and 3,617,291, etc., for improving sharpness is well
known. Thus a high degree of sharpness is obtained when DIR couplers
containing timing groups as disclosed in Japanese Patent Application (OPI)
No. 145,135/79 (the term "OPI" refers to an "unexamined Japanese patent
application which has been opened for public inspection" are used, but
there are problems with the stability, etc., of these compounds and they
cannot be said to be ideal.
Furthermore the timing type DIR couplers disclosed in Japanese Patent
Application (OPI) Nos. 114,946/81 (corresponding to U.S. Pat. No.
4,409,323), 98,728/83, 209,738/83, 209,739/83 and 209,740/83 are better
with respect to the weakness mentioned above, but when they are used the
de-silvering operation during processing is slow and it is clear that
sufficient time must be allowed for de-silvering especially in the case of
an oxidation process for reduced silver using a bleach.
On the other hand the use of bleach acceleration agent releasing type
couplers in silver halide color photographic materials has been disclosed
in Research Disclosure, 1973, Item No. 11449 and in Japanese Patent
Application (OPI) No. 201,247/86 (corresponding to U.S. patent application
Ser. No. 707,115).
The bleach accelerating agents which are formed by the eliminated groups of
these bleach accelerating agent releasing type couplers have some effect
under conditions where the developer bath has not yet been used, but there
is some deterioration of the bleach accelerating effect under normal
running conditions where developer, etc., is carried over into the bleach
bath or bleach-fix bath.
Hence the development of a novel method which enables the de-silvering
process time to be shortened even under normal running conditions when
processing photosensitive materials of which the sharpness has been
improved using DIR couplers is clearly desirable.
SUMMARY OF THE INVENTION
Hence the first aim of the invention is to provide color photographic
materials which have a high level of sharpness and with which the
de-silvering process can be executed in a short period of time.
The second aim of the invention is to provide silver halide color
photographic materials in which timing type DIR couplers are used and
which have excellent de-silvering properties even under running
conditions.
The problems mentioned above are overcome by the present invention
indicated below:
A silver halide color photographic material comprising at least one silver
halide emulsion layer on a support and containing at least one type of
development inhibitor releasing type coupler which, by means of a coupling
reaction with the oxidized form of a primary aromatic amine developing
agent, releases a precursor of a compound, the precursor inhibiting the
development of silver halide which subsequently, by means of an electron
transfer reaction via an ethylenic conjugated chain, releases a compound
which inhibits the development of silver halide, and at least one type of
bleach accelerating agent releasing type coupler which, by means of a
coupling reaction with the oxidized form of a primary aromatic amine
developing agent, release a bleach accelerating agent or a precursor
thereof.
DETAILED DESCRIPTION OF THE INVENTION
In the silver halide color photographic material of this invention the
aforementioned bleach accelerating agent releasing type coupler can be
represented by the general formula [I], [II], [III] or [IV] are shown
below.
General Formula [I]
A--(Time).sub.n --S--R.sub.1 --R.sub.2
General Formula [II]
##STR1##
General Formula [III] A--(Time).sub.n --S--R.sub.4 (R.sub.3).sub.m
General Formula [IV]
##STR2##
In these general formulae [I]-[IV] A represents the coupler residual group,
TIME represents a timing group, n is an integer of value 0 or 1, Z.sub.1,
Z.sub.2 and Z.sub.3 each independently represent a nitrogen atom or a
methine group, Z.sub.4 represents an oxygen atom, sulfur atom or an imino
group, Z.sub.5, Z.sub.6, Z.sub.7, Z.sub.8 and Z.sub.9 each independently
represent a nitrogen atom or a methine group (except that at least one of
Z.sub.5, Z.sub.6, Z.sub.7, Z.sub.8 and Z.sub.9 represents a nitrogen
atom), R.sub.1 represents a divalent aliphatic group which has from 1 to 8
carbon atoms (but excluding alicyclic groups or an aromatic group which
has from 6 to 10 carbon atoms, R.sub.2 represents a water soluble
substituent group, R.sub.3 represents a water soluble substituent group, m
is an integer from 0 to 2 and R.sub.4 is an alicyclic group which has from
3 to 10 carbon atoms or a saturated heterocyclic group which has from 3 to
10 carbon atoms.
In this invention, the aliphatic groups may be saturated or unsaturated,
substituted or unsubstituted and they may have linear chains, branched
chains. Typical examples include a methyl group, an ethyl group, a butyl
group, an allyl group, a propargyl group, a methoxyethyl group, a n-decyl
group, a n-dodecyl group, a n-hexadecyl group, a trifluoromethyl group, a
heptafluoropropyl group, a dodecyloxypropyl group, a
2,4-di-tert-amylphenoxypropyl group, a 2,4-di-tert-amylphenoxybutyl group
etc.
Furthermore, the alicyclic groups may be saturated or unsaturated and may
be substituted or unsubstituted. A typical examples includes a cyclohexyl
group.
Furthermore, the aromatic groups may also be either substituted or
unsubstituted groups and typical examples include a phenyl group, a tolyl
group, a 2-tetradecyloxyphenyl group, a pentafluorophenyl group, a
2-chloro-5-dodecyloxycarbonylphenyl group, a 4-chlorophenyl group, a
4-cyanophenyl group, a 4-hydroxyphenyl group, etc.
Furthermore, the heterocyclic groups may also be either substituted or
unsubstituted groups and typical examples include a 2-pyridyl group, a
4-pyridyl group, a 2-furyl group, a 4-thienyl group, a quinolinyl group,
etc.
The development inhibitor releasing type couplers which release by means of
a coupling reaction with the oxidized form of a primary aromatic amine
developing agent the precursors of compounds which inhibit the development
of the silver halide and the precursors subsequently by means of an
intramolecular electron transfer reaction via an ethylenic conjugated
chain release compounds which inhibit the development of the silver halide
which are used in the present invention are described in detail below.
The development inhibitor releasing type couplers used in the present
invention can be represented by the general formula [V] shown below.
General Formula [V]
##STR3##
In this formula A' represents a coupler residual group which release the
remaining section of the molecule including Q on undergoing a coupling
reaction with the oxidized form of a primary aromatic amine developing
agent, Q represents an oxygen atom, sulfur atom or a substituted imino
group, L represents a vinylene group, l is an integer of value 1 or 2,
R.sub.5 and R.sub.6 each independently represent a hydrogen atom, an alkyl
group or an aryl group and W represents a component (compound) which
inhibits the development of silver halide. Furthermore, when l is 2 the
two vinylene groups may be the same or different. The vinylene groups
represented by L are preferably structural elements of a benzene ring or a
heterocyclic ring.
Furthermore, when Q represents a substituted imino group the substituent is
preferably linked with L and forms together with the nitrogen atom and L a
five to seven membered nitrogen-containing ring.
Moreover, of the compounds which can be represented by the general formula
[V] those which can be represented by the general formulae [VI]-[IX] shown
below are preferred.
General Formula [VI]
##STR4##
General Formula [VII]
##STR5##
General Formula [VIII]
##STR6##
General Formula [IX]
##STR7##
In the general formula [V] to [IX], A', R.sub.5, R.sub.6 and W have the
same significance as A', R.sub.5, R.sub.6 and W in general formula [V] and
V.sub.1 and V.sub.2 represent the non-metallic atomic groups which are
required to form, along with the linked atomic groups, a five to seven
membered nitrogen-containing heterocyclic ring (which may have
substituents or which may take the form of a condensed ring system) and
V.sub.3 represents the non-metallic atomic group which is required to
form, along with the linked atomic groups, a five to seven membered
heterocyclic ring (which may have substituents or which may take the form
of a condensed ring system) or a benzene ring (which may have substituents
or which may take the form of a condensed ring system), Z represents a
substituted or unsubstituted methine group or a nitrogen atom, R.sub.7
represents a hydrogen atom or a univalent group and R.sub.15 and R.sub.16
each independently represent a univalent group. However R.sub.7 may be
linked to V.sub.2 to form a ring.
A', R.sub.5, R.sub.6, R.sub.7, R.sub.15, R.sub.16, Z and W in the general
formulae [V]-[IX] are described in detail below. The coupler residual
group which is represented by A' may be a yellow image forming coupler, a
magenta image forming coupler, a cyan image forming coupler or a so-called
colorless coupler, such that the product of the coupling reaction is
essentially colorless etc.
The yellow image forming coupler residual group which is represented by A'
may, for example, be a coupler residual group of the pivaloylacetanilide
type, the benzoylacetanilide type, the malonic diester type, malonic
diamide type, the dibenzoylmethane type, the benzothiazolylacetamide type,
the malonic ester monoamide type, the benzothiazolylacetate type, the
benzoxazolylacetamide type, the benzoxazolylacetate type, the malonic
diester type, the benzimidazolylacetamide type or the
benzimidazolylacetate type; a coupler residual group derived from a
heterocyclic substituted acetamide or a heterocyclic substituted acetate
as included in U.S. Pat. No. 3,841,880, a coupler derived from the
acylacetamides disclosed in U.S. Pat. No. 3,770,446, British Patent No.
1,459,171, West German Patent (OLS) No. 2,503,009, Japanese Patent
Application (OPI) No. 139,738/75 and Research Disclosure No. 15737 or a
heterocyclic type coupler residual group as disclosed in U.S. Pat. No.
4,046,574.
The magenta image forming coupler residual group represented by A' is
preferably a coupler residual group which has a 5-oxo-2-pyrazoline
nucleus, a pyrazolo-[1,5-a]benzimidazole nucleus, a pyrazoloimidazole
nucleus, a pyrazolotriazole nucleus, a pyrazolotetrazole nucleus or a
cyanoacetophenone type coupler residual group.
The cyan image forming coupler residual group represented by A' is
preferably a coupler residual group which has a phenol nucleus or an
.alpha.-naphthol nucleus.
Moreover, couplers which couple with the oxidized form of the developing
agent and release a development inhibitor, but which in essence do not
subsequently form a dye have the same effect as a DIR coupler. Examples of
coupler residual groups of this type which can be represented by A'
include those which are disclosed in U.S. Pat. Nos. 4,052,213, 4,088,491,
3,632,345, 3,958,993 and 3,961,959.
Examples of the preferred coupler residual groups which can be represented
by A' are represented by the general formulae (Cp-1)-(Cp-9) which will be
described later.
R.sub.5 and R.sub.6 each independently represent a hydrogen atom, an alkyl
group which has from 1 to 36 carbon atoms (for example, a methyl group, an
ethyl group, a benzyl group, a dodecyl group, a cyclohexyl group, etc.) or
an aryl group which has from 6 to 36 carbon atoms (for example, a phenyl
group, a 4-methoxyphenyl group, a 4-chlorophenyl group, a 4-nitrophenyl
group, a naphthyl group, etc.), but they preferably represent hydrogen
atoms.
R.sub.7 represents a group which can link with V.sub.2 and the groups
indicated by R.sub.5 and R.sub.6 to form a benzene ring or a five to seven
membered heterocyclic ring (for example a pyrrole, a pyrazole, a
1,2,3-triazole, a pyridine, a pyridazine, a pyrimidine, a thiophene or
furan ring, etc.)
R.sub.15 and R.sub.16 each independently represent a hydrogen atom, an
aliphatic group which has from 1 to 30 carbon atoms (for example, a methyl
group, an ethyl group, an n-undecyl group, etc.), an alicyclic group which
has from 3 to 30 carbon atoms, an aromatic group which has from 6 to 30
carbon atoms (for example, a phenyl group, a p-tolyl group, a 1-naphthyl
group, a p-nitrophenyl group, etc.), a halogen atom (for example a
fluorine atom, a chlorine atom, a bromine atom, etc.), a substituted or
unsubstituted aliphatic oxy group which has from 1 to 30 carbon atoms (for
example, a methoxy group, an ethoxy group, a benzyloxy group, a dedecyloxy
group, etc.), an unsubstituted or substituted amino group or cyclic imino
group which has from 0 to 36 carbon atoms (for example an amino group, a
dimethylamino group, a pyrrolidino group, a piperidino group, a morpholino
group, an anilino group, an n-dodecylamino group, an octadecylmethylamino
group, a 2-chloro-5-tetradecanamidophenylamino group, etc.), a nitro
group, a cyano group, a carboxyl group, a substituted or unsubstituted
carboxylamido group which has from 1 to 36 carbon atoms (for example, an
acetamido group, a benzamido group, a tetradecanamido group etc.) a
substituted or unsubstituted sulfonamido group which has from 1 to 36
carbon atoms (for example, a methylsulfonamido group, an
n-hexadecylsulfonamido group, a p-tolylsulfonamido group, etc.), or an
alkoxycarbonyl group which has from 2 to 36 carbon atoms (for example, a
methoxycarbonyl group, a dodecyloxycarbonyl group, etc.). R.sub.15 and
R.sub.16 are preferably hydrogen atoms, aliphatic group or alicyclic
groups.
Z represents a substituted or unsubstituted methine group or a nitrogen
atom and when Z represents a substituted methine group, the substituents
may be those cited as examples of the substituents for R.sub.15 and
R.sub.16.
W may be a triazolyl group, a tetrazoyl group, a 1,3,4-oxadiazol-2-yltho
group, a 1,3,4-thiadiazol-2-ylthio group, a 1-indazolyl group, a
1-benzimidazolyl group, a 1-benzotriazolyl group, a 2-benzotrriazolyl
group, a 2-benzimidazolylthio group, a 2-benzoxazolylthio group, a
2-benzothiazolylthio group, a 2-pyrimidylthio group, a 2-pyridylthio
group, a 4-quinolylthio group, a 1,3,5-triazin-2-ylthio group, a
2-imidazolylthio group, a 1,2,4-triazol-5-ylthio group, a
1,3,4-triazol-2-ylthio group, a 1,2,3,4-tetrazol-5-ylthio group, etc., and
these groups may have substituent groups. The preferred groups for W are
1,2,3,4-tetrazol-5-ylthio groups, 1,3,4-oxadiazol-2-ylthio groups,
1,3,4-thiadiazol-2-ylthio groups, 1-benzotriazolyl groups,
2-benzothiazolylthio groups, 2-benzoxazolylthio groups,
1,3,4-triazol-2-ylthio groups and 2-pyrimidylthio groups, and the more
desirable groups are those which can be represented by the general
formulae [X]-[XVII] shown below.
##STR8##
In the general formulae [X]-[XVII], R.sub.8 represents a substituted or
unsubstituted alkyl group which has from 1 to 16 carbon atoms (for
example, a methyl group, an ethyl group, a hexyl group, a benzyl group, an
octyl group, etc.) or a substituted or unsubstituted aryl group which has
from 6 to 24 carbon atoms (for example, a phenyl group, a 4-hydroxyphenyl
group, a 3-hydroxyphenyl group, a 3-sulfamoylphenyl group, a
3-succinimidophenyl group, a 4-methylphenyl group, a 4-methoxyphenyl
group, a 3-nitrophenyl group, a 3-acetamidophenyl group, a
3-methylsulfonamidophenyl group, a 4-methoxycarbonylphenyl group, etc.).
R.sub.9 represents a hydrogen atom, a halogen atom, an amino group, a
substituted or unsubstituted alkyl group which has from 1 to 16 carbon
atoms (for example, a methyl group, an ethyl group, a hydroxyethyl group,
a methyoxyethyl group, a butyl group, etc.), a substituted or
unsubstituted aryl group which has from 6 to 24 carbon atoms (for example,
a phenyl group, a 4-methoxyphenyl group, a 4-chlorophenyl group, etc.), a
substituted or unsubstituted carboxylamido group which has from 1 to 24
carbon atoms (for example, an acetamido group, a benzamido group, etc.), a
substituted or unsubstituted alkylthio group which has from 1 to 16 carbon
atoms (for example, a methylthio group, an ethylthio group, a benzylthio
group, an octylthio group, a methoxycarbonylmethylthio group, etc.) a
substituted or unsubstituted arylthio group which has from 6 to 24 carbon
atoms (for example, a 4-acetamidophenylthio group, a
4-methylsulfonamidophenylthio group, etc.) or a substituted or
unsubstituted sulfonamido group which has from 1 to 24 carbon atoms (for
example, a methylsulfonamido group, a tolylsulfonamido group, an
octylsulfonamido group, etc.).
R.sub.10 represents a hydrogen atom, a halogen atom, a hydroxyl group, an
alkyl group which has from 1 to 16 carbon atoms (for example, a methyl
group, an ethyl group, a butyl group, etc.), a substituted or
unsubstituted alkoxy group which has from 1 to 16 carbon atoms (for
example, a methoxy group, an ethoxy group, a butoxy group, a methoxyethoxy
group, a benzyloxy group, etc.), a nitro group, a cyano group, an amino
group, a substituted or unsubstituted carboxylamido group which has from 1
to 24 carbon atoms (for example, an acetamido group, a benzamido group,
etc.), a substituted or unsubstituted sulfonamido group which has from 1
to 24 carbon atoms (for example, a methylsulfonamido group, a
phenylsulfonamido group, etc.), an alkoxycarbonyl group which has from 2
to 16 carbon atoms (for example, a methoxycarbonyl group, an
ethoxycarbonyl group, etc.), a substituted or unsubstituted
aryloxycarbonyl group which has from 6 to 16 carbon atoms (for example, a
phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, etc.), or a
substituted or unsubstituted sulfamoyl group which has from 0 to 16 carbon
atoms (for example, a sulfamoyl group, a dimethylsulfamoyl group, a
butylsulfamoyl group, etc.).
R.sub.11 and R.sub.12 represent hydrogen atoms hydroxyl groups, amino
groups, alkyl groups which have from 1 to 8 carbon atoms (for example,
methyl groups, ethyl groups, etc.), or alkoxy groups which have from 1 to
8 carbon atoms (for example, methoxy groups, ethoxy groups, methoxyethoxy
groups etc.).
Of the aforementioned compounds which can be represented by the general
formulae [VI]-[IX], those which can be represented by the general formula
[VIII] are preferred and of the compounds which can be represented by the
general formula [VIII], those which can be represented by the general
formula [VXIII] below are especially desirable.
##STR9##
In general formula [XVIII], A', R.sub.5, R.sub.6, and W are the same as A',
R.sub.5, R.sub.6 and W in the aforementioned general formula [V], R.sub.13
represents a substituted or unsubstituted alkyl group which has from 1 to
24 carbon atoms (for example, a methyl group, a benzyl group, a dodecyl
group, etc.) or a substituted or unsubstituted aryl group which has from 6
to 36 carbon atoms (for example, a phenyl group, a 4-tetradecyloxyphenyl
group, a 4-methoxyphenyl group, a 4-chlorophenyl group, a
2,5-dichlorophenyl group, a 4-methylphenyl group, a 4-nitrophenyl group,
etc.) and R.sub.14 represents a hydrogen atom, an alkyl group which has
from 1 to 24 carbon atoms (for example, methyl group, ethyl group, undecyl
group, etc.), a substituted or unsubstituted aryl group which has from 6
to 36 carbon atoms (for example, a phenyl group, a 4-methoxyphenyl group,
etc.), an alkoxy group which has from 1 to 24 carbon atoms (for example,
a methoxy group, ethoxy group, dodecyloxy group, etc.), a cyano group, a
substituted or unsubstituted amino group or cyclic imino group which has
from 0 to 36 carbon atoms (for example, an amino group, a dimethylamino
group, a piperidino group, a dihexylamino group, an anilino group, etc.),
a substituted or unsubstituted carboxylamido group which has from 1 to 24
carbon atoms (for example, an acetamido group, a benzamido group, a
tetradecanamino group, etc.), a substituted or unsubstituted sulfonamido
group which has from 1 to 24 carbon atoms (for example, a
methylsulfonamido group, a phenylsulfonamido group, etc.), a carboxyl
group, an alkoxycarbonyl group which has from 2 to 24 carbon atoms (for
example, a methoxycarbonyl group, dodecyloxycarbonyl group, etc.) or a
substituted or unsubstituted carbamoyl group which has from 1 to 24 carbon
atoms (for example, a carbamoyl group, a dimethylcarbamoyl group, a
pyrrolidinecarbamoyl group, etc.).
A' in general formula [XVIII] is preferably a cyan image forming coupler
residual group (for example, a phenol based cyan coupler residual group,
an .alpha.-naphthol based cyan coupler residual group, etc.), R.sub.5 and
R.sub.6 are preferably hydrogen atoms, R.sub.13 is preferably an aryl
group, R.sub.14 is preferably an alkyl group and W is preferably a group
which can be represented by the general formula [X], [XI] or [XII].
The bleach accelerating agent eliminating type couplers which can be used
in the present invention are described in detail below.
The term "bleach accelerating agent eliminating type coupler" signifies a
coupler which releases a bleach accelerating agent or a precursor thereof
by means of a coupling reaction with the oxidized form of a primary
aromatic amine developing agent and such couplers can be represented
typically by the general formula [I], [II], III] or [IV].
General Formula [I]
A--(Time).sub.n --S--R.sub.1 --R.sub.2
General Formula [II]
##STR10##
General Formula [III] A--(Time).sub.n --S--R.sub.4 (R.sub.3).sub.m
General FOrmula [IV]
##STR11##
In these general formulae [I]-[IV], A represents the coupler residual
group, TIME represents a timing group, n is an integer of value 0 or 1,
Z.sub.1, Z.sub.2 and Z.sub.3 each independently represent a nitrogen atom
or a methine group, Z.sub.4 represents, an oxygen atom, a sulfur atom, or
an imino group, Z.sub.5, Z.sub.6, Z.sub.7, Z.sub.8 and Z.sub.9 each
independently represent a nitrogen atom or a methine group (except that at
least one of Z.sub.5, Z.sub.6, Z.sub.7, Z.sub.8 and Z.sub.9 represents a
nitrogen atom), R.sub.1 represents a divalent aliphatic group which has
from 1 to 8 carbon atoms (but excluding alicylic groups) or an aromatic
group which has from 6 to 10 carbon atoms, R.sub.2 represents a water
soluble substituent group, R.sub.3 represents a water soluble substituent
group, m is an integer of value from 0 to 2 and R.sub.4 is an alicyclic
group which has from 3 to 10 carbon atoms or a saturated heterocyclic
group which has from 3 to 10 carbon atoms.
The bleach accelerating agent releasing couplers of general formulae
[I]-[IV] which are preferably used in the invention are described in
detail below.
In these formulae, the group represented by R.sub.2 preferably has not more
than 8 carbon atoms and contains at least one group from among carboxyl
groups, sulfo groups, hydroxyl group, and the substituted or unsubstituted
amino groups, acyl groups, alkoxy groups, acylamino groups, sulfonamido
groups, sulfamoyl groups, carbamoyl groups, ureido groups, alkylthio
groups or sulfonyl groups as substituent groups.
The most desirable of the substituent groups mentioned above include those
which have a n-substituent constant of less than 0.5 and which is
preferably negative. The n-substituent constant is the value calculated
for R.sub.2 using the method proposed by C. Hansch and A. Leo in
"Substituent Constants for Correlation Analysis in Chemistry and Biology",
published by John Wiley in 1979. Some of these values are indicated below.
--CONH.sub.2 (-1.49), --CO.sub.2 H (0.32), --COCH.sub.3 (-0.55),
--NHCOCH.sub.3 (-0.97), --CH.sub.2 CH.sub.2 CO.sub.2 H (-0.29), --CH.sub.2
CH.sub.2 NH.sub.2 (0.08), --SCH.sub.2 CO.sub.2 H (0.31),
##STR12##
(0.43), --CH.sub.2 CO.sub.2 H (0.68), --SCH.sub.2 CONH.sub.2 (-0.97),
##STR13##
(0.43), --SCH.sub.2 CH.sub.2 CO.sub.2 H (-0.01).
The aliphatic groups represented by R.sub.1 in the formulae has from 1 to 8
carbon atoms and may be saturated or unsaturated, have a linear or
branched chain and it may or may not have substituent groups. Typical
examples of substituent groups include those indicated for the group
represented by R.sub.2 and halogen atoms.
When R.sub.1 represents an aromatic group, it is preferably a substituted
or unsubstituted phenelene. Typical examples of substituent groups include
those indicated for the group indicated by R.sub.2 and halogen atoms.
R.sub.3 has the same significance as R.sub.2 which has been described
above. When m has a value of 2 the two R.sub.3 groups may be the same or
different or may be divalent groups which are joined together to form a
ring structure. Examples of divalent groups for forming ring structures
include the
##STR14##
group, for example.
When Z.sub.1, Z.sub.2, Z.sub.3, Z.sub.5, Z.sub.6, Z.sub.7, Z.sub.8 and
Z.sub.9 represent substituted or unsubstituted methine groups, the
unsubstituted groups are preferred, but typical examples of substitutents
include methyl groups, ethyl groups, halogen atoms etc.
When Z.sub.4 represents a substituted or unsubstituted imino group, then
aliphatic groups which have from 1 to 4 carbon atoms or phenyl groups are
typical substituents.
When both Z.sub.2 and Z.sub.3 represents a methine group, Z.sub.2 and
Z.sub.3 may contain a group which makes condensation ring (e.g., benzo,
pyrido) at this position. An example of such Z.sub.2 and Z.sub.3 includes,
e.g.,
##STR15##
Actual examples of the --S--R.sub.1 --R.sub.2 group in general formula [I]
are indicated below.
--SCH.sub.2 CH.sub.2 CO.sub.2 H, --SCH.sub.2 CO.sub.2 H,
##STR16##
--SCH.sub.2 CH.sub.2 NH.sub.2,
##STR17##
--S--CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH, --SCH.sub.2 CH.sub.2
NHCOCH.sub.3, --S(CH.sub.2).sub.4 CH.sub.2 H,
##STR18##
--SCH.sub.2 CONHCH.sub.2 CO.sub.2 H, --SCH.sub.2 CH.sub.2 OCH.sub.2
CH.sub.2 CO.sub.2 H, --SCH.sub.2 COOCH.sub.2 CH.sub.2 OH.
Actual examples of the group represented in general formula [II] by
##STR19##
are shown below.
##STR20##
Actual examples of the group represented in general formula [III] by
##STR21##
are indicated below.
##STR22##
Known coupler residual groups can be used for the group represented by A.
For example, A may represent a yellow coupler residual group (for example,
an open chain ketomethylene type coupler residual group, etc.), a magenta
coupler residual group (for example, a 5-pyrazolone type coupler residual
group, a pyrazoloimidazole type coupler residual group, or a
pyrazolotriazole type coupler residual group, etc.), a cyan coupler
residual group (for example, a phenol type coupler residual group or a
naphthol type coupler residual group, etc.) or a colorless coupler
residual group (for example, an indanone type coupler residual group or an
acetophenone type coupler residual group, etc.). Furthermore, it may also
take the form of a heterocyclic type coupler residual group as disclosed
in U.S. Pat. Nos. 4,315,070, 4,183,752, 3,961,959 or 4,171,223.
Preferred examples of A are those coupler residual groups which can be
represented by the general formulae (Cp-1), (Cp-2), (Cp-3), (Cp-4),
(Cp-5), (Cp-6), (Cp-7), (Cp-8), and (Cp-9) which are shown below. These
couplers have a high coupling rate and are preferred.
##STR23##
In these formulae, the free bond at the coupling position indicates the
bonding position of the group which is eliminated by the coupling
reaction.
In cases where the groups R.sub.51, R.sub.52, R.sub.53, R.sub.54, R.sub.55,
R.sub.56, R.sub.57, R.sub.58, R.sub.59, R.sub.60, R.sub.61, R.sub.62, and
R.sub.63 in the above mentioned formulae contain groups which are fast to
diffusion, they are selected in such a way that the total number of carbon
atoms is from 8 to 40 and preferably from 10 to 30 while in order cases
the total number of carbon atoms is preferably not more than 15. In the
case of bis type, telomer type and polymer type couplers, any of the above
mentioned substituents may take the form of a divalent group for
connecting the repeating units together, etc., in which case the number of
carbon atoms may be outside the range specified above.
The group R.sub.51 -R.sub.63, d and e are described in detail below. Here
R.sub.41 represents an aliphatic group, an alicyclic group, an aromatic
group or a heterocyclic group, R.sub.42 represents an aromatic group or a
heterocyclic group and R.sub.43, R.sub.44 and R.sub.45 represent hydrogen
atoms, aliphatic groups, aromatic groups or heteroxcyclic groups.
R.sub.51 has the same significance as R.sub.41. R.sub.52 and R.sub.53 both
have the same significance as R.sub.42. R.sub.54 is a group which has the
same significance as R.sub.41, an
##STR24##
group, an
##STR25##
an
##STR26##
an R.sub.41 S-- group, an R.sub.43 O-- group, an
##STR27##
an R.sub.41 OOC-- group, an
##STR28##
group or an N.dbd.C-- group.
R.sub.55 represents a group which has the same significance as R.sub.41.
R.sub.56 and R.sub.57 are each groups of the same significance as an
R.sub.43 group, R.sub.41 S-- groups, R.sub.43 O-- groups,
##STR29##
groups,
##STR30##
groups,
##STR31##
groups or
##STR32##
groups. R.sub.58 represents a group which has the same significance as
R.sub.41. R.sub.59 represents a group which has the same significance as
R.sub.41, an
##STR33##
group, an
##STR34##
an R.sub.41 O-- group, an R.sub.41 S-- group, a halogen atoms or an
##STR35##
group.
Moreover d represents 0-3.
When d is greater than 1, the plurality of R.sub.59 groups may represent
the same or different substituents. Furthermore, the R.sub.59 groups may
be divalent groups which are joined together to form a ring structure.
Examples of divalent groups for forming ring structures include
##STR36##
Here f is an inteqer of value 0 to 4 and g is an integer of value 0 to 2.
R.sub.60 represents a group which has the same significance as R.sub.41.
R.sub.61 represents a group which has the same significance as R.sub.41.
R.sub.62 represents a group which has the same significance as R.sub.41,
an R.sub.41 CONH-- group, an R.sub.41 OCONH-- group, an R.sub.41 SO.sub.2
NH-- group, an
##STR37##
group, an
##STR38##
group, an R.sub.43 O-- group, an R.sub.41 S-- group, a halogen atom or an
##STR39##
group. R.sub.63 represents a group of the same significance as R.sub.41,
an
##STR40##
group, an
##STR41##
group, an
##STR42##
group, an
##STR43##
group, an R.sub.41 SO.sub.2 -- group, an R.sub.43 OCO-- group, an R.sub.43
O--SO.sub.2 -- group, a halogen atom, a nitro group, a cyano group or an
R.sub.43 CO-- group. Moreover, e represents an integer of value 0 to 4.
When there is more than one R.sub.62 or R.sub.63 group these groups may be
the same or different.
In the description above, an aliphatic group is an aliphatic hydrocarbyl
group, which has from 1 to 32, and preferably from 1 to 22, carbon atoms,
which may be saturated or unsaturated, which may have a linear or branched
chain structure and which may or may not have substituent groups. Typical
examples include a methyl group, an ethyl group, a propyl group, an
isopropyl group, a butyl group, a tert-butyl group, an iso-butyl group, a
tert-amyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a
1,1,3,3-tetramethylbutyl group, a decyl group, a dodecyl group, a
hexadecyl group and an octadecyl group.
In the description above, an alicyclic group is an alicyclic hydrocarbyl
groups, which has from 3 to 32, and preferably from 3 to 22, carbon atoms,
which may be saturated or unsaturated and which may or may not have
substituent groups. A typical example includes a cyclohexyl group.
The aromatic groups are a group which have from 6 to 20 carbon atoms,
preferably substituted or unsubstituted phenyl groups or substituted or
unsubstituted naphthyl groups.
The heterocyclic groups are preferably three to eight membered substituted
or unsubstituted heterocyclic groups, which have atoms selected from among
nitrogen, oxygen and sulfur atoms as the hetero atoms and which have from
1 to 20, and preferably from 1 to 7, carbon atoms. Typical examples of
heterocyclic groups include the 2-pyridyl group, 4-pyridyl group,
2-thienyl group, 2-furyl group, 2-imidazolyl group, pyrazinyl group,
2-pyrimidyl group, 1 imidazolyl group, 1 indolyl group, phthalimido group,
1,3,4-thiadiazol 2-yl group, benzoxazol-2-yl group, 2-quinolyl group,
2,4-dioxo-1,3-imidazolidin-5-yl group, 2,4-dioxo-1,3-imidazolidin-3-yl
group, succinimido group, phthalimido group, 1,2,4-triazol-2-yl group and
1-pyrazolyl group.
Typical substituents in cases where the aforementioned aliphatic
hydrocarbyl groups, alicyclic hydrocarbyl groups, aromatic groups and
heterocyclic groups have substituents include halogen atoms, R.sub.47 O--
groups, R.sub.46 S-- groups,
##STR44##
groups,
##STR45##
groups,
##STR46##
groups,
##STR47##
groups,
##STR48##
groups, R.sub.46 SO.sub.2 -- groups, R.sub.47 OCO-- groups,
##STR49##
groups, groups represented by R.sub.46,
##STR50##
groups, R.sub.46 COO-- groups, R.sub.47 OSO.sub.2 -- groups, cyano groups
and nitro groups. Here, R.sub.46 represents an aliphatic group, an
aromatic group or a heterocyclic group and R.sub.47, R.sub.48 and R.sub.49
each represent aliphatic groups, aromatic groups, heterocyclic groups or
hydrogen atoms. The significance of the terms aliphatic group, aromatic
group and heterocyclic group as used here is the same as that defined
above.
The preferred scope of R.sub.51 -R.sub.63, d and e is described below.
R.sub.51 is preferably an aliphatic group or an aromatic group. R.sub.52,
R.sub.53 and R.sub.55 are preferably aromatic groups. R.sub.54 is
preferably an R.sub.41 CONH-- group or an
##STR51##
group. R.sub.56 and R.sub.57 are preferably aliphatic groups, R.sub.41 O--
groups or R.sub.41 S-- groups. R.sub.58 is preferably an aliphatic group
or an aromatic group. R.sub.59 in general formula (Cp-6) is preferably a
chlorine atom, an aliphatic group or an R.sub.41 CONH-- group. Moreover d
preferably has a value of 1 or 2. R.sub.60 is preferably an aromatic
group. R.sub.59 in general formula (Cp-7)is preferably an R.sub.41 CONH--
group. Moreover d in general formula (Cp-7) is preferably 1. R.sub.61 is
preferably an aliphatic group, an alicyclic group or an aromatic group. In
general formula (Cp-8) the value of e is preferably 0 or 1. R.sub.62 is
preferably an R.sub.41 OCONH-- group, an R.sub.41 CONH-- group or an
R.sub.41 SO.sub.2 NH-- group and the preferred substitution position of
these groups is the 5-position of the naphthol ring. R.sub.63 is
preferably an R.sub.41 CONH-- group, an R.sub.41 SO.sub.2 NH-- group, an
##STR52##
group, an R.sub.41 SO.sub.2 -- group, an
##STR53##
group, a nitro group or a cyano group.
Typical examples of R.sub.51 -R.sub.63 are described below.
Thus R.sub.51 may be a tert butyl group, 4-methoxyphenyl group, phenyl
group, 3-{2-(2,4-di-tert-amylphenoxy)butanamido}phenyl group,
4-octadecyloxyphenyl group or a methyl group. R.sub.52 and R.sub.53 may be
2-chloro-5-tetradecyloxycarbonylphenyl groups,
2-chloro-5-hexadecylsulfonamidophenyl groups,
2-chloro-5-tetradecanamidophenyl groups,
2-chloro-5-{4-(2,4-di-tert-amylphenoxy)butanamido}phenyl groups,
2-chloro-5-{2-(2,4-di-tert-amylphenoxy)butanamido)phenyl groups,
2-methoxyphenyl groups, 2-methoxy-5-tetradecyloxycarbonylphenyl groups,
2-chloro-5-(1-ethoxycarbonylethoxycarbonyl)phenyl groups, 2-pyridyl
groups, 2-chloro-5-octyloxycarbonylphenyl groups, 2,4-dichlorophenyl
groups, 2-chloro-5-(1-dodecyloxycarbonylethoxycarbonyl)phenyl groups,
2-chlorophenyl groups or 2-ethoxyphenyl groups.
R.sub.54 may be a 3-{2-(2,4-di-tert-amylphenoxy)butanamido}benzamido group,
3-{4-(2,4-di-tert-amylphenoxy)butanamido}benzamido group,
2-chloro-5-tetradecanamidoanilino group,
5-(2,4-di-tert-amylphenoxyacetamido)benzamido group,
2-chloro-5dodecenylsuccinimidoanilino group,
2-chloro-5-(2-(3-tert-butyl-4-hydroxyphenoxy)tetradecanamido)anilino
group, 2,2dimethylpropanamido group, 2-(3-pentadecylphenoxy)butanamido
group, pyrrolidino group or an N,N-dibutylamino group. R.sub.55 is
preferably a 2,4,6-trichlorophenyl group, 2-chlorophenyl group,
2,5-dichlorophenyl group, 2,3-ichlorophenyl group,
2,6-dichloro-4-methoxyphenyl group,
4-{2-(2,4-di-tert-amylphenoxy)butanamido}phenyl group or a
2,6-dichloro-4-methanesulfonylphenyl group. R.sub.56 may be a methyl
group, ethyl group, isopropyl group, methoxy group, ethoxy group,
methylthio group, ethylthio group, 3-phenylureido group, 3-butylureido
group or a 3-(2,4-di-tert-amylphenoxy)propyl group. R.sub.57 may be a
3-(2,4-di-tert-amy(phenoxy)propyl group,
3-[4-{2-[4-(4-hydroxyphenylsulfonyl)phenoxy]-tetradecanamido}phenyl]-propy
l group, methoxy group, ethoxy group, methylthio group, ethylthio group,
methyl group, 1-methyl-2-{ 2-octyloxy-5-[2-octyloxy-5-(
1,1,3,3-tetramethylbutyl)phenylsulfonamido]-phenylsulfonamido}ethyl group,
3-{4-(4-dodecyloxyphenylsulfonamido)phenyl}propyl group,
1,1-dimethyl-2-{2-octyloxy-5-(1,1,3,3-tetramethylbutyl)phenylsulfonamido}e
thyl group or a dodecylthio group. R.sub.58 may be a 2 chlorophenyl group,
pentafluorophenyl group heptafluoropropyl group,
1-(2,4-di-tert-amylphenoxy)propyl group, 3-(2,4-di-tert-amylphenoxy)propyl
group, 2,4-di-tert-amylphenoxymethyl group or a furyl group. R.sub.59 may
be a chlorine atom, methyl group, ethyl group, propyl group, butyl group,
iso-propyl group, 2-(2,4-di-tert-amylphenoxy)butanamido group, 2
(2,4-di-tert-amylphenoxy)hexanamido group,
2-(2,4-di-tert-octylphenoxy)octanamido group, 2-(2
chlorophenoxy)-tetradecanamido group, 2,2-dimethylpropanamido group,
2-{4-(4-hydroxyphenylsulfonyl)phenoxy}tetradecanamido group or a
2-{2-(2,4-di-tert-amylphenoxyacetamido)p | | |
