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FIELD OF THE INVENTION
The present invention relates to a method for processing a silver halide
color photographic material, and more particularly, to a method for
processing a silver halide color photograhic material which is capable of
rapidly processing a silver halide color photographic material containing
silver chloride or silver chlorobromide having a high silver chloride
content.
BACKGROUND OF THE INVENTION
Methods for processing silver halide color photographic materials
(hereinafter referred to as color light-sensitive materials) generally
comprise a color development step to form color images, a desilvering step
to remove developed silver and undeveloped silver halide, and a water
washing step and/or an image stabilizing step.
Heretofore, attempts have been made to reduce the processing time necessary
for processing color light-sensitive materials. Recently, however, further
reduction of the required processing time has been highly desirable in
terms of reducing the total time period needed to finish processing,
simplification of laboratory work, and miniaturization and simple
operation of the processing system for small scale laboratories known as
mini-labs, etc.
A method in which the time required to perform the color development step
is reduced is known, and comprises processing a color light-sensitive
material containing silver chloride or silver chlorobromide having a high
silver chloride content. The color development speed of color
light-sensitive materials containing silver chloride or silver
chlorobromide having a high silver chloride content is extremely high as
compared with, e.g., the color development speed of color light-sensitive
materials containing silver chlorobromide having a high silver bromide
contents, silver bromide, or silver iodobromide as employed in
conventional color papers, etc. Therefore, the potential exists at present
for reduction of developing time to a large extent.
Further, the color light-sensitive materials containing silver chloride or
silver chlorobromide having a high silver chloride content is preferred
since halogen ions released in a processing solution upon development are
mainly or wholly chloride ions. On the contrary, halogen ions released are
mainly or wholly bromide ions when color developing the other types of
color light-sensitive materials referred to above. The chloride ions are
characterized in that they have a remarkably small development inhibiting
effect in comparison with bromide ions, and thus do not decrease the color
development activity of the color developing solution even when accumulate
therein in high concentrations. As a result, the amount of replenishing
solution for the color developing solution can be reduced in the case of
processing the color light-sensitive materials containing silver chloride
or silver chlorobromide having a high silver chloride content using an
automatic developing machine, as compared with color developing
conventional color light-sensitive materials containing mainly silver
bromide.
Hitherto, the desilvering step in the processing of color light-sensitive
materials has been conducted by two different types of systems. One is a
processing system wherein a bleaching step (by which developed silver is
oxidized) and a fixing step (by which undeveloped silver halide and silver
halide formed in the bleaching step are solubilized using a silver halide
solvent) are carried out separately; the other is a processing system
wherein the bleaching step and the fixing step are carried out at the same
time in a single bath, that is, a so-called bleach-fixing system. Of these
systems, the bleach-fixing system has the advantage of using only one
processing solution, which is effective for purposes of miniaturization
and simplification of the processing system, and thus, is practically
employed in the processing of color light-sensitive materials such as
color paper, color reversal paper, etc.
While various compounds have been proposed to be added to the bleach-fixing
bath, a bleach-fixing solution containing a ferric complex salt of
aminopolycarboxylic acid as a bleaching agent and a thiosulfate as a
fixing agent is usually employed in practice, at present.
However, ferric complex salts of aminopolycarboxylic acids, such as a
ferric complex salt of ethylenediaminetetraacetic acid, have a
comparatively small oxidizing power and therefore, have insufficient
bleaching power, although they are advantageous as to prevention of
environmental pollution because of their low toxic character. As a result,
color light-sensitive materials to which such a bleach-fixing system can
be applied are limited to those having a low coating amount of silver.
With respect to methods for accelerating such a bleach-fixing step, a small
number of techniques are known and only restricted number of accelerators
have been investigated. For instance, compounds having a mercapto group or
a disulfide group as described in U.S. Pat. No. 3,893,858, West German
Pat. No. 1,290,812, etc., thiourea derivatives as described in U.S. Pat.
No. 3,706,561, Japanese Patent Application (OPI) No. 32735/78, etc. (the
term "OPI" as used herein means an "unexamined published application"),
polyethyleneoxides as described in West German Pat. No. 2,748,430, etc.,
are exemplified. However, when these compounds having a mercapto group or
a disulfide group, or the thiourea derivatives are employed as
bleach-fixing accelerators for silver halide color photographic materials
containing silver chloride or silver chlorobromide and having a low
coating amount of silver, they tend to hinder the bleach-fixing reaction,
and thus do not provide preferred results. Also, in the case of using
polyethyleneoxides, sufficient effects are not obtained.
In British Pat. No. 990,846, a method in which an intermediate bath
containing an iodide salt is provided between a color developing bath and
a bleach-fixing bath in the overall processing sequence described.
However, providing such an intermediate bath is not a preferred processing
method in view of the recent trend aiming at simplification and
miniaturization of the overall processing system. Further, a method of
processing using a bleach-fixing solution containing an iodide salt is
described in British Pat. No. 926,569. This method is effective in
restrainig the hindrance of the bleach-fixing reaction during
bleach-fixing processing of color light-sensitive material containing
silver chlorobromide wide a low coating amount of silver and hydrophilic
and diffusion-resistant couplers. However, addition of the iodide salt to
the bleach-fixing solution rather adversely affects on the bleach-fixing
reaction of color light-sensitive materials containing silver
chlorobromide having a high silver bromide content and oil-protected type
couplers which are generally used in practice at present, and preferred
results can not be obtained.
Moreover, in Japanese Patent Publication No. 11854/78 and Japanese Patent
Application (OPI) No. 87036/76, a method of processing color
light-sensitive materials containing silver chlorobromide or silver
iodobromide having a high silver bromide content in the presence of a
halide salt or ammonium bromide is described. However, in this method, a
small amount of silver or silver salt can not be removed and remains in
the photographic materials, particularly when color light-sensitive
materials containing silver chlorobromide having a high silver chloride
content with a low coating amount of silver (such as color paper) are
subjected to bleach-fixing processing. Such a small amount of remaining
silver is particularly present at image portions having high density, and
deteriorates color reproduction of the color images. This tendency is
especially remarkable in yellow and red images.
The amount of remaining silver in high density portions is larger when
color light-sensitive materials containing silver chloride or silver
chlorobromide having a high silver chloride content as described above are
subjected to bleach-fixing processing after color development processing
in comparison with the case wherein conventional color light-sensitive
materials containing silver chlorobromide having a high silver bromide
content are processed in the same manner as above.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to provide a rapid method
for processing a color light-sensitive material.
Another object of the present invention is to provide a method for
processing a color light-sensitive material, which is excellent in
desilvering ability and by which resulting images having a small remaining
amount of silver are obtained.
A further object of the present invention is to provide a method for
processing a color light-sensitive material, which provides excellent
color reproducibility.
These and other objects of the present invention will become apparent from
the following description and examples.
That is, these objects of the present invention can be attained by a method
for processing a silver halide color photographic material comprising
processing an imagewise exposed silver halide color photographic material
comprising a support having thereon at least one silver halide emulsion
layer comprising silver chloride or silver chlorobromide containing at
least about 80 mol% of silver chloride with a color developing solution
and thereafter processing the material with a bleach-fixing solution,
wherein the bleach-fixing solution contains a ferric complex salt of an
organic acid and from about 1.times.10.sup.-2 to about 2 mol of bromide
ions and/or from about 5.times.10.sup.-4 to about 5.times.10.sup.-2 mol of
iodide ions per liter.
DETAILED DESCRIPTION OF THE INVENTION
In the method for processing a silver halide color photographic material
according to the present invention, the color developing solution
preferably contains substantially no benzyl alcohol.
The term "color developing solution containing substantially no benzyl
alcohol" as used herein specifically refers to a color developing solution
containing benzyl alcohol in a concentration of not more than about 1 g,
preferably from 0 to 0.5 g per liter of the solution.
It has been determined that the amount of remaining silver is remarkably
small when a color light-sensitive material containing silver chloride or
silver chlorobromide having a high silver chloride content is subjected to
a bleach-fixing processing in the presence of bromide ions and/or iodide
ions according to the present invention, in comparison with the case
wherein a conventional color light-sensitive material containing silver
chlorobromide having a high silver bromide content is subjected to the
bleach-fixing processing in accordance with the present invention, as
illustrated in the examples hereinafter. This discovery is considered to
be completely unexpected from conventional knowledge possessed by those
skilled in the art. As a result, it is now possible to process color
photographic light-sensitive materials rapidly and with good color
reproducibility according to the method of the present invention.
The bromide ions or iodide ions which are used in the bleach-fixing
solution according to the present invention are preferably added to the
bleach-fixing solution in the form of water soluble bromide salts or
iodide salts. Specific examples of useful water soluble salts include
alkali metal salts, ammonium salts, alkaline earth metal salts of these
ions, etc., such as ammonium bromide, sodium bromide, potassium bromide,
ammonium iodide, sodium iodide, potassium iodide, etc.
Preferred results can be obtained when these ions are present in the range
of from about 1.times.10.sup.-2 to about 2 mol of bromide ions or in the
range of from about 5.times.10.sup.-4 to about 5.times.10.sup.-2 mol of
iodide ions per liter of the bleach-fixing solution. In particular, it is
preferred that the bromide ions are in a range of from 1.times.10.sup.-2
to 5.times.10.sup.-1 mol per liter and the iodide ions are in a range of
from 5.times.10.sup.-4 to 1.times.10.sup.-2 mol per liter of the solution.
When the concentration of bromide ions is less than about 1.times.10.sup.-2
mol per liter of the bleach-fixing solution, no bleach-fixing accelerating
effect is observed, and such low amounts are not preferred in view of
reduction in the amount of remaining silver. On the other hand, when the
concentration of bromide ions exceeds about 2 mol per liter of the
solution, insufficient fixing may tend to occur, and such high
concentrations are not preferred in view of desilvering ability of the
solution.
Further, it is not preferred that the concentration of iodide ions be less
than about 5.times.10.sup.-4 mol per liter of the solution in view of
reduction in the amount of remaining silver, the same concern as in the
case of the bromide ion concentration being less than about
1.times.10.sup.-2 mol per liter of the solution. On the other hand,
concentrations of iodide ions exceeding about 5.times.10.sup.-2 mol per
liter of the solution is not preferred in view of desilvering ability of
the solution, the same concern as in the case of using more than about 2
mol of the bormide ions per liter of the solution.
Moreover, when the bleach-fixing solution contains both bromide ions and
iodide ions, the bromide ions are desirably present in an amount from
about 1.times.10.sup.-2 to about 2 mol per liter of the solution, and the
iodide ions are present in an amount from about 5.times.10.sup.-4 to about
5.times.10.sup.-2 mol per liter of the solution.
The above-noted objects of the present invention can be achieved by the use
of any of bromide ions and iodide ions, alone or in combination, and the
selection of using bromide ions and/or iodide ions can be made depending
on the conditions to be employed during processing.
In order to control the concentration of bromide ions and/or iodide ions
within the above described ranges, they can be directly added to the
bleach-fixing solution, or may be added together with a replenisher.
Further, they can be partially carried over from a pre-bath.
The silver halide emulsion which can be used in the present invention
comprises silver halide containing at least about 80 mol% of silver
chloride and substantially no silver iodide. The content of silver
chloride in the silver halide emulsion is preferably at least 90 mol%, and
more preferably at least 95 mol%. A pure silver chloride emulsion can be
employed, if desired. When the content of silver chloride in the emulsion
is lower than about 80 mol% color development proceeds slowly, whereby it
is difficult to obtain sufficiently high color density.
The term "silver halide emulsion containing substantially no silver iodide"
as used in the present invention means a silver halide emulsion wherein
the silver iodide content is not more than about 1 mol%, and more
preferably not more than 0.5 mol%. Most preferably, the silver halide
emulsion does not contain silver iodide at all. Silver iodide is not
preferred in the emulsion due to retardation in development speed and
increase in fog formation in some cases.
The amount of silver halide coated on a reflective support (calculated in
terms of silver) is preferably not more than about 0.78 g/m.sup.2. When
the amount of the silver halide coated is too great, color development
again proceeds slowly, whereby it is difficult to obtain sufficiently high
color density.
The average grain size of silver halide grains in the silver halide
emulsion used in the present invention (the grain size being defined as
grain diameter if the grains are spherical, wherein the average is based
on projected areas of the grains) is preferably from about 0.1 .mu.m to
about 2 .mu.m, and more preferably from 0.2 .mu.m to 1.3 .mu.m. Further,
it is preferred to employ a monodispersed silver halide emulsion. The
grain size distribution, representing the degree of monodispersibility, is
preferably not more than about 0.2, and more preferably not more than 0.15
in terms of a ratio (s/d) of a statistical standard deviation(s) to an
average grain size (d).
Silver halide grains which can be used in the present invention may have
different layers in the inner portion and the surface portion, multi-phase
structures containing junctions, or may be uniform throughout the grains.
Further, a mixture of these silver halide grains having different
structures may be employed.
Silver halide grains which can be used in the present invention may have a
regular crystal structure, for example, a cubic, octahedral, dodecahedral
or tetradecahedral structure, etc., an irregular crystal structure, for
example, a spherical structure, etc., or a composite structure thereof.
Further, tabular silver halide grains can be used. Particularly, a silver
halide emulsion can be employed wherein tabular silver halide grains
having a ratio of diameter/thickness of not less than about 5, and
preferably not less than 8, account for at least about 50% of the total
projected area of the silver halide grains present. In addition, mixtures
of silver halide grains having different crystal structures may be used.
The above-described silver halide emulsions may be of the surface latent
image type, in which latent images are formed mainly on the surface
thereof, and of the internal latent image type, in which latent images are
formed mainly in the interior thereof.
Photographic emulsions as used in the present invention can be prepared in
any suitable manner, for example, by the methods as described in P.
Glafkides, Chimie et Physique Photographique, Paul Montel (1967), G. F.
Duffin, Photographic Emulsion Chemistry, The Focal Press (1966), and V. L.
Zelikman et al., Making and Coating Photographic Emulsion, The Focal Press
(1964), etc. That is, any of an acid process, a neutral process, an
ammonia process, etc., can be employed.
Soluble silver salts and soluble halogen salts can be reacted by techniques
such as a single jet process, a double jet process, or a combination
thereof. In addition, a method (a so-called reversal mixing process) in
which silver halide grains are formed in the presence of an excess of
silver ions can be employed. As one type of double jet process, a
so-called controlled double jet process in which the pAg in a liquid phase
where silver halide is formed is maintained at a pre-determined level, can
be employed. This process can result in a silver halide emulsion in which
the crystal form is regular and the particle size is nearly uniform.
Further, a silver halide emulsion which is prepared by a so-called
conversion method employing a process in which a silver halide previously
formed is converted to a silver halide having a lower solubility product
before the completion of formation of silver halide grains, or in which a
silver halide emulsion which is subjected to similar halogen conversion
after the completion of formation of silver halide grains, may also be
employed.
During the step of formation or physical ripening of silver halide grains,
cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or
complex salts thereof, rhodium salts or complex salts thereof, iron salts
or complex salts thereof, etc. may be present.
After the formation of silver halide grains, silver halide emulsions are
usually subjected to physical ripening, removal of soluble salts and
chemical ripening prior to coating.
Known silver halide solvents (for example, ammonia, potassium thiocyanate,
and the thioethers and thione compounds a described in U.S. Pat. No.
3,271,157, Japanese Patent Application (OPI) No. 12360/76, 82408/78,
144319/78, 100717/79 and 155828/79, etc.) can be employed during the steps
of formation, physical ripening or chemical ripening of the silver halide.
For removal of soluble silver salts from the emulsion after physical
ripening, a noodle washing process, a flocculation process or an
ultrafiltration process, etc. can be employed.
The silver halide emulsion which can be used in the present invention may
be sensitized by, e.g., a sulfur sensitization method using active gelatin
or compounds containing sulfur capable of reacting with silver (for
example, thiosulfates, thioureas, mercapto compounds and rhodanines,
etc.), a reduction sensitization method using reducing substances (for
example, stannous salts, amines, hydrazine derivatives,
formamidinesulfinic acid and silane compounds, etc.), a noble metal
sensitization method using metal compounds (for example, complex salts of
Group VIII metals in the Periodic Table, such as Pt, Ir, Pd, Rh, Fe, etc.,
as well as gold complex salts); and so forth; these sensitization methods
can be applied to the emulsion alone or in combination with each other.
Of the above-described chemical sensitization methods, sulfur sensitization
alone is preferred.
Further, in order to achieve the desired gradation of the color
photographic light-sensitive material, two or more monodispersed silver
halide emulsions which have substantially the same spectral sensitivity
but have differing grain sizes from each other can be mixed in one
emulsion layer, or can be coated in the form of superimposed layers
(regarding monodispersity, the coefficient of variation described above is
preferred). Moreover, two or more polydispersed silver halide emulsions,
or combinations of a monodispersed emulsion and a polydispersed emulsion,
may be employed in admixture or in the form of superimposed layers.
Each of blue-sensitive, green-sensitive and red-sensitive emulsions used in
the present invention can be spectrally sensitized with methine dyes or
other dyes so as to each have color sensitivity. Suitable sensitizing dyes
which can be employed include cyanine dyes, merocyanine dyes, complex
cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes,
hemicyanine dyes, styryl dyes, and hemioxonol dyes. Of these dyes, cyanine
dyes, merocyanine dyes and complex merocyanine dyes are particularly
useful.
Any conventionally utilized nuclei for cyanine dyes are applicable to these
dyes as basic heterocyclic nuclei. That is, a pyrroline nucleus, an
oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole
nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a
tetrazole nucleus, a pyridine nucleus, etc.; further, nucleui formed by
condensing alicyclic hydrocarbon rings with these above-described nuclei,
and nuclei formed by condensing aromatic hydrocarbon rings with these
above-descubed nuclei, that is, an indolenine nucleus, a benzindolenine
nucleus, an indole nucleus, a benzoxadole nucleus, a naphthoxazole
nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a
benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus,
etc., are appropriate. The carbon atoms of these nuclei can also be
substituted.
The merocyanine dyes and the complex merocyanine dyes that can be employed
contain as nuclei having a keto-methylene structure, 5- or 6-membered
heterocyclic nuclei such as a pyrazolin-5-one nucleus, a thiohydantoin
nucleus, a 2-thioxazolidin-2,4-dione nucleus, a thiazolidine-2,4-dione
nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus, and the like.
These sensitizing dyes can be employed individually, and can also be
employed in combination, if desired a combination of sensitizing dyes is
often used particularly for the purpose of supersensitization. Typical
examples of supersensitizing dye combinations are described in U.S. Pat.
Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293,
3,628,964, 3,666,480, 3,762,898, 3,679,428, 3,703,377, 3,769,301,
3,814,609, 3,837,862 and 4,026,707, British Pat. Nos. 1,344,281 and
1,507,803, Japanese Patent Publication Nos. 4936/68 and 12375/78, Japanese
Patent Application (OPI) Nos. 110618/77 and 109925/77, etc.
The sensitizing dyes may be present in the emulsion together with dyes
which themselves do not give rise to spectrally sensitizing effects but
exhibit a supersensitizing effect, or together with materials which do not
substantially absorb visible light but exhibit a supersensitizing effect.
It is preferred that couplers which are incorporated into photographic
light-sensitive materials are rendered diffusion resistant by means of
containing a ballast group, or by polymerization. It is also preferred
that the coupling active positions of couplers are substituted with a
group capable of being released (two-equivalent couplers) other than being
substituted with a hydrogen atom (four-equivalent couplers) from the
standpoint that the coating amount of silver may be reduced. Further,
couplers which form dyes having an appropriate diffusibility, non-color
forming couplers, or couplers capable of releasing development inhibitors
(DIR couplers) or development accelerators accompanying the coupling
reaction can be employed.
Typical yellow couplers used in the present invention include oil-protected
acylacetamide type couplers. Specific examples thereof are described in
U.S. Pat. Nos. 2,407,210, 2,875,057 and 3,265,506, etc. In the present
invention, two-equivalent yellow couplers are preferably employed, and
typical examples thereof include yellow couplers of an oxygen atom
releasing type as described in U.S. Pat. Nos. 3,408,194, 3,447,928,
3,933,501 and 4,022,620, etc., and yellow couplers of a nitrogen atom
releasing type as described in Japanese Patent Publication No. 10739/83,
U.S. Pat. Nos. 4,401,752 and 4,326,024, Research Disclosure, No. 18053
(April, 1979), British Pat. No. 1,425,020, West German Patent Application
(OLS) Nos. 2,219,917, 2,261,361, 2,329,587 and 2,433,812, etc.
.alpha.-Pivaloylacetanilide type couplers are characterized by good
fastness, particularly good light fastness, of dyes formed, and
.alpha.-benzylacetanilide type couplers are characterized by providing
high color density.
Magenta couplers which may be used in the present invention include
oil-protected indazolone type couplers, cyanoacetyl type couplers, and
preferably 5-pyrazolone type couplers and pyrazoloazole type couplers,
such as pyrazolotriazoles. Of the above-noted 5-pyrazolone type couplers,
those substituted with an arylamine group or an acylamino group at the
3-position thereof are preferred in view of the resulting hue and color
density of the dyes formed. Typical examples thereof are described in U.S.
Pat. Nos. 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896
and 3,936,015, etc. Suitable releasing groups for two-equivalent
5-pyrazolone type couplers include nitrogen atom releasing groups as
described in U.S. Pat. No. 4,310,619, and arylthio groups as described in
U.S. Pat. No. 4,351,897. Further, 5-pyrazolone type couplers having a
ballast group as described in European Pat. No. 73,636 are advantageous
because they provide high color density.
Examples of pyrazoloazole type couplers include pyrazolobenzimidazoles as
described in U.S. Pat. No. 3,369,879, and preferably
pyrazolo[5,1-c]-[1,2,4]triazoles as described in U.S. Pat. No. 3,725,067,
pyrazolotetrazoles as described in Research Disclosure, No. 24220 (June,
1984) and pyrazolopyrazols as described in Research Disclosure, No. 24230
(June, 1984). Imidazo[1,2-b]pyrazoles as described in European Pat. No.
119,741 are preferred, and pyrazolo[1,5-b]-[1,2,4]triazoles as described
in European Pat. No. 119,860 are particularly preferred in view of less
yellow subsidiary absorption and light fastness of the dyes formed.
Suitable cyan couplers which may be used in the present invention include
oil-protected naphthol type and phenol type couplers. Typical examples
thereof include naphthol type couplers as described in U.S. Pat. No.
2,474,293, and preferably oxygen atom releasing type two-equivalent
naphthol type couplers as described in U.S. Pat. Nos. 4,052,212,
4,146,396, 4,228,233 and 4,296,200, etc. Specific examples of phenol type
couplers are described in U.S. Pat. Nos. 2,369,929, 2,801,171, 2,772,162
and 2,895,826, etc.
Cyan couplers which are fast to humidity and temperature are preferably
used in the present invention. Typical examples thereof include phenol
type cyan couplers having an alkyl group higher than a methyl group at the
metaposition of the phenol nucleus as described in U.S. Pat. No.
3,772,002, 2,5-diacylamino-substituted phenol type couplers as described
in U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011 and
4,327,173, West German Patent Application (OLS) No. 3,329,729, and
Japanese Patent Application No. 42671/83, etc., and phenol type couplers
having a phenylureido group at the 2-position thereof and an acylamino
group at the 5-position thereof as described in U.S. Pat. Nos. 3,446,622,
4,333,999, 4,451,559 and 4,427,767, etc.
Further, couplers capable of forming appropriately diffusible dyes can be
used together with the above-described dyes in order to improve
graininess. Specific examples of such diffusible dye types of magenta
couplers are described in U.S. Pat. No. 4,366,237 and British Pat. No.
2,125,570, etc. and those of yellow, magenta and cyan couplers are
described in European Pat. No. 96,570 and West German Patent Application
(OLS) No. 3,234,533, etc.
These dye forming couplers and special couplers described above may be used
in the form of polymers, including dimers or higher polymers. Typical
examples of dye forming polymer couplers are described in U.S. Pat. Nos.
3,451,820 and 4,080,211, etc. Specific examples of magneta polymer
couplers are described in British Pat. No. 2,102,173 and U.S. Pat. No.
4,367,282, etc.
Two or more kinds of these various couplers which can be used in the
present invention can be incorporated together into the same layer for the
purpose of satisfying the properties required of the color photographic
light-sensitive materials, or the same compound can be incorporated into
two or more different layers, as desired.
Couplers which can be used in the present invention may be introduced into
the color photographic light-sensitive material using an oil
droplet-in-water type dispersing method, wherein couplers are dissolved in
either an organic solvent having a high boiling point of about 175.degree.
C. or more, a so-called auxiliary solvent having a low boiling point, or a
mixture thereof. Then, the solution is finely dispersed in an aqueous
medium such as water or an aqueous gelatin solution, etc., in the presence
of a surface active agent. Specific examples of the organic solvents
having a high boiling point are described in U.S. Pat. No. 2,322,027, etc.
Preparation of such a dispersion may be accompanied by phase inversion.
Further, dispersions can be utilized for coating after removing or
reducing the amount of the auxiliary solvent therein by distillation,
noodle washing or ultrafiltration, etc., if desired.
Specific examples of the organic solvent having a high boiling point
include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl
phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, etc.), phosphoric
or phosphonic acids esters (for example, triphenyl phosphate, tricresyl
phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate,
tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate,
trichlorophenyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.),
benzoic acid esters (for example, 2-ethylhexyl benzoate, dodecyl benzoate,
2-ethylhexyl-p-hydroxybenzoate, etc.), amides (for example,
diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols
(for example, isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic
carboxylic acid esters (for example, dioctyl azelate, glycerol
tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline
derivatives (for example, N,N-dibutyl-2-butoxy-5-tert-octylaniline, etc.),
hydrocarbons (for example, paraffin, dodecylbenzene,
diisopropylnaphthalene, etc.), etc.
Suitable auxiliary solvents include organic solvents having a boiling point
of about 30.degree. C. or more, preferably from about 50.degree. C. to
about 160.degree. C., etc. Typical examples of such auxiliary solvents
include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl
ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, etc.
The processes and effects of latex dispersing methods for incorporating the
couplers into the photographic material, as well as specific examples of
suitable latexes to be used in this type of incorporation, are described
in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos.
2,541,274 and 2,541,230, etc.
The color couplers are generally employed in an amount of from about 0.001
mol to about 1 mol per mol of the light-sensitive silver halide contained
in a layer into which the couplers are to be incorporated. It is preferred
that the amounts of yellow couplers, magenta couplers and cyan couplers
employed are in ranges of from about 0.01 mol to about 0.5 mol, from about
0.003 mol to about 0.3 mol and from about 0.002 mol to about 0.3 mol per
mol of the light-sensitive silver halide, respectively.
The color photographic light-sensitive material used in the present
invention may contain hydroquinone derivatives, aminophenol derivatives,
amines, gallic acid derivatives, catechol derivatives, ascorbic acid
derivatives, non-color-forming couplers, sulfonamidophenol derivatives,
etc., as color fog preventing agents or color mixing preventing agents.
Further, in the color photographic light-sensitive material used in the
present invention, various known color fading preventing agents can be
employed. Typical examples of organic color fading preventing agents
include hindered phenols (for example, hydroquinones, 6-hydroxychromans,
5-hydroxycoumarians, spirochromans, p-alkoxyphenols, bisphenols, etc.),
gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered
amines, or ether or ester derivatives thereof derived from each of these
compounds by sililation or alkylation of the phenolic hydroxy group
thereof. Further, metal complexes represented by (bissalicylaldoxymato)
nickel complexes and (bis-N,N-dialkyldithiocarbamato) nickel complexes may
be employed as color fading preventing agents.
For the purpose of preventing degradation of yellow dye images due to heat,
humidity and light, compounds having both a hindered amine partial
structure and a hindered phenol partial structure in the molecule, as
described in U.S. Pat. No. 4,268,593, provide good results. For the
purpose of preventing degradation of magenta dye images, particularly
degradation due to light, spiroindanes as described in Japanese Patent
Application (OPI) No. 159644/81 and chromans substituted with a
hydroquinone diether or monoether, as described in Japanese Patent
Application (OPI) No. 89835/80, provide preferred results.
In order to improve preservability, particularly light fastness of cyan dye
images, it is preferred to also employ a benzotriazole type ultraviolet
ray absorbing agent. Such an ultraviolet ray absorbing agent may be
emulsified together with a cyan coupler. The coating amount of the
ultraviolet ray absorbing agent is selected so as to sufficiently improve
the light stability of cyan dye images. When the amount of the ultraviolet
ray absorbing agent employed is too large, however, undesirable yellow
coloration may occur in unexposed areas (white background areas) of color
photographic materials containing them. Therefore, the amount is usually
preferred to be in a range from about 1.times.10.sup.-4 mol/m.sup.2 to
about 2.times.10.sup.-3 mol/m.sup.2 and particularly from
5.times.10.sup.-4 mol/m.sup.2 to 1.5.times.10.sup.-3 mol/m.sup.2.
In color paper having a conventional light-sensitive layer structure, the
ultraviolet ray absorbing agent is incorporated into one of two layers
adjacent to a red-sensitive emulsion layer containing a cyan coupler, and
preferably incorporated into both adjacent layers thereof. When the
ultraviolet ray absorbing agent is incorporated into an intermediate layer
positioned between a green-sensitive emulsion layer and a red-sensitive
emulsion layer, it may be emulsified together with a color mixing
preventing agent. In the case of adding the ultraviolet ray absorbing
agent to a protective layer, another protective layer may be separately
provided thereon as an outermost layer. A matting agent having an
appropriate particle size, etc. can be incorporated into the outermost
protective layer.
The color photographic light-sensitive ma | | |
