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| United States Patent | 4962014 |
| Link to this page | http://www.wikipatents.com/4962014.html |
| Inventor(s) | Ishikawa; Takatoshi (Kanagawa, JP);
Nakajima; Junya (Kanagawa, JP) |
| Abstract | A process for processing a silver halide color photographic material after
imagewise exposing said silver halide color photographic material,
comprising color developing, blixing, and then washing, wherein the
processing time for said blixing is from about 30 seconds to about 70
seconds, the blixing liquid for said blixing contains from about 0.08 to
about 0.30 mol/liter of sulfite ion, and the replenishing amount of
washing water for said washing is from about 3 times to about 50 times the
amount of processing liquid carried from the previous bath per unit area
of said color photographic material. |
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Title Information  |
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| Publication Date |
October 9, 1990 |
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| Filing Date |
January 19, 1989 |
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| Parent Case |
This is a continuation, of application Ser. No. 06/927,615, filed 11/6/86
now abandoned.
FIELD OF THE INVENTION
This invention relates to a process for processing silver halide color
photographic materials, and more particularly to a process for processing
silver halide color photographic materials capable of shortening the
processing time for the bleach-fix (blix) process and greatly reducing the
amount of replenisher required for the water-wash step without reducing
the stability or storage property of color images formed.
BACKGROUND OF THE INVENTION
Hitherto, many investigations have been made for the reduction of
processing time for silver halide color photographic materials. In these
investigations, in regard to shortening of the processing time of a blix
process, the development of new blixing agents or bleaching agents have
been the main purpose.
However, in these previous attempts, typically, the cost of compounds is
high, or the effect of accelerating blix is insufficient, and fully
satisfactory procedures and compounds have not yet been discovered. Thus,
the actual practice has been to shorten the processing time by controlling
the coated silver amount of the silver halide color photographic materials
to be processed as well as the bleaching agent, fixing agent, pH and/or
the concentrations of salts in the blix solution.
On the other hand, in the washing step of photographic processing, a
processing process capable of greatly saving water has recently been
proposed, mainly for saving water resources and reducing conduits for
washing at installations of processors. These techniques are disclosed,
for example, in Japanese Patent Application (OPI) Nos. 70549/81,
132146/82, 8543/82, 18631/83, 184343/84, 184345/84, 14834/83 (the term
"OPI" as used herein refers to a "published unexamined Japanese patent
application"), etc.
However, the attempt of performing the combination of shortening of the
processing time of a blix process and the water saving process encounters
a new problem, in that the storage property of color images of color
photographic materials after processing is reduced. In other words, when
the blixing time is shortened and then a washing step with water saving is
employed, yellow stains and/or magenta stains are more liable to occur on
the color photographic materials thus processed, e.g., prints with the
passage of time. In particular, it has been found that when 2-equivalent
magenta couplers showing high coloring property are used, the aforesaid
occurrence of magenta stain becomes more severe.
It is presumed that the magenta stain occurs because washing of color
developer components carried from the previous bath is insufficient as a
result of shortening of the blixing time and also the color developer
components are not sufficiently washed away as a result of the great
saving of wash replenisher in the wasing step.
SUMMARY OF THE INVENTION
The object of this invention is, therefore, to provide a process for
processing silver halide color photographic materials, which gives color
images having good storage properties even in the processing step of
greatly shortening the blixing time and also greatly saving the amount of
replenisher for washing step.
As a result of extensive investigations, it has now been discovered that
the above and other objects of the present invention can be attained by a
process for processing a silver halide color photographic material after
imagewise exposing the silver halide color photographic material,
comprising color developing, blixing and then washing, wherein the
processing time for the blix step is from about 30 seconds to about 70
seconds, the blix liquid which is used for the blix step contains from
about 0.08 to about 0.30 mol/liter of sulfite ion, and the replenishing
amount of wash water for the washing step is from about 3 times to about
50 times the amount of processing liquid carried from the previous bath
per unit area of the color photographic material.
DETAILED DESCRIPTION OF THE INVENTION
The invention is explained below in more detail.
The processing time for the blix step in the present invention is from
about 30 seconds to about 70 seconds, which is greatly shortened as
compared with the processing time (about 1 minute 30 seconds) for a
conventional blix step. The processing time for the blix step (hereinafter
referred to simply as "blixing time") is the time required for a
light-sensitive material from being brought into contact with a blix
liquid to being brought into contact with wash water of the subsequent
wash bath. That is, the blixing time is the sum of the time that a
light-sensitive material is immersed in a blix bath and the time required
for moving the light-sensitive material from the blix bath to the
subsequent wash bath, i.e., the time that the light-sensitive material is
in the air between both of the baths. The preferred blixing time in this
invention is from 40 seconds to 60 seconds.
The blix liquid for use in the present invention contains a sulfurous acid
ion releasing compound such as a sulfite (e.g., sodium sulfite, potassium
sulfite, ammonium sulfite, etc.), a hydrogensulfite (e.g., ammonium
hydrogensulfite, sodium hydrogensulfite, potassium hydrogensulfite, etc.),
a metahydrogensulfite (e.g., potassium metahydrogensulfite, sodium
metahydrogensulfite, ammonium metahydrogensulfite, etc.), etc., as
preservatives. It is necessary that such a compound is contained in the
blix liquid in an amount of from about 0.08 to 0.30 mol/liter, and
preferably from about 0.10 to 0.20 mol/liter of sulfite ion. If the
concentration of the sulfite ion is less than 0.08 mol/liter, the
above-described stain preventing faculty is insufficient and if the
concentration is about 0.30 mol/liter, the removal of silver becomes
insufficient.
Other preservatives which can be used in this invention include
hydroxylamine, hydrazine, a hydrogensulfite addition product of an
aldehyde compound (e.g., sodium acetaldehyde hydrogensulfite), etc.
Bleaching agents which can be used for the blix liquid in the present
invention include organic complex salts of iron(III) (e.g., iron(III)
complex salts of aminopolycarboxylic acids such as
ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc.,
or organic phosphonic acids such as aminopolyphosphonic acid,
phosphonocarboxylic acid, etc.); organic acids such as citric acid,
tartaric acid, malic acid, etc.; persulfates; hydrogen peroxide, etc. In
these substances, organic complex salts of iron(III) are preferred from
the viewpoints of quick processing and the prevention of environmental
pollution.
Examples of the useful aminopolycarboxylic acid, aminopolyphosphonic acid,
and organic phosphonic acid for forming the organic complex salts of
iron(III) include:
Ethylenediaminetetraacetic acid,
Diethylenetriaminepentaacetic acid,
Ethylenediamine-N-(.beta.-oxyethyl)-N,N',N'-triacetic acid,
1,2-Diaminopropanetetraacetic acid,
Triethylenetetraminehexaacetic acid,
Propylenediaminetetraacetic acid,
Nitrilotriacetic acid,
Nitrilotripropionic acid,
Cyclohexanediaminetetraacetic acid,
1,3-Diamino-2-propanoltetraacetic acid,
Methyliminodiacetic acid,
Iminodiacetic acid,
Hydroxyliminodiacetic acid,
Dihydroxyethylglycine ethyl ether diaminetetraacetic acid,
Glycol ether diaminetetraacetic acid,
Ethylenediaminetetrapropionic acid,
Ethylenediaminedipropionic acid,
Phenylenediaminetetraacetic acid,
2-Phosphonobutane-1,2,4-triacetic acid,
1,3-Diaminopropanol-N,N,N',N'-tetramethylenephosphonic acid,
Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid,
1,3-Propylenediamine-N,N,N',N'-tetramethylenephosphonic acid,
1-Hydroxyethylidene-1,1'-diphosphonic acid, etc.
The above-described compounds may be in the forms of sodium salts,
potassium salts, lithium salts, or ammonium salts. In these compounds, the
iron(III) complex salts of ethylenediaminetetraacetic acid,
diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
1,2-diaminopropanetetraacetic acid, and methyliminodiacetic acid are
preferred because of their high blixing power.
The amount of the bleaching agent per liter of the blix liquid is
preferably from 0.15 mol to 0.5 mol, and more preferably from 0.2 to 0.4
mol, for the purpose of increasing the processing speed.
As fixing agents which can be used for the blix liquid in the present
invention, known fixing agents, e.g., thiosulfates such as sodium
thiosulfate, ammonium thiosulfate, etc.; thiocyanates such as sodium
thiocyanate, ammonium thiocyanate, etc.; thioether compounds such as
ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol, etc.; and
water-soluble silver halide solvents such as thioureas, etc., can be used
singly or as a mixture thereof.
Also, a special blix liquid comprising a combination of the fixing agents
described in Japanese Patent Application (OPI) No. 155354/80 and a large
amount of a halide such as potassium iodide can be used.
In the present invention, the use of thiosulfates, particularly ammonium
thiosulfate is preferred.
The amount of the fixing agent per liter of the blix liquid is generally
from 0.3 to 2 mols, and preferably from 0.5 to 1.0 mol.
The pH region of the blix liquid for use in the present invention is
preferably from 4 to 8, more preferably from 5 to 7.5. If the pH is lower
than 4, the deterioration of the blix liquid and the conversion of cyan
dyes into leuco compounds are accelerated, although the silver removal may
be improved. If the pH is higher than 8, the silver removal is delayed and
stain is liable to form.
For adjusting the pH of the blix liquid, if necessary, hydrochloric acid,
sulfuric acid, nitric acid, acetic acid, hydrogencarbonates, ammonia,
potassium hydroxide, sodium hydroxide, sodium carbonate, potassium
carbonate, etc., can be used.
Also, the blix liquid for use in the present invention may further contain
an optical whitening agent, a defoaming agent, a surface active agent,
polyvinylpyrrolidone, an organic solvent such as methanol, etc.
Furthermore, the blix liquid for use in the present invention can, if
necessary, contain a bleaching accelerator. Specific examples of useful
bleaching accelerators include compounds having a mercapto group or a
disulfide group described in U.S. Pat. No. 3,893,858, West German Pat.
Nos. 1,290,812, 2,059,988, Japanese Patent Application (OPI) Nos.
32736/78, 57831/78, 37418/78, 65723/78, 72623/78, 95630/78, 95631/78,
104232/78, 124424/78, 141623/78, 28426/78, Research Disclosure, No. 17129
(July, 1978), etc.; thiazolidine derivatives as described in Japanese
Patent Application (OPI) No. 140129/75; thiourea derivatives described in
Japanese Patent Publication No. 8506/70, Japanese Patent Application (OPI)
Nos. 20832/77, 32735/78, U.S. Pat. No. 3,706,561, etc.; iodides described
in West German Pat. No. 1,127,715, Japanese Patent Application (OPI) No.
16235/83, etc.; polyethylene oxides described in West German Pat. Nos.
966,410, 2,748,430, etc.; polyamine compounds described in Japanese Patent
Publication No. 8836/70, etc.; the compounds described in Japanese Patent
Application (OPI) Nos. 42434/74, 59644/74, 94927/78, 35727/79, 26506/80,
and 163940/83; and iodine ions and bromine ions. In these compounds, the
compounds having a mercapto group or a disulfide group are preferred from
the viewpoint of high acceleration effect, and the compounds described in
U.S. Pat. No. 3,893,858, West German Pat. No. 1,290,812, and Japanese
Patent Application (OPI) No. 95630/78 are particularly preferred.
Still further, the blix liquid for use in the present invention may contain
a rehalogenating agent such as bromides (e.g., potassium bromide, sodium
bromide, ammonium bromide, etc.), chlorides (e.g., potassium chloride,
sodium chloride, ammonium chloride, etc.), or iodides (e.g., ammonium
iodide, etc.). Also, the blix liquid may further contain, if necessary,
inorganic acids or organic acids having a pH buffer faculty and the alkali
metal or ammonium salts thereof, such as boric acid, borax, sodium
metaborate, acetic acid, sodium acetate, sodium bromate, potassium borate,
phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium
citrate, tartaric acid, etc., and a corrosion preventing agent, such as
ammonium nitrate, guanidine, etc.
The silver halide color photographic materials of the present invention are
washed after blix processing. It is a feature of the present invention
that in the washing process in the present invention, the replenishing
amount of water required is greatly reduced. That is, the replenishing
amount of washing water in the present invention is from about 3 to about
50 times the amount of the liquid carried from the previous bath per unit
area of the light-sensitive material. In other words, the replenishing
amount of wash water required in accordance with the present invention can
be greatly reduced, to an amount of from about 1/70 to 1/4 of the
replenishing amount of wash water (about 200 times the amount of the
liquid carried from the previous bath per unit area of light-sensitive
material) in ordinary washing process.
The optimum water replenishment amount utilized in the practice of the
present invention depends upon the amount of liquid carried by
light-sensitive materials from the previous bath and the washing process
system (e.g., the number of baths in multistage countercurrent washing
process), and, hence, it is difficult to specifically define the amount.
However, in the case, for example, of three bath countercurrent washing
process, it is preferred that the amount of replenishing wash water is
from about 5 times to about 15 times the amount of the processing liquid
carried from the previous bath per unit area of light-sensitive material.
The washing process in the present invention includes a process of
performing so-called "stabilization process" without employing a
substantial washing step in place of ordinary "washing process". Thus,
"washing process" or "water washing process" in the present invention is
used in a broad sense as described above.
The washing time in the present invention is typically from 30 seconds to 5
minutes, and preferably from 40 seconds to 4 minutes. The washing time in
the present invention means a time required for a light-sensitive material
to proceed from being brought into contact with wash water to reaching a
drying zone, which is a final step. Also, when the washing step is a
multistage countercurrent washing step, the washing time means the whole
washing time required for a light-sensitive material from being brought
into contact with wash water in the first wash bath to reaching the drying
zone. When the so-called "stabilization process" is employed in place of
ordinary washing process, the abovedescribed definition for washing time
is applied.
The washing temperature in the present invention is typically from
15.degree. C. to 45.degree. C., and preferably from 20.degree. C. to
35.degree. C.
For the washing step, various kinds of compounds may be used for the
prevention of occurrence of precipitation or the stabilization of washing
water. For example, various antibacterial and antifungal agents described,
for example, in Journal of Antibacterial and Antifungal Agents, Vol. 11,
No. 5, pp. 207 to 223 (1983) and Hiroshi Horiguchi, Bokin Bobai no Kagaku
(Antibacterial and Antifunqal Chemistry), published by Sankyo Shuppan Co.,
Ltd. on Jan. 10, 1982, for preventing the generation of various bacteria,
algae, and fungi; metal salts such as magnesium salts, aluminum salts,
etc.; alkali metal salts; ammonium salts; or surface active agents for
reducing drying load or preventing uneven drying may be, according to
requirement, added to wash water. Also, the compounds described in West,
Photograohic Science and Engineering, Vol. 6, pp. 344 to 359 (1965) may be
added to wash water. The addition of a chelating agent or an antibacterial
or antifungal agent is particularly effective.
The employment of a multistage countercurrent washing step (e.g., with 2 to
9 baths) as the washing step is advantageous for saving the amount of
replenishing wash water required. Furthermore, the multistage
countercurrent stabilizaticn processing step (so-called stabilization
process) described in Japanese Patent Application (OPI) No. 8543/82 may be
employed in place of an ordinary washing step. The stabilization bath(s)
contains various kinds of compounds for the purpose of stabilizing color
images formed. For example, there are various buffers (e.g., a combination
of borates, metaborates, borax, phosphates, carbonates, potassium
hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids,
dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as
formalin, etc., for adjusting the pH of films or layers. Still further,
chelating agents (e.g., inorganic phosphoric acids, aminopolycarboxylic
acids, organic phosphonic acids, aminopolyphosphonic acids,
phosphonocarboxylic acids, etc.), sterilizers (e.g., thiazoles,
isothiazoles, halogenated phenols, sulfanylamides, benzotriazoles, etc.),
surface active agents, optical whitening agents, hardening agents, etc.,
may be used. They can be used solely or as a combination of two or more
same kind of or different kinds of compounds.
Also, various ammonium salts such as ammonium chloride, ammonium nitrate,
ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium
thiosulfate, etc., may be added to the stabilization bath(s) as a film pH
adjusting agent for the processor.
The color development step which can be used in the present invention is
explained below.
The processing time for the color developmenr step for use in this
invention is generally from about 40 seconds to about 10 minutes, and
preferably from about 50 seconds to about 4 minutes. The developing time
in the present invention is preferably as short as practicably possible
for the purpose of shortening the total processing time for all of the
processing steps.
The color developer which is used for the color development processing in
the present invention is an aqueous alkaline solution, preferably
containing an aromatic primary amine developing agent as the main
component. As such color developing agent, p-phenylenediamine series
compounds are preferably used. Specific examples of the p-phenylenediamine
series compounds include 3-methyl-4-amino-N,N-diethylaniline,
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-.beta.-methanesulfonamidoethylaniline,
3-methyl-4-amino-N-ethyl-N-.beta.-methoxyethylaniline, etc., and sulfates,
hydrochlorides, phosphates, p-toluenesulfonates, tetraphenylborates,
p-(t-octyl)benzenesulfonates, etc., of the above-described compounds.
Also, for shortening the development time, the concentration of the
developing agent in the color developer and the pH of the color developer
are very important factors. In the present invention, the concentration of
the developing agent is generally from about 1.0 g to about 15 g, and
preferably from about 3.0 g to about 8.0 g, per liter of the color
developer. The pH of the color developer is generally higher than 9, and
preferably from about 9.5 to about 12.0.
The processing temperature of the color developer in the present invention
is generally from 30.degree. C. to 50.degree. C., and preferably from
31.degree. C. to 45.degree. C.
Also in the present invention, various development accelerators may be
used, if desired.
As the development accelerator, benzyl alcohol is effectively used, but
other compounds, for example, the various pyrimidium compounds described
in U.S. Pat. No. 2,648,604, Japanese Patent Publication No. 9503/69, U.S.
Pat. No. 3,171,247, etc., other cationic compounds, cationic dyes such as
phenosafranine, etc., neutral salts such as thallium nitrate, potassium
nitrate, etc., the polyethylene glycol and the derivatives thereof
described in Japanese Patent Publication No. 9304/69, U.S. Pat. Nos.
2,533,990, 2,531,832, 2,950,970, 2,577,127, etc., nonionic compounds such
as polythioethers, etc., the thioether compounds described in U.S. Pat.
No. 3,201,242, etc., may be used.
For the development step in the present invention, various antifoggants may
be used for preventing the formation of development fog. As the
antifoggants in the development step, alkali metal halides such as
potassium bromide, sodium bromide, potassium iodide, etc., and organic
antifoggants are preferable. Useful organic antifoggants include, for
example, nitrogen-containing heterocyclic compounds such as benzotriazole,
6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
5-nitrobenzotriazole, 5-chlorobenzotriazole,
2-thiazolylmethylbenzimidazole, hydroxyazaindolizine, etc.,
mercapto-substituted heterocyclic compounds such as
1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole,
2-mercaptobenzothiazole, etc., and mercapto-substituted aromatic compounds
such as thiosalicylic acid, etc. In the compounds described above, the
halides as described above are particularly preferred. In addition, the
antifoggant also includes an antifoggant which is dissolved from color
photographic materials during processing and accumulates in the color
developer.
Furthermore, the color developers for use in the present invention may
contain a pH buffer such as carbonates, borates, or phosphates of an
alkali metal; preservatives such as hydroxylamine, triethanolamine, the
compounds described in West German Patent Application (OLS) No. 2,622,950,
sulfites, hydrogensulfites, etc.; organic solvents such as diethylene
glycol, etc.; dyeforming couplers; competing couplers; nucleating agents
such as sodium boron hydride, etc.; auxiliary developing agents such as
1-phenyl-3-pyrazolidone, etc.; tackifiers; and chelating agents such as
aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid,
nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic
acid, N-hydroxymethylethylenediaminetriacetic acid,
diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid,
and the compounds described in Japanese Patent Application (OPI) No.
195845/83), aminophosphonic acids (1-hydroxyethylidene-1,1'-diphosphonic
acid, the organic phosphonic acids described in Research Disclosure, No.
18170 (May, 1979), aminotris(methylenephosphonic acid),
ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, etc.), and the
phosphonocarboxylic acids described in Japanese Patent Application (OPI)
Nos. 102726/77, 42730/78, 121127/79, 4024/80, 4025/80, 126241/80,
65955/80, 65956/80 and Research Disclosure, No. 18170 (May, 1979).
Also, the color development bath can be divided into two or more baths, if
desired, whereby a color developer replenisher is supplied to the first
bath or the final bath to shorten the developing time or reduce the amount
of the replenisher.
The silver halide color photographic materials which are processed by the
process of the presenr invention may contain therein various kinds of
1-phenyl-3-pyrazolidones for accelerating the color development. Specific
examples of these 1-phenyl-3-pyrazolidones are described in Japanese
Patent Application (OPI) Nos. 64339/81, 144547/82, 211147/82, 50532/83,
50536/83, 50533/83, 50534/83, 50535/83, 115438/83, etc.
Also, in the case of performing continuous processing, a constant finish is
obtained by preventing the deviation of liquid compositions by using
replenisher for each processing liquid. The amount of each replenisher may
be reduced to a half or less of a standard amount of the replenisher of
conventional processes for the reduction of cost, etc.
Each processing bath may, if desired, be equipped with a heater, a
temperature sensor, a liquid level sensor, a circulation pump, a filter, a
floating lid, a squeezer, a nitrogen stirrer, an air stirrer, etc.
Silver halide color photographic materials to which the process of the
present invention is applied are explained below in more detail.
For the photographic emulsion layers of the color photographic materials
for use in the present invention, silver chloride, silver chlorobromide,
silver bromide, silver iodochlorobromide, or silver iodobromide may be
used as the silver halide, but for shortening the blixing time, silver
chloride, silver chlorobromide, or silver bromide is preferred, and in the
case of using silver iodochlorobromide or silver iodobromide, it is
preferred that the content of iodide is less than 1 mol %. Also, for the
coated amount of silver (silver coverage) of the silver halide emulsion(s)
to have an influence on, in particular, shortening of the blixing time in
accordance with the present invention, the coated amount of silver is
preferably not more than 2.0 g, and more preferably 1.0 g or less, per
square meter of the color photographic material.
The silver halide photographic emulsions of the color photographic
materials for use in the present invention may contain dye-forming
couplers, that is, compounds capable of coloring by oxidative coupling
with an aromatic primary amine developing agent (e.g., phenylenediamine
derivatives and aminophenol derivatives) in color development. For
example, magenta couplers include 5-pyrazolone couplers,
pyrazolobenzimidazole couplers, cyanoacetylcumarone couplers, open chain
acylacetcnitrile couplers, etc.; yellow couplers include acylacetamide
couplers (e.g., benzoylacetanilides, pivaloylacetanilides, etc.), etc.;
and cyan couplers include naphthol couplers and phenol couplers.
It is preferred that these couplers are non-diffusible couplers having a
hydrophobic group referred to as ballast group in the coupler molecule or
are polymerized couplers. The couplers may be 4-equivalent or 2-equivalent
with respect to silver ions. Furthermore, the couplers may be colored
couplers having a color correction effect or so-called DIR couplers or DAR
couplers, i.e., couplers releasing a development inhibitor or development
accelerator with the development.
Also, in place of DIR couplers, a non-coloring DIR coupling compound which
gives a colorless product by the coupling reaction and releases a
development inhibitor may be used.
Furthermore, the light-sensitive material may contain compounds releasing a
development inhibitor with the color development in place of the
above-described DIR couplers.
The above-described couplers, etc., may exist in one emulsion layer as a
combination of two or more, and the same coupler or compound may exist in
two or more emulsion layers in order to satisfy the characteristics
required for a particular light-sensitive material.
The process of the present invention is particularly preferably applied to
silver halide color photographic materials containing a magenta coupler
represented by at least one of formulae (I) and (II), i.e.,
##STR1##
wherein R.sub.1 represents a hydrogen atom or a monovalent organic
substituent; X represents a hydrogen atom or a group capable of releasing
upon occurrence of a coupling reaction with the oxidation product of an
aromatic primary amine developing agent; and Za, Zb and Zc each represents
a methine group, a substituted methine group, .dbd.N-- or --NH--; at least
one of said Za, Zb and Zc represents .dbd.N-- or --NH--; one of the Za--Zb
bond and the Zb--Zc bond is a double bond and the other is a single bond;
and when the Zb--Zc bond is a carbon-carbon double bond, it may be a part
of an aromatic ring; or said magenta coupler represented by formula (I)
forms a dimer or oligomer at said R.sub.1 or X; or when said Za, Zb or Zc
is a substitured methine group, said magenta coupler forms a dimer or
oligomer at said substituted methine group; and
##STR2##
wherein W represents an aryl group; Z represents an alkyl group, an aryl
group or a heterocyclic group; and Y represents an acylamino group, a
ureido group or an anilino group.
The magenta couplers represented by formula (I) above are explained in more
detail below.
The dimer or oligomer in formula (I) means the coupler having at least 2
moieties represented by formula (I) in 1 molecule and includes a bis
compound, an oligomer, and a polymeric coupler. The polymeric coupler may
be a homopolymer composed of 2 or more monomers (preferably a monomer
having a vinyl group, hereinafter referred to as a vinyl monomer) having
the moiety represented by formula (I) or a copolymer of the
above-described monomer and a non-coloring ethylenical monomer which does
not cause coupling with the oxidation product of an aromatic primary amine
developing agent.
Preferred examples of the magenta couplers represented by formula (I)
include 1H-imidazo[1,2-b]pyrazoles, 1H-pyrazolo[1,5-b]pyrazoles,
1H-pyrazolo[5,1-c][1,2,4]triazoles, 1H-pyrazolo[1,5-b][1,2,4]triazoles,
1H-pyrazolo[1,5-d]tetrazoles, and 1H-pyrazolo[, 1,5-a]benzimidazoles.
These compounds are represented by formulae (III), (IV), (V), (VI), (VII)
and (VIII) shown below, respectively, and in these compounds, the
compounds represented by formulae (v) and (vI) are particularly preferred.
##STR3##
In formulae (III) to (VIII) described above, R.sub.2, R.sub.3 and R.sub.4
each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl
group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy
group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a
silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group,
a ureido group, an imido group, a sulfamoylamino group, a carbamoylamino
group, an alkylthio group, an arylthio group, a heterocyclic thio group,
an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido
group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl
group, a sulfinyl group, an alkoxycarbonyl group or an aryloxycarbonyl
group; and X represents a hydrogen atom, a halogen atom, a carboxy group
or a group which is bonded to the carbon atom at the coupling position
through an oxygen atom, a nitrogen atom or a sulfur atom, and is released
by coupling reaction.
The compounds of formulae (III) to (VIII) shown above include the case that
R.sub.2, R.sub.3, R.sub.4 or X forms a divalent group and the compound
forms a bis compound at the divalent group. Also, when the moiety
represented by formula (III) to (VIII) is in the vinyl monomer, said
R.sub.2, R.sub.3 or R.sub.4 represents a single bond or a linking group
and in this case the moiety represented by formulae (III) to VIII) is
bcnded to a vinyl group through the bond or linking group.
Preferably, R.sub.2, R.sub.3 and R.sub.4 each represents a hydrogen atom, a
halogen atom (e.g., a chlorine atom, a bromine atom, etc.), an alkyl group
(e.g., a methyl group, a propyl group, a t-butyl group, a trifluoromethyl
grcup, a tridecyl group, a 3-(2,4-di-t-amylphenoxy)propyl group, a
2-dodecyloxyethyl group, a 3-phenoxypropyl group, a 2-hexylsulfonylethyl
group, a cyclopentyl group, a benzyl group, etc.), an aryl group (e.g., a
phenyl group, a 4-t-butylphenyl group, a 2,4-di-t-amylphenyl group, a
4-tetradecanamidophenyl group, etc.), a heterocyclic group (e.g., a
2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a
2-benzothiazolyl group, etc.), a cyano group, an alkoxy group (e.g., a
methoxy group, an ethoxy group, a 2-methoxyethoxy group, a
2-dodecyloxyethoxy group, a 2-methanesulfonylethoxy group, etc.), an
aryloxy group (e.g., a phenoxy group, a 2-methylphenoxy group, a 4-t
butylphenoxy group, etc.), a heterocyclic oxy group (e.g., a
2-benzimidazolyloxy group, etc.), an acyloxy group (e.g., an acetcxy
group, a hexadecanoyloxy group, etc.), a cartamoyloxy group (e.g., an
N-phenylcarbamoyloxy group, an N-ethylcarbamoyloxy group, etc.), a
silyloxy group (e.g., a trimethylsilyloxy group, etc.), a sulfonyloxy
group (e.g., a dodecylsulfonloxy group, etc. , an acylamino group (e.g.,
an acetamido group, a benzamido group, a tetradecanamido group, an
.alpha.-(2,4-di-t-amylphcnoxy) butyramido group, a
.gamma.-(3-t-butyl-4-hydroxyphenoxy)butylamino group, an
.alpha.-[4-(4-hydroxyphenylsulfonyl)phenoxy]decanamido group, etc.), an
anilino group (e.g., a phenylamino group, a 2-chloroanilino group, a
2-chloro-5-tetradecananilino group, a 2-chloro-5-dodecyloxycarbonylanilino
group, an N-acetylanilino group, a
2-chloro-5-[.alpha.-(3-t-butyl-4-hydroxyphenoxy)dodecanamido]anilino
group, etc.), a ureido group (e.g., a phenylureido grcup, a methylureido
group, an N,N-dibutylureido grcup, etc.), an imido group (e.g., an
N-succinimido group, a 3-benzylhydantoinyl group, a
4-(2-ethylhexanoylamino)phthalimido group, etc.), a sulfamoylamino group
(e.g., an N,N-dipropylsulfamoylamino group, an
N-methyl-N-decylsulfamoylamino group, etc.), a carbamoylamino group (e.g.,
an N-ethylcarbamoylamino group, an N,N-dimethylcarbamoylamino group,
etc.), an alkylthio group (e.g., a methylthio group, an octylthio group, a
tetradecylthio group, a 2-phenoxyethylthio group, a 3-phenoxypropylthio
group, a 3-(4-t-butylphenoxy)propylthio group, etc.), an arylthio group
(e.g., a phenylthio group, a 2-butoxy-5-t-octylphenylthio group, a
3-pentadecylphenylthio group, a 2-carboxyphenylthio group, a
4-tetradecanamidophenylthio group, etc. , a heterocyclic thio group (e.g.,
a 2-benzothiazolylthio group, etc.), an alkoxycarbonylamino grcup (e.g., a
methoxycarbonylamino group, a tetradecyloxycarbonylamino group, etc.), an
aryloxycarbonylamino group (e.g., a phenoxycarbonylamino group, a
2,4-di-tert-butylphenoxycarbonylamino group, etc.), a sulfonamido group
(e.g., a methanesulfonamido group, a hexadecane-sulfonamido group, a
benzenesulfonamido group, a p-toluenesulfonamido group, an
octadecanesulfonamido group, a 2-methyloxy-5-t-butylbenzenesulfonamido
group, etc.), a carbamoyl group (e.g., an N-ethylcarbamoyl group, an
N,N-dibutylcarbamoyl group, an N-(2-dodecyloxyethyl)carbamoyl group, an
N-methyl-N-dodecylcarbamoyl group, an
N-[3-(2,4-di-tert-amylphenoxy)prcpyl]carbamoyl group, etc.), an acyl group
(e.g., an acetyl group, a (2,4-di-tert-amylPhenoxy)acetyl group, a benzoyl
group, etc.), a sulfamoyl group (e.g., an N-ethylsulfamoyl group, an
N,N-dipropylsulfamoyl group, an N-(2-dodecyloxyethyl)sulfamoyl group, an
N-ethyl-N-dodecylsulfamoyl group, an N,N-diethylsulfamoyl group, etc.), a
sulfonyl group (e.g., a methanesulfonyl group, an octanesulfonyl group, a
benzenesulfonyl group, a toluenesulfonyl group, etc.), a sulfinyl group
(e.g., an octanesulfinyl group, a dodecylsulfinyl group, a phenylsulfinyl
group, etc.), an alkoxycarbonyl group e.g., a methoxycarbonyl group, a
butyloxycarbonyl group, a dcdecyloxycarbonyl group, an
octadecyloxycarbonyl group, etc.), or an aryloxycarbonyl group (e.g., a
phenyloxycarbonyl group, a 3-pentadecylphenyloxycarbonyl group, etc.).
Also, X represents a hydrogen atom, a halogen atom (e.g., a chlorine atom,
a bromine arom, an iodine atom, etc.), a carboxy group, a group which is
bonded to the carbon atom at the coupling position by an oxygen atom
(e.g., an acetoxy group, a propanoyloxy group, a benzoyloxy group, a
2,4-dichlorobenzoyloxy group, an ethoxyoxaloyloxy group, a pyruvinyloxy
group, a cinnamoylcxy group, a phenoxy group, a 4-cyanophenoxy group, a
4-methanesulfonamidophenoxy group, a 4-methanesulfonylphenoxy group, an
o-naphthoxy group, a 3-pentadecylphenoxy group, a benzyloxycarbonyloxy
group, an ethoxy grcup, a 2-cyanoethoxy group, a benzyloxy group, a
2-phenethyloxy group, a 2-phenoxyethoxy group, a 5-phenyltetrazolyloxy
group, a 2-benzothiazolyloxy group, a 2-benzothiazolylcxy group, etc.), a
group which is bonded by a nitrogen atom (e.g., a benzenesulfonamido
group, an N-ethyltoluenesulfonamido group, a heptafluorobutanamido group,
a 2,3,4,5,6-pentafluorobenzamido group, an octanesulfonamido group, a
p-cyanophenylureido group, an N,N-diethylsulfamoylamino group, a
1-piperidyl group, a 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl group, a
1-benzylethoxy-3-hydantoinyl group, a
2N-1,1-dioxo-3(2H)-oxo-1,2-benzoisoisothiazolyl group, a
2-oxo-1,2-dihydro-1-pyridinyl group, an imidazolyl group, a pyrazolyl
group, a 3,5-diethyl-1,2,4-triazol-1-yl group, a 5- or
6-bromobenzotriazol-1-yl group, a 5-methyl-1,2,3,4-tetrazol-1yl group, a
benzimidazolyl group, a 3-benzyl-1-hydantoinyl group, a
1-benzyl-5-hexadecyloxy-3-hydantoinyl group, a 5-methyl-1-tetrazolyl
group, a 4-methoxyphenylazo group, a 4-pivaloylaminophenylazo group, a
2-hydroxy-4-propanoylphenylazo group, etc.), or a group which is bonded by
a sulfur atom (e.g., a phenylthic group, a 2-carboxyphenylthio group, a
2-methoxy-5-t-octylphenylthio group, a 4-methanesulfonylphenylthio group,
a 4-octanesulfonamidophenylthio group, a 2-butoxyphenylthio group, a
2-(2-hexanesulfonylethyl)-5-tert-octylphenylthio group, a benzylthio
group, a 2-cyanoethylthio group, a 1-ethoxycarbonyltridecylthio group, a
5-phenyl-2,3,4,5-tetrazolylthio group, a 2-benzothiazolylthio group, a
2-dodecylthio-5-thiophenylthio group, a
2-phenyl-3-dodecyl-1,2,4-triazolyl-5-thio group, etc.).
As described above, the compounds represented by formulae (III) to (VIII)
described above include the case where R.sub.2, R.sub.3, R.sub.4 or X
forms a divalent group and the compound forms a bis compound at the
divalent group. Examples of the divalent group include a substituted or
unsubstituted alkylene group (e.g., a methylene group, an ethylene group,
a 1,10-decylene group, --CH.sub.2 CH.sub.2 --O--CH.sub.2 CH.sub.2 --,
etc.), a substituted or unsubstituted phenylene group (e.g., a
1,4-phenylene group, a 1,3-phenylene group,
##STR4##
etc.) and --NHCO--R.sub.5 --CONH-- (wherein R.sub.5 represents a
substituted or unsubstituted alkylene or phenylene group).
Also, when the moiety represented by formulae (III) to (VIII) is in the
vinyl monomer, examples of the linking group represented by R.sub.2,
R.sub.3 or R.sub.4 include the groups formed by the combination of the
groups selected from a substituted or unsubstituted alkylene group (e.g.,
a methylene group, an ethylene group, a 1,10-decylene group, --CH.sub.2
CH.sub.2 OCH.sub.2 CH.sub.2 --, etc.), a substituted or unsubstituted
phenylene group (e.g., a 1,4-phenylene group, a 1,3-phenylene group,
##STR5##
etc.), --NHCO--, --CONH--, --O--, --OCO-- and an aralkylene group (e.g.,
##STR6##
etc.).
In addition, the vinyl group in the vinyl monomer may have a substituent in
addition to the morety represented by formulae (III) to (VIII) described
above. Examples of the preferred substituent for the vinyl group other
than the moiety represented by formulae (III) to (VIII) include a hydrogen
atcm, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms.
As described above, the polymer coupler includes a copolymer of the vinyl
monomer and a non-coloring ethylenical monomer which does not cause
coupling reaction with the oxidation product of an aromatic primary amine
developing agent. Examples of the non-coloring ethylenical monomer include
acrylic acid, .alpha.-chloroacrylic acid, .alpha.-alkylacrylic acid (e.g.,
methacrylic acid, etc.), and esters and amides derived from these acrylic
acids (e.g., acrylamide, n-butylacrylamide, t-butylacrylamide,
diacetonacrylamide, methacrylamide, methyl acrylate, ethyl acrylate,
n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate,
2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl
methacrylate, ethyl methacryate, n-butyl methacrylate, .beta.-hydroxy
methacrylate, etc. , methylenedibisacrylamide, vinyl esters (e.g., vinyl
acetate, vinyl propionate, vinyl laurate, etc.), acrylonitrile,
methacrylonitrile, aromatic vinyl compounds (e.g., styrene and the
derivatives thereof, vinyltoluene, divinylbenzene, vinylacetophenone,
sulfostyrene, etc.), itaconic acid, citraconic acid, crotonic acid,
vinylidene chloride, vinyl alkyl ethers (e.g., vinyl ethyl ether, etc.),
maleic acid, maleic anhydride, maleic acid esters, N-vinyl-2-pyrrolidone,
N-vinylpyridine, 2- or 4-vinylpyridine, etc.). In this case, two or more
kinds of the non-coloring ethylenical monomers may be used.
Specific examples and the methods for producing the couplers represented by
formulae (III) to (VIII) described above are described in the following
literature.
That is, the compounds represented by formula (III) are described in
Japanese Patent Application (OPI) Nc. 162548/84, the compounds represented
by formula (IV) are described in Japanese Patent Application (OPI) No.
43659/85, the compounds represented by formula (V) are described in
Japanese Patent Publication No. 27411/72, the compounds represented by
formula (VI) are described in Japanese Patent Application (OPI) Nos.
171956/84 and 172982/85, the compounds represented by formula (VII) are
described in Japanese Patent Application (OPI) No. 33552/85, and the
compounds represented by formula (VIII) are described :n U.S. Pat. No.
3,061,432.
Also, the high coloring ballast groups described in Japanese Patent
Application (OPI) Nos. 42045/83, 214854/84, 177553/84, 177554/84,
177557/84, etc., can be applied to the compounds represented by formulae
III) to (VIII) described above.
Specific examples of the pyrazoloazole series couplers represented by the
above-described formulae, which can be used in the present invention, are
illustrated below although the invention is not limited to these
compounds.
##STR7##
The magenta couplers represented by formula (II) described above are
explained in more detail below.
In formula (II), W represents a phenyl group or a naphthyl group
substituted by at least one of a halogen atom, an alkyl group, an alkoxy
group, an alkoxycarbonyl group and a cyano group.
The alkyl group represented by Z in formula (II) includes a straight chain
or branched chain alkyl, alkenyl, cycloalkyl, aralkyl, or alkynyl group
having from 1 to 42 carbon atoms, and these groups may be substituted by a
halogen atom, a hydroxy group, a mercapto group, a cyano group, a nitro
group, a carboxy group, an aryl group, an alkoxy group, an aryloxy group,
a heterocyclic oxy group, an acyloxy group, an alkoxycarbonyloxy group, an
aryloxycarbonyloxy group, a silyloxy group, a carbamoyloxy grcup, a
phosphoric acid oxy group, an acylamino group, a sulfonamido group, an
alkoxycartonylamino group, an aryloxycarbonylamino group, a diacylamino
group, a carbamoylamino group, a sulfamoylamino group, an aromatic
heterocyclic group (e.g., a pyrazolyl group, an imidazolyl group, a
triazolyl group, etc.), an imido group, a monooxo nitrogen-containing
heterocyclic group (e.g., a pyridone, saccharin, etc.), an acyl group, an
alkoxycarbcnyl group, an aryloxycarbonyl group, a carbamoyl group, a
sulfamoyl group, a silyl group, an alkylthio group, an arylthio group, a
heterocyclic thio group, a sulfonyl group, an alkenyl group, an anilino
group, etc.
The aryl group represented by Z in formula (II) is a phenyl group or a
naphthyl group having from 6 to 46 carbon atoms, which may be substituted
by an alkyl group or each of the substituents described above with respect
to the substituents for the alkyl group.
The heterocyclic group represented by Z in formula (II) is a 5-membered or
6-membered heterocyclic group containing a nitrogen atom, an oxygen atom,
and a sulfur atom, solely or simultaneously, and may be condensed with a
benzene ring. Typical heterocyclic skeletons for the heterocyclic groups
are as follows.
##STR8##
In the above formulae, R.sub.6 represents a hydrogen atom, an alkyl grcup,
or the substituents described above on the substituents for the alkyl
grcup represented by Z, and R.sub.7 represents a hydrogen atom, an alkyl
group, an aryl group, an acyl group, an alkylsulfonyl group, or an
arylsulfonyl group.
Z in formula (II) is preferably an aryl group, which will be described in
detail hereinafter.
The acylamino group represented by Y in formula (II) is ar. alkanamido
group having 1 to 42 carbon atoms or a benzamido group having 6 to 46
carbon atoms, the ureido group represented by Y is an alkylureido group
having from 1 to 42 carbon atoms or a phenylureido group having from 6 to
46 carbon atoms, and the anilino group represented by Y is a phenylamino
group having from 6 to 46 carton atoms. The alkyl group for the
alkylureido group described above may have a substituent as described
above with respect to the substituents for the alkyl group represented by
X, and also the phenyl group of the phenylureido group described above
with respect to the substituents for the alkyl group represented by X.
Particularly preferred couplers in the 4-mercapto-5-pyrazolone type magenta
couplers represented by formula (II) are represented by formula (IX) or
(X) described below.
##STR9##
In formulae (IX) and (X), Ar represents a phenyl group substituted by at
least one halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group,
or cyano group; A represents a halogen atom or an alkoxy group; R.sub.8
represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy
group, an acylamino group, a sulfonamido group, a sulfamoyl group, a
carbamoyl group, a diacylamino group, an alkoxycarbonyl group, an
alkoxysulfonyl group, an aryloxysulfonyl group, an alkanesulfonyl group,
an arysulfonyl group, an alkylthio group, an arylthio group, an
alkyloxycarbonylamino group, a ureido group, an acyl group, a nitro group,
or a carboxy group; R.sub.9 represents a halogen atom, a hydroxy group, an
amino group, an alkyl group, an alkoxy group, an aryloxy group, or an aryl
group; R.sub.10 represents a hydrogen atom, an amino group, an acylamino
group, a ureido group, an alkoxycarbonylamino group, an imido group, a
sulfonamido group, a sulfamoylamino group, a nitro group, an
alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group, or
an alkylthio group; R.sub.11 represents a hydrogen atom, a halogen atom, a
hydroxy group, an alkyl group, an alkoxy group or an aryl group; at least
one of said R.sub.9 and R.sub.10 represents an alkoxy group; m represents
an integer of 1 to 3; n represents an integer of 1 to 4; l represents an
integer of 1 to 3; R.sub.12 represents an alkyl group or an aryl group;
R.sub.13 represents a hydrogen atom, a halogen atom, an alkyl group, an
alkoxy group, an aryloxy group, or an aryl group, and a and b each
represents an integer of 1 to 5.
The couplers represented by formulae (IX) and (X) described above are
explained below in further detail.
Ar in these formulae is a substituted phenyl group, and examples of the
substituent include a halogen atom (e.g., a chlorine atom, a bromine atom,
a fluorine atom, etc. , an alkyl group having from 1 to 22 carbon atoms
(e.g., a methyl group, an ethyl group, a tetradecyl group, a t-butyl
group, etc.), an alkoxy group having from 1 to 22 carbon atoms (e.g., a
methoxy group, an ethoxy group, an octyloxy group, a dodecyloxy group,
etc.), ar alkoxycarbonyl group having from 2 to 23 carbon atoms (e.g., a
methoxycarbonyl group, an ethoxycarbonyl group, a tetradecyloxycarbonyl
group, etc.), or a cyano group.
Z in the formulae represents a halogen atom (e.g., a chlorine atom, a
bromine atom, a fluorine atom, etc.) or an alkoxy group having 1 to 22
carbon atoms (e.g., a methoxy group, an octyloxy group, a dodecyloxy
group, etc.).
R.sub.8 in the formulae represents a hydrogen atom, a halogen atom (e.g., a
chlorine atom:, a bromine atom, a fluorine atom, etc.), an alkyl group
(e.g., a methyl group, a t-butyl group, a 2-methanesulfonamidoethyl group,
a t-butanesulfonylethyl group, a tetradecyl group, etc.), an alkoxy group
(e.g., a methoxy group, an ethoxy group, a 2-ethylhexyloxy group, a
tetradecyloxy group, etc.), an acylamino group (e.g., an acetamido group,
a tenzamido group, a butanamido group, a tetradecanamido group, an
.alpha.-(2,4-di-tert-amylphenoxy)acetamido group, an
.alpha.-(2,4-di-tert-amylphenoxy)butyramido group, an
.alpha.-(3-pentadecylphenoxy)hexanamido group, an
.alpha.-(4-hydroxy-3-tert-butylphenoxy)tetradecanamido group, a
2-oxo-pyrrolidin-1-yl group, an N-methyltetradecanamido group, an
.alpha.-(3-methanesulfonamidophenoxy)tetradecanamido group, etc.), a
sulfonamido group (e.g., a methanesulfonamido group, a benzenesulfonamido
group, a p-toluenesulfonamido group, an octanesulfonamido group, a
p-dodecylbenzenesulfonamido group, an N-methyltetradecanesulfonamido
group, etc.), a sulfamoyl group (e.g., an N-methylsulfamoyl group, an
N-hexadecylsulfamoyl group, an N-(3-dodecyloxypropyl)sulfamoyl group, an
N-[4-(2,4-di-tert-amylphenoxy)butyl]sulfamoyl group, an
N-methyl-N-tetradecylsulfamoyl group, etc.), a carbamoyl group (e.g., an
N-methylcarbamoyl group, an N-octadecylcarbamoyl group, an
N-[4-(2,4-di-tert-amylphenoxy)butyl]carbamoyl group, an
N-methyl-N-tetradecylcarbamoyl group, etc.), a diacylamino group (e.g., an
N-succinimido group, an N-phthalimido group, a 2,5-dioxo-1-oxazolidinyl
group, a 3-dodecyl-2,5-dioxo-1-hydantoinyl group, a
3-(N-acetyl-N-dodecylamino)succinimido group, etc.), an alkoxycarbonyl
group (e.g., a methoxycarbonyl group, a tetradecyloxycarbonyl group, a
benzyloxycarbonyl group, etc.), an alkoxysulfonyl group (e.g., a
methcxysulfonyl group, an octyloxysulfonyl group, a tetradecyloxysulfonyl
group, etc.), an aryloxysulfonyl group (e.g., a phenoxysulfonyl group, a
2,4-di-tert-amylphenoxysulfonyl group, etc.), an alkanesulfonyl- group
(e.g., a methanesulfonyl group, an octanesulfonyl group, a
2-erhylhexanesulfonyl group, a hexadecanesulfonyl group, etc.), an
arylsulfonyl group (e.g., a benzenesulfonyl group, a
4-nonylbenzenesulfonyl group, etc.), an alkylthio group (e.g., an
ethylthio group, a hexylthio group, a benzylthio group, a tetradecylthio
group, a 2-(2,4-di-tert-amylphenoxy)ethylthio group, etc.), an arylthio
group (e.g., a phenylthio group, a p-tolylthio group, etc.), an
alkyloxycarbonylamino group (e.g., ar. ethyloxycarbonylamino group, a
benzyloxycarbonylamino, group, a hexanedecyloxycarbonylamino group, etc.),
a ureido group (e.g., an N-methylureido group, an N-phenylureido group, an
N,N-dimethylureido group, an N-methyl-N-dodecylureido group, an
N-hexadecylureido group, an N,N-dioctanedecylureido group, etc.), an acyl
group (e.g., an acetyl group, a benzoyl group, an octadecanoyl group, a
p-dodecanamidobenzoyl group, etc.), a nitro group, or a carboxy group.
In the above-described groups, the alkyl moiety has 1 to 42 carbon atoms
and the aryl moiety has 6 to 46 carbon atoms.
R.sub.9 to R.sub.11 in formulae (IX) and (X) are explained in further
detail below.
R.sub.9 represents a halogen atom (e.g., a chlorine atom, a bromine atom,
etc.), a hydroxy group, a subsituted or unsubstituted amino group (e.g.,
an N-alkylamino group, an N,N-dialkylamino group, an N-anilino group, an
N-alkyl-N-arylamino group, and a heterocyclic amino group, such as an
N-butylamino group, an N,N-dibutylamino group, an N,N-dihexylamino group,
an N-piperidino group, an N,N-bis(2-dodecyloxyethyl)amino group, an
N-cyclohexylamino group, an N-phenylamino group, an
N,N-bis(2-hexanesulfonylethyl)amino group, etc.), an alkyl group (e.g., a
straight chain or branched alkyl group, an aralkyl group, an alkenyl
group, a cycloalkyl group, or a cycloalkenyl group, such as a methyl
group, a butyl group, an octyl group, a dodecyloxy group, a benzyl group,
a cyclopentyl group, a 2-methanesulfonylethyl group, a 3-phenoxypropyl
group, etc.), an alkoxy group (e.g., a methoxy group, a butoxy group, a
benzyloxy group, a 2-ethylhexyloxy group, a dodecyloxy group, a
2-methanesulfonylethyloxy group, a 2-butanesulfonylethyloxy group, an
isopropyloxy group, a 2-chloroethyloxy group, a
3-(2,4-di-tert-amylphenoxy)propyloxy group, a 2-(N-methylcarbamoyl)ethoxy
group, a cyclopentyloxy group, a 2-ethoxytetradecyloxy group, a
4,4,4,3,3,2,2-heptafluorobutyloxy group, a 3-(N-butylcarbamoyl)propyloxy
group, a 3-(N,N-dimethylcarbamoyl)propyloxy group, a
4-methanesulfonylbutoxy group, a 2ethanesulfonamidoethyloxy group, etc.),
an aryloxy group (e.g., a phenoxy group, a 2,4-dichlorophenoxy group,
etc.), or an aryl group (substituted or unsubstituted phenyl group, and an
.alpha.- or .beta.-naphthyl group having from 6 to 38 carbon atoms, such
as a phenyl group, an .alpha.- or .beta.-naphthyl group, a 4-chlorophenyl
group, a 4-t-butylphenyl group, a methanesulfonamidophenyl group, a
2,4-dimethylphenyl group, etc.).
R.sub.10 in these formulae represents a hydrogen atom, a substituted or
unsubstituted amino group (e.g., an N-alkylamino group, an
N,N-dialkylamino group, an N-anilino group, an N-alkyl-N-arylamino group,
and a heterocyclic amino group, such as an N-butylamino group, an
N,N-diethylamino group, an N-[2-(2,4-di-tert-amylphenoxy)ethyl]amino
group, an N,N-dibutylamino group, an N-piperidino group, an
N,N-bis(2-dodecyloxyethyl)amino group, an N-cyclohexylamino group, an
N,N-dihexylamino group, an N-phenylamino group, a
2,4-di-tertamylphenylamino group, an
N-(2-chloro-5-tetradecanamidophenyl)amino group, an N-methyl-N-phenylamino
group, an N-(2-pyridyl)amino group, etc.), an acylamino group (e.g., an
acetamido group, a benzamido group, a tetradecanamido group, a
(2,4-di-tert-amylphenoxy)acetamido group, a 2-chlorobenzamido group, a
3-pentadecylbenzamido group, a 2-(2-methanesulfonamidophenoxy)dodecanamido
group, a 2-(2-chlorophenoxy)tetradecanamido group, etc.), a ureido group
e.g., a methylureido group, a phenylureido group, a 4-cyanophenylureido
group, etc.), an alkoxycarbonylamino group (e.g., a methoxycarbonylamino
group, a dodecyloxycarbonylamino group, a 2-ethylhexyloxycarbonylamino
group, etc.), an imido group (e.g., an N-succinimido group, an
N-phthalimido group, an N-hydantoinyl group, a
5,5-dimethyl-2,4-dioxooxazol-3-yl group, an N-(3-octadecenyl)succinimido
group, etc.), a sulfonamido group (e.g., a methanesulfonamido group, an
octanesulfonamido group, a benzenesulfonamido group, a
4-chlorobenzenesulfonamido group, a 4-dodecylbenzenesulfonamido group, an
N-methyl-N-benzenesulfonamido group, a 4-dodecyloxybenzenesulfonamido
group, a hexadecanesulfonamido group, etc.), a sulfamoylamino group (e.g.,
an N-octylsulfamoylamino group, an N,N-dipropylsulfamoylamino group, an
N-ethyl-N-phenylsulfamoylamino group, an N-(4-butyloxy)sulfamoylamino
group, etc.), a nitro group, an alkoxycarbonyl group (e.g., a
methoxycarbonyl group, a butoxycarbonyl group, a dodecyloxycarbonyl group,
a benzyloxycarbonyl group, etc.), a carbamoyl group (e.g., an
N-octylcarbamoyl group, an N,N-dibutylcarbamoyl group, an
N-phenylcarbamoyl group, an N-[3-(2,4-di-tert-amylphenoxy)propyl]carbamoyl
group, etc.), an acyl group (e.g., an acetyl group, a benzoyl group, a
hexanoyl group, a 2-ethylhexanoyl group, a 2ethylhexanoyl group, a
2-chlorobenzoyl group, etc.), a cyano group, or an alkylthio group e.g., a
dodecylthio group, a 2-ethylhexylthio group, a benzylthio group, a
2-oxocyclohexylthio group, a 2-(ethyltetradecanoate)thio group, a
2-(dodecylhexanoate)thio group, a 3-phenoxypropylthio group, a
2-dodecanesulfonylethylthio group, etc.).
R.sub.11 in these formulae described above represents a hydrogen atom, a
hydroxy group, or, in addition, a halogen atom, or an alkyl, alkoxy or
aryl group as described for R.sub.9, and at least one of said R.sub.9 and
R.sub.11 represents an alkoxy group.
R.sub.12 represents an alkyl or aryl group as described above for R.sub.9.
R.sub.13 represents a hydrogen atom, or, in addition, a halogen atom, or an
alkyl, alkoxy, aryloxy, or aryl group as described above for R.sub.9.
Specific examples of the magenta couplers represented by formula (II)
described above are illustrated below, but the invention is not limited
thereto.
##STR10##
The magenta couplers for use in this invention represented by formula (II)
described above can be synthesized according to the methods described, for
example, in Japanese Patent Publication No. 34044/78, Japanese Patent
Application (OPI) No. 62454;80, U.S. Pat. No. 3,701,783, etc.
These couplers are each present in a silver halide emulsion layer generally
from 2.times.10.sup.-3 to 5.times.10.sup.-1 mol, and preferably from
1.times.10.sup.-2 to 5.times.10.sup.-1 mol, per mol of silver in the
emulsion layer.
The above-described magenta couplers may be present in one emulsion layer
as a combination of two or more kinds thereof, or a single coupler may be
present in two or more emulsion layers, in order to satisfy the
characteristics required for a particular color photographic graphic
material.
The above-described magenta coupler(s) can be introduced into a silver
halide emulsion by an oil-in-water dispersion method or the method
described in U.S. Pat. No. 2,322,027. For example, the magenta coupler is
dispersed in a hydrophilic colloid layer as fine oil drops thereof in the
existence of a phthalic acid alkyl ester (e.g., dibutyl phthalate, dioctyl
phthalate, etc.), a phosphoric acid ester (e.g., diphenyl phosphate,
triphenyl phosphate, tricresyl phosphate, dioctylbutyl phosphate, etc.), a
citric acid ester (e.g., tributyl acetylcitrate, etc.), a benzoic acid
ester (e.g., octyl benzoate, etc.), an alkylamide (e.g.,
diethyllaurylamide, etc.), an aliphatic ester (e.g., dibutoxyethyl
succinate, diethyl azelate, etc.), trimesic acid ester (e.g., tributyl
trimesate, etc.), etc.
The silver halide particles in the silver halide photographic emulsions may
be so-called regular particles having a regular crystal form such as
cubic, octahedral, tetradecahedral, etc., irregular particles having an
irregular crystal form such as spherical, particles having a crystal
defect such as twin face, etc., or the particles may have a composite form
thereof.
The silver halide particles for use in the present invention may be fine
particles having a diameter of the projected area of less than about 0.1
micron or large particles having a diameter of the projected area of up to
about 10 microns. The silver halide emulsion for use in the present
invention may be a monodispersed emulsion having a narrow particle size
distribution, or a polydispersed emulsion having a broad particle size
distribution.
Two or more kinds of silver halide emulsions prepared separately may be
used as a mixture thereof.
Also, in a typical monodispersed emulsion for use in the present invention,
at least about 95% by weight of silver halide particles having a mean
particle size of at least about 0.1 micron are in .+-.40% of the mean
particle size of all of the silver halide particles. A silver halide
emulsion wherein at least about 95% by weight or by number of silver
halide particles having a mean particle size of from about 0.25 to about 2
microns are in the range of .+-.20% of the mean particle size of all of
the silver halide particles can be used in the present invention.
Also, tabular grain silver halide emulsion having an aspect ratio of at
least about 5 can be used in the present invention. The tabular silver
halide grains can be prepared by the methods described in Gutoll,
Photographic Science and Engineering, Vol. 14, pp. 248 to 257 (1970), U.S.
Pat. Nos. 4,431,226, 4,414,310, 4,433,048, 4,439,520, British Pat. No.
2,112,157, etc. When the tabular grain silver halide emulsion is used,
advantages such as the improvement of color sensitizing effect by
sensitizing dye(s), the improvement of graininess, and the increase of
sharpness can be obtained, as described in detail in U.S. Pat. No.
4,434,226.
The crystal structure of silver halide particles may be homogeneous through
the particle, may differ in halogen composition between the inside and the
outer portion thereof, or may have a layer structure. These silver halide
particles are disclosed in British Pat. No. 1,027,146, U.S. Pat. Nos.
3,505,068, 4,444,877, and Japanese Patent Application (OPI) No. 143331/85.
Also, silver halide particles formed by bonding silver halides each having
different halogen composition by epitaxial junction may be used in the
present invention. Furthermore, a mixture of silver halide particles
having various crystal forms can be used.
The silver halide emulsions for use in the present invention may be
physically ripened, chemically ripened, and spectrally sensitized. The
additives used in these steps are described in Research Disclosure, RD No.
17643 (December, 1978) and ibid., RD No. 18716 (November, 1979) and the
corresponding portions are shown in the following table.
Also, known photographic additives which can be used in the present
invention are also described in the above-described two Research
Disclosures the portions thereof indicated in the table below.
__________________________________________________________________________
Additive RD No. 17643
RD No. 18716
__________________________________________________________________________
Chemical Sensitizer
Page 23 Page 648, right column
Sensitivity Increasing
Page 23 Page 648, right column
Agent
Spectral Sensitizer
Pages 23 and
Page 648, right column
and Super Color Sensi-
24 to page 649, right
tizer column
Whitening Agent
Page 24
Antifoggant and
Pages 24 and
Page 649, right column
Stabilizer 25
Light Absorbent,
Pages 25 and
Page 649, right column
Filter Dye, Ultra-
26 to page 650, left
violet Absorbent column
Stain Preventing Agent
Page 25, Page 650, left to
right column
right column
Dye Image Stabilizer
Page 25
Hardener Page 26 Page 651, left column
10.
Binder Page 26 Page 651, left column
Plasticizer, Page 27 Page 650, right column
Lubricant
Coating Aid, Surface
Pages 26 and
Page 650, right column
Active Agent 27
Antistatic Agent
Page 27 Page 650, right column
__________________________________________________________________________
Examples of the typical yellow coupler for use in the present invention
include hydrophobic acylacetamide series couplers having a ballast group.
Specific examples of these yellow couplers are described, for example, in
U.S. Pat. Nos. 2,407,210, 2,875,057 and 3,265,506.
In the present invention 2-equivalent yellow couplers are preferably used,
and examples of such couplers include oxygen atom releasing type yellow
couplers as described in U.S. Pat. Nos. 3,408,194, 3,447,928, 3,933,501,
4,022,620, etc., and nitrogen atom releasing type yellow couplers as
described in Japanese Patent Publication No. 10739/83, U.S. Pat. Nos.
4,401,752, 4,326,024, Research Disclosure, RD 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, 2,433,812, etc.
Also, .alpha.-pivaloylacetanilide series couplers are excellent in
fastness, particularly light fastness of colored dyes obtained therewith.
On the other hand, .alpha.-benzoylacetanilide series couplers give high
coloring density.
Examples of the cyan couplers for use in the present invention include
hydrophobic and nondiffusible naphtholic or phenolic couplers, such as the
naphtholic couplers described in U.S. Pat. No. 2,474,293, and preferably
the oxygen atom releasing type 2-equivalent naphtholic couplers as
described in U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and
4,296,200.
Specific examples of the phenolic couplers are described in U.S. Pat. Nos.
2,369,929, 2,801,171, 2,772,162, 2,895,826, etc. Cyan couplers capable of
forming cyan dyes having high fastness to humidity and temperature are
preferably used in the present invention, and specific examples of these
cyan couplers are the phenolic cyan couplers having an alkyl group having
two or more carbon atoms at the meta-position of the phenol nucleus as
described in U.S. Pat. No. 3,772,002, etc., the
2,5-diacylamino-substituted phenolic couplers as described in U.S. Pat.
Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011, 4,327,175, West German
Patent Application (OLS) No. 3,329,729, European Pat. No. 121,365, etc.,
the phenolic cyan couplers having a phenylureido group at the 2-position
and an acylamino group at the 5-position as described in U.S. Pat. Nos.
3,446,622, 4,333,999, 4,451,559, 4,427,767, etc. Furthermore, the
naphtholic cyan couplers having a sulfonamido group, an amido group, etc.,
at the 5-position of the naphthol nucleus described in Japanese Patent
Application (OPI) No. 237448/85 are excellent in the fastness of colored
images formed and can preferably be used in the present invention.
For correcting unnecessary absorptions of colored dyes, it is preferred to
use colored couplers for color photographic materials for photographing in
order to provide masking. Typical examples of such colored couplers are
the yellow-colored magenta couplers described in U.S. Pat. No. 4,162,670,
Japanese Patets Publication No. 39413/82, etc., and the magenta-colored
cyan couplers described in U.S. Pat. Nos. 4,004,929, 4,138,258, British
Pat. No. 1,146,368, etc. Other examples of the colored couplers for use in
the present invention are described in Research Disclosure, RD No. 17643
(December, 1978), Paragraph VII-G.
In the present invention, the graininess can be improved by using couplers
providing colored dyes having suitable diffusibility can be used.together
with the above-described couplers. Specific examples of such couplers
include magenta couplers described in U.S. Pat. No. 4,366,237 and British
Pat. No. 2,125,570, etc., and yellow, magenta and cyan couplers in
European Pat. No. 96,570 and West German Patent Application (OLS) No.
3,234,533.
The dye-forming couplers and the special couplers described above may form
a polymer including a dimer or more. Specific examples of the polymerized
dye-forming couplers are described in U.S. Pat. Nos. 3,451,920 and
4,080,211. Also, specific examples of polymerized magenta couplers are
described in British Pat. No. 2,102,173 and U.S. Pat. No. 4,367,282.
Couplers releasing photographically useful residues upon coupling can also
be preferably used in the present invention. DIR couplers, e.g., couplers
releasing a development inhibitor, are described in Research Disclosure,
RD No. 17653 (December, 1978), Paragraph VII-F.
Examples of the supports which can be used in the present invention are
described in Research Disclosure, RD No. 17643, page 28 and ibid., RD No.
18716, page 647, right column to page 648, left column.
The process of the present invention can be applied to various kinds of
color photographic materials such as cinematic color negative photographic
films, color reversal photographic films for lantern slide or television,
color photographic papers, color positive photographic films, color
reversal photographic papers, etc. The present invention can also be
applied to black-and-white photographic materials utilizing a mixture of
three color couplers, as described in Research Disclosure, RD No. 17123
(July, 1978).
The following examples are intended to illustrate the present invention but
not to limit it in any way. |
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| Priority Data |
Nov 06, 1986[JP]60-247220 |
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Title Information |
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