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Claims  |
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What is claimed is:
1. A color image-forming process which comprises image-wise exposing a
silver halide color photographic material, processing said photographic
material with a color developer, then processing said photographic
material with a solution having a pH of not more than about 6.5 and having
a bleaching ability within about 75 seconds, said photographic material
comprising a reflective support having thereon a blue-sensitive silver
halide emulsion layer containing a yellow dye-forming coupler, a
green-sensitive silver halide emulsion layer containing a magenta
dye-forming coupler and a red-sensitive silver halide emulsion layer
containing a cyan dye-forming coupler, the total silver amount of said
silver halide on said reflective support being up to about 0.78 g/m.sup.2,
and at least one of said emulsion layers comprising a silver halide
emulsion substantially excluding silver iodide and comprising about 80 mol
% or more silver chloride and containing a spectral sensitizing dye
represented by the following general formula (I), (II) or (III):
##STR29##
wherein: Z.sub.11 represents an oxygen atom, a sulfur atom or a selenium
atom;
Z.sub.12 represents a sulfur atom or a selenium atom;
R.sub.11 and R.sub.12, which may be the same or different, each represents
an optionally substituted alkyl group or alkenyl group containing up to 6
carbon atoms, with at least one of R.sub.11 and R.sub.12 being a
sulfo-substituted alkyl group;
when Z.sub.11 represents an oxygen atom, V.sub.11 and C.sub.13 each
represents a hydrogen atom, and V.sub.12 represents an optionally
substituted phenyl group, or V.sub.11 and V.sub.12, or V.sub.12 and
V.sub.13, may be linked to each other to form a fused benzene ring;
when Z.sub.11 represents a sulfur atom or a selenium atom, V.sub.11
represents an alkyl group containing up to 4 carbon atoms, an alkoxy group
containing up to 4 carbon atoms or a hydrogen atom, V.sub.12 represents an
alkyl group containing up to 5 carbon atoms, an alkoxy group containing up
to 4 carbon atoms, a chlorine atom, a hydrogen atom, an optionally
substituted phenyl group or a hydroxy group, and V.sub.13 represents a
hydrogen atom, or V.sub.11 and V.sub.12, or V.sub.12 and V.sub.13, may be
linked to each other to form a fused benzene ring;
when Z.sub.12 represents a selenium atom, V.sub.14, V.sub.15, and V.sub.16
are respectively the same as defined for V.sub.11, V.sub.12, and V.sub.13
in connection with the case where Z.sub.11 represents a selenium atom;
when Z.sub.12 represents a sulfur atom and Z.sub.11 represents a selenium
atom, V.sub.14 represents a hydrogen atom, an alkoxy group containing up
to 4 carbon atoms or an alkyl group containing up to 5 carbon atoms,
V.sub.15 represents an alkoxy group containing up to 4 carbon atoms, an
optionally substituted phenyl group, an alkyl group containing up to 4
carbon atoms, a chlorine atom or a hydroxy group, and V.sub.16 represents
a hydrogen atom, or V.sub.14 and V.sub.15, or V.sub.15 and V.sub.16, m ay
be linked to each other to form a fused benzene ring;
when Z.sub.11 and Z.sub.12 both represent a sulfur atom, V.sub.14 and
V.sub.16 each represents a hydrogen atom, and V.sub.15 represents an
optionally substituted phenyl group, or V.sub.14 and V.sub.15, or V.sub.15
and V.sub.16, may be linked to each other to form a ring;
when Z.sub.11 represents an oxygen atom and z.sub.12 represents a sulfur
atom, V.sub.14 and V.sub.16 each represents a hydrogen atom, and V.sub.15
represents a chlorine atom, an optionally substituted phenyl group or an
alkoxy group containing up to 4 carbon atoms, or V.sub.15 and V.sub.16 may
be linked to each other to form a fused benzene ring;
X.sub.11 represents a counter ion which is required to neutralize a charge
on a cyanine dye of formula (I) or (II); and
m.sub.11 represents 0 or 1;
##STR30##
wherein: Z.sub.21 represents an oxygen atom, a sulfur atom, a selenium
atom, or
##STR31##
Z.sub.22 represents an oxygen atom or
##STR32##
R.sub.21 and R.sub.22 are the same as defined for R.sub.11 or R.sub.12 in
general formula (I), or R.sub.21 and R.sub.24, or R.sub.22 and R.sub.25,
may be linked to each other to form a 5- or 6-membered carbon ring;
R.sub.23 represents a hydrogen atom when at least one of z.sub.21 and
Z.sub.22 represents
##STR33##
or represents an ethyl group, a propyl group or a butyl group in other
cases;
R.sub.26 and R.sub.27 are the same as defined for R.sub.11 in general
formula (I), provided that R.sub.21 and R.sub.26, and R.sub.22 and
R.sub.27, do not represent a sulfo group-containing substituent at the
same time;
R.sub.24 and R.sub.25 each represents a hydrogen atom;
V.sub.21 represents a hydrogen atom when Z.sub.21 represents an oxygen
atom, or represents a hydrogen atom, an alkyl group containing up to 5
carbon atoms or an alkoxy group containing up to 5 carbon atoms when
Z.sub.21 represents a sulfur atom or a selenium atom, or represents a
hydrogen atom or a chlorine atom when Z.sub.21 represents
##STR34##
V.sub.22 represents a hydrogen atom, an alkyl group containing up to 5
carbon atoms, an alkoxy group containing up to 5 carbon atoms, a chlorine
atom or an optionally substituted phenyl group, or V.sub.22 may be bonded
to V.sub.21 or V.sub.23 to form a fused benzene ring when Z.sub.21
represents an oxygen atom and Z.sub.22 represents
##STR35##
or V.sub.22 represents an optionally substituted phenyl group or may be
bonded to V.sub.21 or V.sub.23 to form a fused benzene ring when Z.sub.21
and Z.sub.22 both represent an oxygen atom, or V.sub.22 represents a
hydrogen atom, an alkyl group containing up to 5 carbon atoms, an
alkoxycarbonyl group containing up to 5 carbon atoms, an alkoxy group
containing up to 4 carbon atoms, an acylamino group containing up to 4
carbon atoms, a chlorine atom, or an optionally substituted phenyl group
when Z.sub.21 represents a sulfur atom or a selenium atom, or may be
bonded to V.sub.23 to form a fused benzene ring when Z.sub.21 represents a
sulfur atom, or represents a chlorine atom, a trifluoromethyl group, a
cyano group, an alkylsulfonyl group containing up to 4 carbon atoms or an
alkoxycarbonyl group containing up to 5 carbon atoms when Z.sub.21
represents
##STR36##
V.sub.24 represents a hydrogen atom when Z.sub.22 represents an oxygen
atom, or represents a hydrogen atom or a chlorine atom when Z.sub.22
represents
##STR37##
V.sub.25 represents an alkoxy group containing up to 4 carbon atoms, a
chlorine atom or an optionally substituted phenyl group or may be bonded
to V.sub.24 or V.sub.26 to form a fused benzene ring when Z.sub.22
represents an oxygen atom, or is bonded to V.sub.24 or V.sub.26 to form a
fused benzene ring when Z.sub.21 represents
##STR38##
an oxygen atom, a sulfur atom or a selenium atom, or, when Z.sub.22
represents
##STR39##
V.sub.25 represents a chlorine atom, a trifluoromethyl group, a cyano
group, an alkylsulfonyl group containing up to 4 carbon atoms or a
carboxyalkyl group containing up to 5 carbon atoms;
V.sub.26 represents a hydrogen atom;
X.sub.21 represents a counter ion which is required to neutralize a charge
on a cyanine dye of formula (I) or (II); and
m.sub.21 represents 0 or 1;
##STR40##
wherein: Z.sub.31 represents atoms forming a heterocyclic nucleus of
thiazoline, thiazole, benzothiazole, naphthothiazole, selenazoline,
selenazole, benzoselenazole, naphthoselenazole, benzimidazole,
naphthoimidazole, oxazole, benzoxazole, zole, selenazoline, selenazole,
benzoselenazole, naphthoselenazole, benzimidazole, naphthoimidazole,
oxazole, benzoxazole, naphthoxazole or pyridine, with the heterocyclic
nucleus being optionally substituted;
when Z.sub.31 represents atoms forming a benzimidozole nucleus, one or more
substituents in the fused benzene ring are selected from among a chloride
atom, a cyano group, an alkoxycarbonyl group containing up to 5 carbon
atoms, an alkylsulfonyl group containing up to 4 carbon atoms, and a
trifluoromethyl group;
when Z.sub.31 represents atoms forming heterocyclic nuclei other than
benzimidozole, thiazoline and selenazoline, one or more substituents in
the fused benzene ring or naphthalene ring are selected from among an
alkyl group containing up to 8 carbon atoms, a hydroxy group, an
alkoxycarbonyl group containing up to 5 carbon atoms, a halogen atom, a
carboxy group, a furyl group, a thienyl group, a pyridyl group, a phenyl
group and a substituted phenyl group;
when Z.sub.31 represents atoms forming a selenazoline or thiazoline
nucleus, one or more substituents in the nucleus is selected from among an
alkyl group containing up to 6 carbon atoms, a hydroxyalkyl group
containing up to 5 carbon atoms and an alkoxycarbonylalkyl group
containing up to 5 carbon atoms;
R.sub.31 is the same as defined for R.sub.11 or R.sub.12 in general formula
(I);
R.sub.32 is the same as defined for R.sub.11 or R.sub.12 in general formula
(I) or represents a hydrogen atom, a furfuryl group or an optionally
substituted aryl group, provided that at least one of R.sub.31 and
R.sub.32 represents a substituent having a sulfo or carboxy group and the
other represents a substituent having no sulfo group;
R.sub.33 represents a hydrogen atom, an alkyl group containing up to 5
carbon atoms, a phenethyl group, a phenyl group or a 2-carboxyphenyl
group;
Q.sub.31 represents an oxygen atom, a sulfur atom, a selenium atom or
##STR41##
provided that, when Z.sub.31 represents atoms forming a thiazoline,
selenazoline or oxazole nucleus, Q.sub.31 represents a sulfur atom, a
selenium atom or
##STR42##
R.sub.34 represents a hydrogen atom, a pyridyl group, a phenyl group, a
substituted phenyl group, or an aliphatic hydrocarbyl group optionally
containing an oxygen atom, a sulfur atom or a nitrogen atom in the carbon
chain, optionally having a substituent or substituents, and containing a
total of up to 8 carbon atoms;
k represents 0 or 1; and
n represents 0 or 1 provided that, when n represents 1 and Z.sub.31
represents atoms forming a pyridine nucleus, Q.sub.31 represents an oxygen
atom.
2. The color image-forming process as claimed in claim 1, wherein said
color developer contains up to about 0.002 mol/liter of bromide ion.
3. The color image-forming process as claimed in claim 1, wherein said
processing with a color developer is conducted within about 2 minutes and
30 seconds, said color developer substantially excluding benzyl alcohol.
4. The color image-forming process as claimed in claim 1, wherein said
solution having a bleaching ability is a bleach-fixing solution.
5. The color image-forming process as claimed in claim 1, wherein said
silver halide substantially excludes silver iodide and comprises 90 mol%
or more silver chloride.
6. The color image-forming process as claimed in claim 1, wherein said
processing with said solution having a bleaching ability occurs within 60
seconds, and said solution has a pH of not more than 6.0.
7. The color image-forming process as claimed in claim 1, wherein said
processing with a color developer is conducted within 10 seconds to two
minutes.
8. The color image-forming process as claimed in claim 1, wherein said
photographic material undergoes water-washing processing after said
processing with a solution having a bleaching ability.
9. The color image-forming process as claimed in claim 5, wherein a silver
halide comprises 95 mol % or more of a silver chloride.
10. The color image-forming process as claimed in claim 3, wherein a
concentration of a benzyl alcohol is not more than 0.5 ml/l.
11. The color image-forming process as claimed in claim 10, wherein a color
developer contains no benzyl alcohol at all.
12. The color image-forming process as claimed in claim 2, wherein a color
developer contains not more than 0.0007 mol/l of a bromine ion.
13. The color image-forming process as claimed in claim 12, wherein a color
developer contains no bromine ion at all.
14. The color image-forming process as claimed in claim 1, wherein a silver
halide emulsion is a monodispersed emulsion having not more than 0.15 of a
degree of monodispersion (s/d).
15. The color image-forming process as claimed in claim 1, wherein an
aromatic primary amine developer is of p-phenylenediamine derivatives.
16. The color image-forming process as claimed in claim 15, wherein an
aromatic primary amine is selected from the group consisting of:
N,N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene,
2-amino-5-(N-ethyl-N-laurylamino)toluene,
4-[N-ethyl-N-(.beta.-hydroxyethyl)amino]aniline,
2-methyl-4-[N-ethyl-N-(.beta.-hydroxyethyl)amino]aniline,
N-ethyl-N-(.beta.-methanesulfonamidoethyl)-3-methyl-4-aminoaniline,
N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide,
N,N-dimethyl-p-phenylenediamine,
4-amino-3-methyl-N-ethyl-N-methoxyethylaniline,
4-amino-3-methyl-N-ethyl-N-.beta.-ethoxyethylaniline, and
4-amino-3-methyl-N-ethyl-N-.beta.-butoxyethylaniline, and salts of said
compounds.
17. The color image-forming process as claimed in claim 16, wherein said
p-phenylenediamine derivative is
N-ethyl-N-(.beta.-methanesulfonamidoethyl)-3-methyl-4-aminoaniline or salt
thereof.
18. The color image-forming process as claimed in claim 1, wherein a color
developer contains a luminescent brightening agent.
19. The color image-forming process as claimed in claim 18, wherein a
luminescent whitening agent is of 4,4-diamino-2,2'-disulfrostilben type.
20. The color image-forming process as claimed in claim 1, wherein a
treating solution having bleaching activity is a ferric ion complex as a
bleaching agent.
21. The color image-forming process as claimed in claim 20, wherein a
ferric ion complex is a complex of a ferric ion and an amino
polycarboxylic acid, amino polysulfonic acid, or each salt thereof. |
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Claims |
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Description |
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FIELD OF THE INVENTION
The present invention relates to a color image-forming process and, more
particularly, to a color image-forming process which provides a high
sensitivity, an improved fog resistance, and an improved silver
removability, and which is capable of undergoing rapid processing. In
addition, the present invention relates to a silver halide color
photographic material suitable for use in the above-described
image-forming process.
BACKGROUND OF THE INVENTION
Recently, in the photographic market there has been an increasing
requirement for rapid photographic processing, and it has become extremely
important to meet this requirement.
Silver halide mainly containing silver bromide and having been
predominantly used in the past are disadvantageous in principle with
respect to rapid processing, since bromide ion to be released upon
development of silver bromide has development-inhibiting properties. Thus,
from the standpoint of achieving rapid processing, the use of silver
halides mainly containing silver chloride is preferable.
So-called "high silver chloride emulsions" containing a high proportion of
silver chloride are advantageous in view of attaining suitable rapid
processing.
It has been found, however, that the use of high silver chloride emulsions
involves the following disadvantage in accelerating photographic
processing. That is, though high silver chloride emulsions undergo rapid
fixing during a silver-removing step, silver deposit produced as a result
of development is much more difficult to bleach than silver deposit
produced from low silver chloride emulsions. It has become apparent that
this is disadvantageous not only in the case of accelerating and
shortening photographic processing, including the silver-removing step,
but also in the case of coping with the bleaching difficulty by prolonging
the silver-removing time. This is because, in the latter case, the
prolonged silver-removing time sometimes negates the shortened or
accelerated photographic processing time.
In the bleaching step, a combination of a bleaching bath and a fixing bath
or a bleach-fixing bath is used. Suitable bleaching agents to be used in
the bleach-fixing bath include organic iron chelating agents, such as iron
aminopolycarboxylates showing a moderate oxidizing power not affecting a
coexisting fixing agent, such as a silver halide solvent. It has been
found that such bleach-fixing baths not having a strong oxidizing power
undergo a reduction in oxidizing power particularly when fatigued after
processing a large amount of silver halide photographic materials, or when
the amount of processing solution used in the foregoing step is increased
so that bleaching of silver deposits is delayed and, in an extreme case, a
portion of silver deposits can hardly be removed, even by indefinitely
prolonged the bleaching time.
In addition, shortening of the exposure time is also important in terms of
decreasing the entire photographic processing time, thus improving
productivity. Therefore, emulsions to be used must be highly sensitive.
However, high silver chloride emulsions are known to have the defect that
they easily form fog and possess a low sensitivity, although they can be
rapidly developed. Further, intrinsic absorption of the high silver
chloride grains occurs in a short wavelength regions; hence, the grains
show an extremely weak absorption of visible light in comparison with
silver halide grains comprising mainly silver bromide. Particularly, high
silver chloride grains containing 99 mol % or more silver chloride are
known to scarcely absorb visible light. In order to render silver halide
responsive to light in longer wavelength regions than the silver
halide-intrinsic absorption region, spectral sensitizing techniques are
commonly employed. However, as is different from silver halide emulsions
comprising mainly silver bromide, high silver chloride emulsions require
spectral sensitization even when used as an emulsion sensitive to light of
the blue region. These facts have long been known. Various spectral
sensitizing dyes have recently been proposed in Japanese patent
application (OPI) Nos. 106,538/83, 107,531/83 and 107,532/83 (U.S. Patent
No. 4,469,785); Nos. 107,533/83, 91,444/83; No.95,339/83 (U.S. Patent No.
4,517,284), etc. (the term "OPI" as used herein means an "unexamined
published application"). As is different from emulsions comprising mainly
silver bromide, high silver chloride emulsions show very poor spectral
sensitizing properties, even when subjected to spectral sensitization. For
example, the spectral sensitizing agents described in the above-mentioned
specifications, which are usually used for emulsions comprising mainly
silver bromide and show high sensitizing ability therefor, do not
necessarily show high sensitizing ability for high silver chloride
emulsions. Further, with respect to spectral sensitizing agents other than
those for used for sensitizing emulsions to blue light, many of these
spectral sensitizing agents which are effective for emulsions comprising
mainly silver bromide have been found to exhibit low sensitizing ability
for high silver chloride emulsions. Still further, it has been found that
many of the spectral sensitizing agents described in the aforesaid
specifications and spectral sensitizing agents used usually for silver
halide emulsions comprising mainly silver bromide seriously inhibit
bleaching of silver deposits formed in high silver chloride emulsions.
Bleaching of silver deposits depends not only upon the oxidizing power of
the bleaching solution, but also upon the shape or form of the silver
deposits or the amount of silver deposited. Bleaching difficulty of the
silver deposits produced from high silver chloride emulsions in comparison
with that from low silver chloride emulsions in attributed to the
difference in the shape of silver deposits based on observation of these
silver deposits using an electron microscope.
More importantly, bleaching of silver deposits can be delayed or inhibited
by some compounds absorbed on the surface of the silver deposits. Silver
halide color photographic materials are designed to exert various steps of
development processing, from imagewise exposure to development and color
formation, and various compounds are incorporated therein for performing
such functions. It is important not to cause the aforesaid inhibition of
silver removal while meeting these requirements.
It has been observed that the inhibition of removal of silver deposits
formed from high silver chloride emulsions is also caused by bromide ion
which is usually added to a color developer for assuring uniform
development. This bromide ion is considered to change the shape or form of
silver deposits.
SUMMARY OF THE INVENTION
As a result of various investigations, the present inventors have found
that the dyes represented by the general formula (I), (II) or (III)
described hereinafter show high special sensitizing ability for high
silver chloride emulsions.
Of these compounds, cyanine dyes particularly show excellent J-association
product-forming ability, including so-called J-band type spectral
sensitizing ability for high silver chloride emulsions containing 95 mol %
or more silver chloride and show excellent absorptive properties on the
high silver chloride grains and high spectral sensitizing ability.
However, these dyes also strongly absorb on silver deposits produced from
the high silver chloride emulsion, and inhibition of silver removal is
observed during ordinary bleaching.
Therefore, an object of the present invention is to provide a
light-sensitive color photographic material containing a high silver
chloride emulsion and having high spectral sensitivity.
A further object of the present invention is to provide a color
image-forming process capable of rapidly bleaching silver deposits formed
during color development of the light-sensitive color photographic
material.
These and other objects have been attained by an accelerated color
image-forming process which comprises imagewise exposing and subsequently
processing a silver halide color photographic material with a color
developer preferably substantially excluding benzyl alcohol and containing
up to about 0.002 mol/liter of bromide ion, with the developing time being
not longer than 2 minutes and 30 seconds), then processing the silver
halide color photographic material in a solution having of pH of not more
than about 6.5 having a bleaching ability (bleach-fixing solution or
bleaching solution) for a time of not longer than about 75 seconds, said
silver halide photographic material comprising a support having thereon at
least one light-sensitive layer containing at least one coupler capable of
forming a dye upon a coupling reaction with an oxidation product of an
aromatic primary amine color developing agent and a silver halide emulsion
substantially excluding silver iodide and containing about 80 mol % or
more, preferably 90% or more, silver chloride and further containing at
least one of the compounds represented by general formula (I), (II) or
(III) described in detail below.
DETAILED DESCRIPTION OF THE INVENTION
Sensitizing dyes represented by general formula (I) are as follows:
##STR2##
In the above general formula (I), Z.sub.11 represents an oxygen atom, a
sulfur atom or a selenium atom.
Z.sub.12 represents a sulfur atom or a selenium atom.
R.sub.11 and R.sub.12 which may be the same or different, each represents
an optionally substituted alkyl group or alkenyl group containing up to 6
carbon atoms, with at least one of R.sub.11 and R.sub.12 being a
sulfo-substituted alkyl group. Most preferably, at least one of R.sub.11
and R.sub.12 represents a 3-sulfopropyl group, a 2-hydroxy-2-sulfopropyl
group, a 3-sulfobutyl group, or a sulfoethyl group. Examples of suitable
substituents include an alkoxy group containing up to 4 carbon atoms, a
halogen atom, a hydroxy group, a carbamoyl group, a phenyl group which may
be optionally substituted and which contains up to 8 carbon atoms, a
carboxy group, a sulfo group, and an alkoxycarbonyl group containing up to
5 carbon atoms. Specific examples of R.sub.11 and R.sub.12 include a
methyl group, an ethyl group, a propyl group, an allyl group, a pentyl
group, a hexyl group, a methoxyethyl group, an ethoxyethyl group, a
phenethyl group, a 2-p-tolylethyl group, a 2-p-sulfophenethyl group, a
2,2,2-trifluoroethyl group, a 2,2,3-tetrafluoropropyl group, a
carbamoylethyl group, a hydroxyethyl group, a 2-(2-hydroxyethoxy)ethyl
group, a carboxymethyl group, a carboxyethyl group, an
ethoxycarbonylmethyl group, a 2-sulfoethyl group, a 2-chloro-3-sulfopropyl
group, a 3-sulfopropyl group, a 2-hydroxy-3-sulfopropyl group, a
3-sulfobutyl group, a 4-sulfobutyl group, etc.
When Z.sub.11 represents an oxygen atom, V.sub.11 and V.sub.13 each
represents a hydrogen atom, and V.sub.12 represents a phenyl group or a
phenyl group substituted by an alkyl group or an alkoxy group containing
up to 3 carbon atoms or a chlorine atom (particularly preferably a phenyl
group), or V.sub.11 and V.sub.12, or V.sub.12 and V.sub.13, may be linked
to each other to form a fused benzene ring. Most preferably, V.sub.11 and
V.sub.13 each represents a hydrogen atom, and V.sub.12 represents a phenyl
group.
When Z.sub.11 represents a sulfur atom or a selenium atom, V.sub.11
represents an alkyl group containing up to 4 carbon atoms or a hydrogen
atom, V.sub.12 represents an alkyl group containing up to 5 carbon atoms,
an alkoxy group containing up to 4 carbon atoms, a chlorine atom, a
hydrogen atom, an optionally substituted phenyl group (e.g., a tolyl
group, an anisyl group, a phenyl group, etc.) or a hydroxy group, and
V.sub.13 represents a hydrogen atom, or V.sub.11 and V.sub.12, or V.sub.12
and V.sub.13, may be linked to each other to form fused benzene ring. More
preferably, V.sub.11 and V.sub.13 each represents a hydrogen atom and
V.sub.12 represents an alkoxy group containing up to 4 carbon atoms, a
phenyl group or a chlorine atom; V.sub.11 represents an alkoxy group or an
alkyl group containing up to 4 carbon atoms and V.sub.12 represents a
hydroxy group or an alkyl group containing up to 4 carbon atoms; or
V.sub.12 and V.sub.13 are linked to each other to form a fused ring.
When Z.sub.12 represents a selenium atom, V.sub.14, V.sub.15, and V.sub.16
are respectively the same as defined for V.sub.11, V.sub.12, and V.sub.13
in connection with the case where Z.sub.11 represents a selenium atom.
When Z.sub.12 represents a sulfur atom and Z.sub.11 represents a selenium
atom, V.sub.14 represents a hydrogen atom, an alkoxy group containing up
to 4 carbon atoms or an alkyl group containing up to 5 carbon atoms,
V.sub.15 represents an alkoxy group containing up to 4 carbon atoms, an
optionally substituted phenyl group (preferably a phenyl group;
exemplified by a tolyl group and an anisyl group), an alkyl group
containing up to 4 carbon atoms, a chlorine atom or a hydroxy group, and
V.sub.16 represents a hydrogen atom, or V.sub.14 and V.sub.15, or V.sub.15
and V.sub.16, may be linked to each other to form a fused benzene ring.
More preferably, V.sub.14 and V.sub.16 each represents a hydrogen atom, and
V.sub.15 represents an alkoxy group containing up to 4 carbon atoms, a
chlorine atom or a phenyl group; or V.sub.15 and V.sub.16 are linked to
each other to form a fused benzene fing. When Z.sub.11 and Z.sub.12 both
represent a sulfur atom, V.sub.14 and V.sub.16 each represents a hydrogen
atom and V.sub.15 represents an optionally substituted phenyl group (e.g.,
a phenyl group or a tolyl group), or V.sub.14 represents a hydrogen atom
and V.sub.15 and V.sub.16 are linked to each other to form a fused benzene
ring. When Z.sub.11 represents an oxygen atom and Z.sub.12 represents a
sulfur atom, V.sub.14 and V.sub.16 each represents a hydrogen atom, and
V.sub.15 represents a chlorine atom, an optionally substituted phenyl
group or an alkoxy group containing up to 4 carbon atoms, or V.sub.15 and
V.sub.16 may be linked to each other to form a fused benzene ring; more
preferably, V.sub.14 and V.sub.16 each represents a hydrogen atom and
V.sub.15 represents a phenyl group, or V.sub.15 and V.sub.16 are linked to
each other to form a fused benzene ring.
X.sub.11 represents a counter ion which is required to neutralize a charge
on a cyanine dye of formula (I) or (II). Examples of these ions are a
halogen ion such as Cl.sup.-, Br.sup.-, I.sup.-, etc.; No.sub.3.sup.2- ;
SO.sub.4.sup.2- ;
##STR3##
Rhodan ion, etc., as an anion; and an alkali metal ion such as Li.sup.+,
Na.sup.+, K.sup.+, etc., an alkali earth metal ion such as Ca.sup.2+,
etc., as a cation.
m.sub.11 represents 0 or 1 and, in the case of forming inner salt, m.sub.11
represents 1.
Sensitizing dyes represented by general formula (II) are as follows:
##STR4##
In the above general formula (II), Z.sub.21 represents an oxygen atom, a
sulfur atom, a selenium atom, or
##STR5##
and Z.sub.22 represents an oxygen atom or
##STR6##
R.sub.21 and R.sub.22 are the same as the defined for R.sub.11 or R.sub.12
in general formula (I), or R.sub.21 and R.sub.24, or R.sub.22 and
R.sub.25, may be linked to each other to form a 5- or 6-membered carbon
ring.
R.sub.23 represents a hydrogen atom when at least one of Z.sub.21 and
Z.sub.22 represents
##STR7##
or represents an ethyl group, a propyl group or a butyl group (preferably
an ethyl group) in other cases. R.sub.24 and R.sub.25 each represents a
hydrogen atom.
R.sub.26 and R.sub.27 are the same as defined for R.sub.11 in general
formula (I), provided that R.sub.21 and R.sub.26, and R.sub.22 and
R.sub.27, do not represent a sulfo group-containing substituent at the
same time.
V.sub.21 represents a hydrogen atom when Z.sub.21 represents an oxygen
atom, or represents a hydrogen atom, an alkyl group containing up to 5
carbon atoms or an alkoxy group containing up to 5 carbon atoms when
Z.sub.21 represents a sulfur atom or a selenium atom, or represents a
hydrogen atom or a chlorine atom when Z.sub.21 represents
##STR8##
.
V.sub.22 represents a hydrogen atom, an alkyl group containing up to 5
carbon atoms, an alkoxy group containing up to 5 carbon atoms, a chlorine
atom or an optionally substituted phenyl group (e.g., a tolyl group, an
anisyl group, a phenyl group, etc.), or V.sub.22 may be bonded to V.sub.21
or V.sub.23 to form a fused benzene ring when Z.sub.21 represents an
oxygen atom and Z.sub.22 represents
##STR9##
(more preferably V.sub.22 represents an alkoxy group or a phenyl group, or
V.sub.21 and V.sub.22, or V.sub.22 and V.sub.23 are linked to each other
to form a fused benzene ring), or V.sub.22 represents an optionally
substituted phenyl group (e.g., a tolyl group, an anisyl group, a phenyl
group, etc., with a phenyl group being more preferable) or may be linked
to V.sub.21 or V.sub.23 to form a fused benzene ring when Z.sub.21 and
Z.sub.22 both represent an oxygen atom, or V.sub.22 represents a hydrogen
atom, an alkyl group containing up to 5 carbon atoms, an alkoxycarbonyl
group containing up to 5 carbon atoms, an alkoxy group containing up to 4
carbon atoms, an acylamino group containing up to 4 carbon atoms, a
chlorine atom or an optionally substituted phenyl group (more preferably)
an alkyl group or an alkoxy group containing up to 4 carbon atoms, a
chlorine atom or a phenyl group) when Z.sub.21 represents a sulfur atom or
a selenium atom, or may be bonded to V.sub.23 to form a fused benzene ring
when Z.sub.21 represents a sulfur atom. When Z.sub.21 represents
##STR10##
V.sub.22 represents a chlorine atom, a trifluoromethyl group, a cyano
group, an alkylsulfonyl group containing up to 4 carbon atoms or an
alkoxycarbonyl group containing up to 5 carbon atoms (preferably V.sub.21
represents a chlorine atom and V.sub.22 represents a chlorine atom, a
trifluoromethyl group or a cyano group when Z.sub.21 represents
##STR11##
V.sub.24 represents a hydrogen atom when Z.sub.22 represents an oxygen
atom, or represents a hydrogen atom or a chlorine atom when Z.sub.22
represents
##STR12##
V.sub.25 represents an alkoxy group containing up to 4 carbon atoms, a
chlorine atom or an optionally substituted phenyl group (e.g., a n anisyl
group, a tolyl group, a phenyl group, etc.) or may be bonded to V.sub.24
or V.sub.26 to form a fused benzene ring when Z.sub.22 represents an
oxygen atom and, more preferably an alkoxy group containing up to 4 carbon
atoms, a phenyl group or is preferably bonded to V.sub.24 or V.sub.26 to
form a fused benzene ring when Z.sub.21 represents
##STR13##
or V.sub.25 preferably represents a phenyl group or is preferably bonded
to V.sub.24 or V.sub.26 to form a fused benzene ring when Z.sub.21
represents an oxygen atom, a sulfur atom or a selenium atom. When Z.sub.22
represents
##STR14##
V.sub.25 represents a chlorine atom, a trifluoromethyl group, a cyano
group, an alkylsulfonyl group containing up to 4 carbon atoms or a
carboxyalkyl group containing up to 5 carbon atoms. Particularly
preferably, V.sub.24 represents a chlorine atom, and V.sub.25 represents a
chlorine atom, a trifluoromethyl group or a cyano group.
V.sub.26 represents a hydrogen atom.
X.sub.21 represents a counter ion which is required to neutralize a charge
on a cyanine dye of formula (I) or (II). Examples of these ions are a
halogen ion such as Cl.sup.-, Br.sup.-, I.sup.-, etc.; No.sub.3.sup.+ ;
SO.sub.4.sup.2- ;
##STR15##
Rhodan ion, etc., as an anion; and an alkali metal ion such as Li.sup.+,
Na.sup.+, K.sup.+, etc.; an alkali earth metal ion such as Ca.sup.2+,
etc., as a cation.
m.sub.21 represents 0 or 1 and, when an inner salt is formed, m.sub.21
represents 0.
Sensitizing dyes represented by general formula (III) are as follows:
##STR16##
In the above general formula (II), Z.sub.31 represents atoms forming a
heterocyclic nucleus of thiazoline, thiazole, benzothiazole,
naphthothiazole, selenazoline, selenazole, benzoselenazole,
naphthoselenazole, benzimidazole, naphthoimidazole, oxazole, benzoxazole,
naphthoxazole, or pyridine, with the heterocyclic nucleus being optionally
substituted. When Z.sub.31 represents atoms forming a benzimidazole
nucleus or a naphthoimidazole nucleus, substituents for the nitrogen atom
at the 1-position other than R.sub.31 include those illustrated for
R.sub.26 or R.sub.27 of general formula (II) described above. Substituents
in the fused benzene ring of benzimidazole include, for example, a
chlorine atom, a cyano group, an alkoxycarbonyl group containing up to 5
carbon atoms, an alkylsulfonyl group containing up to 4 carbon atoms or a
trifluoromethyl group. Particularly preferably, the benzimidazole nucleus
is substituted by a chlorine atom at the 5-position and by a cyano group,
a chlorine atom or a trifluoromethyl group at the 6-position. Substituents
for heterocyclic nuclei other than the benzimidazole nucleus, selenazoline
nucleus, and thiazoline nucleus include an optionally substituted alkyl
group containing a total of up to 8 carbon atoms (examples of the
substituents being a hydroxy group, a chlorine atom, a fluorine atom, an
alkoxy group, a carboxy group, an alkoxycarbonyl group, a phenyl group or
a substituted phenyl group), a hydroxy group, an alkoxycarbonyl group
containing up to 5 carbon atoms, a halogen atom, a carboxy group, a furyl
group, a thienyl group, a pyridyl group, a phenyl group or a substituted
phenyl group (e.g., a tolyl group, an anisyl group, a chlorophenyl group,
etc.). Substituents for the selenazoline nucleus or thiazoline nucleus
include an alkyl group containing up to 6 carbon atoms, a hydroxyalkyl or
alkoxycarbonylalkyl group containing up to 5 carbon atoms, etc.
R.sub.31 is the same as defined above for R.sub.11 or R.sub.12 in general
formula (I).
R.sub.32 is the same as defined above for R.sub.11 or R.sub.12 in general
formula (I), or represents a hydrogen atom, a furfuryl group or an
optionally substituted aryl group (e.g., a phenyl group, a tolyl group, an
anisyl group, a carboxyphenyl group, a hydroxyphenyl group, a chlorophenyl
group, a sulfophenyl group, a pyridyl group, a 5-methyl-2-pyridyl group, a
5-chloro-2-pyridyl group, a thienyl group, a furyl group, etc.), provided
that at least one of R.sub.31 and R.sub.32 represents a substituent having
a sulfo or carboxy group and the other represents a substituent having no
sulfo group.
R.sub.33 represents a hydrogen atom, an alkyl group containing up to 5
carbon atoms, a phenethyl group, a phenyl group or a 2-carboxyphenyl
group, more preferably a hydrogen atom, a methyl group or an ethyl group.
Q.sub.31 represents an oxygen atom, a sulfur atom, a selenium atom or
##STR17##
provided that, when Z.sub.31 represents atoms forming a thiazoline,
selenazoline or oxazole nucleus, Q.sub.31 preferably represents a sulfur
atom, a selenium atom or
##STR18##
R.sub.34 represents a hydrogen atom, a pyridyl group, a phenyl group, a
substituted phenyl group (e.g., a tolyl group, an anisyl group, etc.), or
an aliphatic hydrocarbyl group optionally containing an oxygen atom, a
sulfur atom or a nitrogen atom in the carbon chain, optionally having a
substituent or substituents, and containing a total of up to 8 carbon
atoms.
k represents 0 or 1, and n represents 0 or 1.
When n represents 1 and Z.sub.31 represents atoms forming a pyridine
nucleus, Q.sub.31 represents an oxygen atom.
The present inventors have completed the novel technique, of providing a
spectrally sensitized silver halide color photographic material containing
a high silver chloride emulsion capable of being processed with a
bleachfixing solution having a pH of not more than about 6.5, more
preferably not more than 6.0, for not longer then about 75 seconds, even
not longer than 60 seconds and with a substantially benzyl alcohol-free
color developer solution containing up to about 0.002 mol/liter of bromide
ion for a time as short as not longer than about 2 minutes and 30 seconds
to form a color image, by incorporating the spectral sensitizing dyes
represented by general formula (I), (II) or (III) described above in
detail into the high silver chloride emulsion.
Specific examples of the compounds represented by general formula (I), (II)
or (III) are illustrated below as a further description of the present
invention which, however, are not to be construed as limiting the scope of
the present invention in any manner whatsoever.
##STR19##
The compounds represented by general formula (I), (II) or (III) to be used
in the present invention are known compounds, and may be synthesized by
reference to, for example, Japanese patent application (OPI) No.
104917/77, Japanese Patent Publication Nos. 22884/68, 25652/73, 22368/82,
etc., F. M. Hamer, The Chemistry of Heterocyclic Compounds, Vol. 18, "The
Cyanine Dyes and Related Compounds", compiled by A. Weissberger and
published by Interscience, New York, 1964, and D. M. Sturmer, The
Chemistry of Heterocyclic Compounds, Vol. 30, compiled by A. Weissberger
and E. C. Taylor and pub | | |
