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Description  |
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FIELD OF THE INVENTION
The present invention relates to a method for processing silver halide
photographic light-sensitive materials, and more particularly to a method
for preventing silver halide photographic light-sensitive materials from
producing a fog in the processing thereof.
BACKGROUND OF THE INVENTION
There have conventionally been known as stabilizers or fog restrainers to
be used for the purpose of preventing silver halide photographic
light-sensitive materials (hereinafter called light-sensitive materials)
from producing a fog with the lapse of time a large number of compounds
including, for example, hydroxypolyazaindenes such as
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, mercapto-substituted
heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole,
2-mercaptobenzothiazole, and azole derivatives such as benzimidazole,
benzotriazole, indazole, and the like.
Further, the combined use in a given ratio of these conventionally known
fog restrainers is also extensively performed in this field.
However, the demand for increasing the speed of light-sensitive materials
has been more and more strongly made in recent years. That is, there are,
for example, light-sensitive materials for amateure use required to meet
the need for the use of a high shutter speed for preventing the camera
blur in photographing due to the miniaturization of the image frame size;
color and black-and-white photographic papers required to meet the need
for the rapid processing in the development process thereof;
light-sensitive materials for graphic arts use required to be so
high-sensitive as suitably usable in the electronically operated,
simplified or automated plate-making and printing processes;
light-senisitive materials for medical radiography use highly demanded to
meet the need for use in a much reduced radiation-exposure dose to be
highly safe to the human body; and the like.
Upon the fog to be produced during the storage over a long period of time
in a light-sensitive material comprising a silver halide emulsion
extremely sensitized or sensitized by a technique different from
conventional ones or to be increased due to the rapid development process
at a high temperature above 30.degree. C. that is performed lately for the
reduction of the access time, those conventional fog restrainers as
mentioned above has no effect at all or on the contrary there are cases
where they rather increase the fog.
Thus, there is a strong demand for developing a fog-restraining technique
which is capable of adequately restraining high-speed light-sensitive
materials from producing a fog during their storage over a long period or
of preventing light-sensitive materials from producing a fog in their
rapid processing at a high temperature, and which has no influence upon
the photographic characteristics (gradation, sharpness, etc.).
SUMMARY OF THE INVENTION
It is a first object of the present invention to provide a method for
processing photographic light-sensitive materials which is capable of
keeping the photographic characteristics stable and of preventing the the
light-sensitive material from producing a fog even where it is preserved
over a long period.
It is a second object of the present invention to provide a processing
method which is hardly apprehensive of inviting the deterioration of the
sensitivity and gradation due to the development restraining.
It is a third object of the present invention to provide a processing
method which is capable of extremely reducing the production of a fog when
a light-sensitive material is developed at a high temperature,
particularly at a temperature of not less than 30.degree. C.
The above objects can be accomplished by a method for processing silver
halide photographic light-sensitive materials which comprises a developing
process in which a silver halide photographic light-sensitive material is
developed in the presence of at least one compound having Formula [Ia] or
[Ib]:
##STR2##
wherein Ar is a benzene ring of a naphthalene ring, each of which rings
may be in the quinone form, F is a fluorine atom, Y and Y' each is a
substituent substitutable to the benzene ring or naphthalene ring, X is a
divalent linkage group, m and m' each is an integer of from 1 to 5, and n
and n' each is an integer of from 1 to 3.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be illustrated further in detail below:
Those compounds having Formulas [Ia] and [Ib] to be used in this invention
are required to be of a benzene ring or a naphthalene ring (each of which
rings may be in the quinone form) having thereon at least one fluorine
atom and at least one substituent (represented by Y and Y') other than the
fluorine atom.
Those groups substitutable to the benzene ring or naphthalene ring
represented by Y or Y', although not particularly restricted, include
preferably halogen atoms excluding fluorine, mercapto group, carboxyl
group and salts thereof, sulfo group and salts thereof, amino group,
acylamino groups, alkylamino groups, nitro group, cyano group, alkyl
groups, alkenyl groups, cycloalkyl groups, aryl groups, alkoxy groups,
aryloxy groups, alkyl-thio groups, aryl-thio groups, alkoxy-carbonyl
groups, carbamoyl group, sulfamoyl group, alkoxyalkyl groups, aminoalkyl
groups, acylaminoalkyl groups, hydroxyalkyl groups, carboxyalkyl groups,
sulfoxalkyl groups, alkylsulfonamidoalkyl groups, and the like.
Those particularly preferred among these substituents, for balancing the
oleophilicity of the fluorine atom, are the hydrophilic groups including,
e.g., the hydroxyl group, mercapto group, carboxyl group and salts
thereof, sulfo group and salts thereof, and the like.
In Formula [Ib], examples of the divalent linkage group represented by the
X, although not restricted either, include, e.g., --O--, --S--, --S--S--,
--(CH.sub.2).sub.l -- (l is an integer of from 1 to 8), and the like.
The following are examples of the compounds having Formulas [Ia] and [Ib]
usable in this invention, but this invention is not limited to and by the
examples.
##STR3##
These compounds can be synthesized in accordance with those methods as
described in the J. Chem. Soc. Sect. C, p. 626, 1965, p. 1347, 1971; J.
Org. Chem., vol. 34, p. 534, 1969; and Japanese Patent Publication Open to
Public Inspection (hereinafter referred to as Japanese Patent O.P.I.
Publication) Nos. 184057/1985 and 204742/1985, and the like. Some part of
these compounds can be commercially available as chemical reagents.
In the present invention, that the development of a light-sensitive
material is made in the presence of a compound having Formula [Ia] or [Ib]
(those having both Formulas will be hereinafter called the "compound of
Formula [I]" or the "antifoggant of this invention") means more
particularly either a method in which a light-sensitive material
containing the compound of this invention in at least one of the component
layers thereof such as the silver halide emulsion layer and/or a layer
adjacent thereto, filter layer, antihalation layer, protective layer,
subbing layer, etc., is developed, or a method in which the development of
a light-sensitive material is carried out in a developer solution or a
bath prior to the developing process into which is incorporated the
compound of this invention. The particularly preferred one of these
methods is the former; i.e., the method in which the compound of this
invention is incorporated into the emulsion layer of a light-sensitive
material.
The adding amount of the antifoggant of this invention, where added to the
silver halide emulsion layer of a light-sensitive material, is desirable
to be used in the range of from 1.times.10.sup.-5 to 1.times.10.sup.-1
mole per mole of the silver halide contained in the emulsion layer, and
more preferably from 1.times.10.sup.-5 to 1.times.10.sup.-4 mole, and,
where added to a non-light-sensitive layer, is desirable to be used in the
range of from 1.times.10.sup.-5 to 1.times.10.sup.-1 mole per m.sup.2.
Where the compound is added to the processing bath, the adding amount is
preferably in the range of from 10.sup.-5 to 10.sup.-1 mole, and more
preferably from 10.sup.-4 to 10.sup.-2 mole.
The compound of this invention may be dissolved in a solvent miscible with
water, such as methanol, ethanol, dimethylformamide, or in an aqueous
alkaline solution, and the solution of the compound may be then
incorporated into the foregoing component layer(s) of a light-sensitive
material or into the foregoing developer solution.
For the processing method of this invention, any known method may be used
except for the presence of the compound of this invention. The processing
may be made at a temperature of from 18.degree. C. to 50.degree. C.
According to purposes, any of the black-and-white photograph processing,
lith-type developing process, or color photograph processing to form dye
images may apply to the processing method.
Examples of the developing agent for the black-and-white photograph
processing include dihydroxybenzenes (such as hydroquinone),
3-pyrazolidones (such as 1-phenyl-3-pyrazolidone), aminophenols (such as
N-methyl-p-aminophenol), ascorbic acid, and the like. These compounds may
be used alone or in combination.
The developer solution may contain other known preservative, alkaline
agent, pH buffer, fog restrainer, etc., and further, if necessary,
solvent, tone control agent, development accelerator, surfactant,
defoaming agent, water softener, hardening agent, and the like.
In addition, the present invention may also apply to a light-sensitive
material of the type of containing a developing agent and of being
processed in an alkaline bath; i.e., the so-called agent-in-emulsion-type
light-sensitive material.
In the case of forming a dye image, a color developing agent-containing
aqueous alkaline solution may be used. As the color developing agent any
of those known primary aromatic amine developers such as phenylenediamines
may be used.
The color developer solution may, in addition to the above agent, also
contain a pH buffer such as a sulfite, carbonate or borate of an alkali
metal, a halogen salt or organic antifoggant, a water softener, a
preservative, an organic solvent such as benzyl alcohol, ethylene glycol,
etc., a development accelerator such as a quaternary salt or amine, and
the like.
The color developing process is usually followed by the bleach-fix process.
The bleaching process may take place either simultaneously with or
sparately from the fixing process. The bleaching agent to be used in the
bleaching or bleach-fix process includes those compounds of polyvalent
metals such as iron (III), cobalt (III), chromium (IV), copper (II),
etc,., and persulfates, and the like; for example, ferrocyanides,
bichromates, organic complex salts of iron and cobalt,
ethylenediaminetetraacetic acid, nitrilotriacetic acid, persulfates,
permanganates, and the like, may be used.
The processing method of this invention may apply to various types of
commercially available light-sensitive materials to prevent them from
producing a fog.
For example, the method may apply to those light-sensitive materials for
general black-and-white use, for X-ray recording use, for graphic arts
use, for low-speed positive use, for color positive use, for color
negative use, for color paper use, for reversal color use, for direct
positive use, for the diffusion transfer process, for the thermal
development process, and the like. The method is particularly effectively
applicable to the rapid development process that is to take place at a
high temperature of not less than 30.degree. C.
In the processing method of this invention, any known antifoggants may be
used in combination with the antifoggant of this invention.
The usable antifoggants include those compounds wellknown to those skilled
in the art, such as, e.g., 5-nitrobenzimidazole, 6-nitroindazole,
5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole,
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 2-mercaptobenzothiazole, and
the like.
In the processing method of this invention, where a compound having Formula
[Ia] or [Ib] is incorporated into a light-sensitive material, a compound
having the following Formula (II) (hereinafter called Compound II) is
particularly desirable to be used in combination.
##STR4##
wherein Q is a group of atoms, including a carbon atom, a nitrogen atom, a
sulfur atom or an oxygen atom, necessary to form a 5- or 6-member
heterocyclic ring, and the ring formed by the Q is allowed to be condensed
further with a hydrocarbon ring or another heterocyclic ring; and Z is an
aromatic group or a heterocyclic group.
In Formula [II], the 5- or 6-member heterocyclic ring formed by the Q is a
nitrogen-containing heterocyclic ring containing a carbon, nitrogen,
sulfur or oxygen atom as the ring-consituting atom, and further the ring
may be condensed with a hydrocarbon ring or with another heterocyclic
ring; examples of the ring include imidazole, triazole, tetrazole,
pyridine, pyrimidine, triazine, thiazole, oxazole, thiadiazole,
oxadiazole, benzimidazole, benzothiazole, benzoxazole, purine,
triazaindene, tetrazaindene, pentazaindene, and the like.
These heterocyclic rings each may have a substituent, such as, for example,
a halogen atom, a hydroxyl, mercapto, amino, nitro, carboxyl, sulfo,
alkyl, alkoxy, aryloxy, alkylthio, arylthio, carbamoyl, sulfamoyl, or the
like group.
The aromatic group represented by the Z is preferably a phenyl group or a
naphthyl group. These phenyl and naphthyl groups each may also have a
substituent, such as, for example, a halogen atom, a hydroxyl, mercapto,
amino, nitro, alkyl, alkoxy, or the like group. The heterocyclic group
represented by the Z may also be condensed, examples of which include
imidazolyl, thiazolyl, pyridyl, pyrimidinyl, piperidinyl, benzothiazolyl,
quinolyl, and the like groups. These heterocyclic groups each may also
have a substituent, such as, e.g., a halogen atom, a hydroxyl, amino,
nitro, alkyl, alkoxy, or the like group.
The preferred ones among the compounds having Formula [II]are those of
which the heterocyclic ring formed by the Q is imidazole, triazole, or
tetrazole. The particularly preferred one is of tetrazole. The aromatic
group represented by the Z is more preferably a phenyl, tolyl or
m-nitrophenyl group, and the heterocyclic group is more preferably a
2-imidazolyl, 2-pyridyl or 2-benzothiazolyl group.
The following are examples of the compound having Formula [II] to be used
in the present invention, but this invention is not limited thereto.
##STR5##
These compounds are numerously reported in abstracts and journals such as
the Beilsteins Handbuch der Organischen Chemie, Chemical Abstracts,
Journal of the American Society, and the like, and can be easily
synthesized in accordance with those methods as described therein.
The compounds having the foregoing Formula [I] are especially excellent in
their fog restrainability in the light-sensitive material's long-period
preservation under a high temperature-high humidity condition (about
50.degree.-60.degree. C./60-90% RH) rather than merely under a high
temperature condition (about 50.degree.-60.degree. C.).
On the other hand, the compounds having Formula [II], which were also
proposed as antifoggants by us in Japanese Patent Application No.
14536/1986, were found out, as a result of our later investigation, to
show an excellent fog restrainability in the preservation under a
high-temperature condition rather than under a high temperature-high
humidity condition in contrast to the above ones having Formula [I].
Where both compounds of Formula [I] and Formula [II] are used in
combination, there can be obtained an unexpected synergistic effect that
their individual single features can be further enhanced in smaller adding
quantities than the quantity of each of them used alone.
Where a compound [II] is used in combination with the compound of this
invention, the adding quantity of each of both compounds having Formula
[I] and Formula [II], when added to a silver halide emulsion, is
preferably in the range of from 10.sup.-6 to 10.sup.-1 mole per mole of
the silver halide contained in the emulsion, and more preferably from
10.sup.-5 to 10.sup.-2 mole. When added to non-light-sensitive layers, the
compounds having Formula [I] and Formula [II] each is in the quantity
range of from 10.sup.-5 mole to 1 mole in the coating liquid on a support
per m.sup.2, and more preferably from 10.sup.-4 to 10.sup.-1 mole. Both
compounds [I] and [II] may be used in a wide proportional range such as of
from 1:0.01 to 1:100 by weight, but preferably from 1:0.1 to 1:50 by
weight.
The silver halide light-sensitive material to which this invention is
applied may use any arbitrary silver halides for usual use in ordinary
silver halide emulsions, such as silver bromide, silver iodobromide,
silver iodochloride, silver chlorobromide, silver chloride, and the like.
The silver halide grains usable in the silver halide emulsion may be ones
obtained by any of the acid process, neutral process and ammoniacal
process. These grains may be grown either at once or after the preparation
of seed grains. The method of preparing seed grains and that of growing
the grains may be either the same or different.
The silver halide emulsion may be prepared either by mixing halide and
silver ions simultaneously or by mixing either one into a liquid in which
the other is present. Also, the halide ion and silver ion may be poured
sequentially simultaneously, taking into account the critical growth rate
of silver halide grains, into a mixing pot with the pH and/or pAg
thereinside being controlled. By this method, silver halide grains in the
regular crystal form with their grain size nearly uniform can be obtained.
After the growth the halogen composition of the obtained grains may be
changed by use of the conversion method.
The silver halide emulsion may have the grain size, grain form, grain size
distribution and grain growth rate thereof controlled, if necessary at the
time of the manufacture thereof, by use of a silver halide solvent.
The silver halide grain may contain metallic elements in the inside and/or
on the surface thereof by adding thereto metallic ions, in the course of
forming and/or growing the grain, by using at least one salt selected from
the group consisting of cadmium salts, zinc salts, lead salts, thalium
salts, iridium salts (including complex salts), rhodium salts (including
complex salts), and iron salts (including complex salts), and may be
provided in the inside and/or on the surface thereof with a reduction
sensitization nucleus by being place in an appropriate reductive
atmosphere.
The silver halide emulsion, after completion of the growth of the silver
halide grains therof, may have the useless water-soluble salt either
removed therefrom or remain thereinside. If desired to remove the salt,
the removal can be made in accordance with the method described in
Research Disclosure (hereinafter abbreviated to RD) No. 17643 Item II.
The silver halide grain, although it may be one having a uniform silver
halide composition distribution thereinside, but is particularly desirable
to be a core/shell type grain whose inside and surface stratusm are
different in the silver halide composition.
The core/shell type silver halide emulsion is of a structure consisting of
two or more strata different in the silver iodide content; the
largest-amount silver iodide-containing stratum (called "core") is other
than the surface stratum (called "shell").
The core/shell type emulsion suitably usable for the light-sensitive
material to be used in this invention is one in which the silver iodide
content of the largest-amount silver iodide-containing inside stratuem
(core) is from 6 to 40 mole %, more preferably from 8 to 30 mole %, and
most preferably from 10 to 20 mole %. The silver iodide content of the
surface stratum is preferably less than 6 mole %, and more preferably from
zero to 4.0 mole %.
The proportion of the shell portion to the core/shell type silver halide
grain should account for preferably 10 to 80%, more preferably 15 to 70%,
and most preferably 20 to 60%.
The core portion should account for preferably 10 to 80% of the whole
grain, and more preferably 20 to 50%.
The difference in the silver iodide content between the large-amount silver
iodide-containing core portion and the small-amount silver
iodide-containing shell portion may either be sharply defined or not
necessarily be clearly defined, continuously changing in the silver iodide
content. In addition, one having a medium-amount silver iodide-containing
intermediate stratum between the core and shell portions may also be
suitably used.
In the case of the core/shell type silver halide grain having the
above-mentioned intermediate stratum, the preferred volume of the
intermediate stratum accounts for 5 to 60% of the whole grain, and more
preferably 20 to 55%.
Each of the differences in the silver iodide content between the shell and
the intermediate stratum and between the intermediate stratum and the core
is preferably not less than 3 mole %, and the difference in the silver
iodide content between the shell and the core is preferably not less then
6 mole %.
In the light-sensitive material to be used in this invention, the
core/shell type silver halide emulsion is of silver iodobromide whose
silver iodide content is preferably from 4 to 20 mole %, and more
preferably from 5 to 15 mole %. The emulsion may also contain silver
chloride as long as it does not hurt the effect of this invention.
The above-mentioned core/shell type emulsion may be prepared in accordance
with those prior-art methods as disclosed in Japanese Patent O.P.I.
Publication Nos. 177535/1984, 138538/1985, 52238/1984, 14331/1985,
35726/1985, 258536/1985, and the like.
Where the core/shell type silver halide grain is grown starting from a seed
grain as in the method described in Japanese Patent O.P.I. Publication
138538/1985, the grain can have in its center a silver halide composition
region different from the core. In such an instance, the halide
composition of the seed grain, although it may be any arbitrary
composition such as silver bromide, silver iodobromide, silver
chloroiodobromide, silver chlorobromide, silver chloride or the like,
should preferably be of silver iodobromide whose silver iodide content is
not more than 10 mole % or silver bromide.
The seed silver halide grains should account for preferably not more than
50% of the whole silver halide, and most preferably not more than 10%.
The distribution condition of the silver iodide in the foregoing core/shell
type silver halide grains can be detected in accordance with various
measuring methods, and can be investigated by the luminescence measurement
at a low temperature or the X-ray diffraction method as described in the
substance book of the annual lecture meeting 1981 of the Society of
Photographic Science and Technology of Japan.
The core/shell type silver halide grain may be of either a regular crystal
such as a cubic, tetradecahedral or octahedral crystal, or a twin. And the
grain may also be a mixture of these crystals, but is desirable to be a
regular crystal.
The silver halide grain may be grown in the presence of a know silver
halide solvent such as ammonia, thioether, thiourea, or the like.
The silver halide grain, including the core/shell type grain, contained in
the light-sensitive material to be used in the method of this invention
may contain metallic elements in the inside and/or on the surface thereof
by adding thereto, in the course of forming and/or growing the grain,
metallic ions, using at least one salt selected from the group consisting
of cadmium salts, zinc salts, lead salts, thalium salts, iridium salts
(including complex salts), rhodium salts (including complex salts), and
iron salts (including complex salts), and also may be provided in the
inside and/or on the surface thereof with a reduction sensitization
nucleus.
The silver halide emulsion, after completion of the growth of the silver
halide grains thereof may have the useless water-soluble salt either
removed therefrom or remain thereinside. In the case of removing the salt,
the removal may be made in accordance with the method described in RD
17643, Item II.
The silver halide grain may be either one that a latent image is mainly
formed on the surface thereof or one that a latent image is mainly formed
thereinside. The usable silver halide grain size should be from 0.05 to
30.mu., and preferably from 0.1 to 20.mu..
The silver halide emulsion used may be of any grain size distribution. A
wide grain size distribution-having emulsion (called polydisperse
emulsion) may be used, and differently narrower grain size
distribution-having emulsions may also be used alone or in a mixture
thereof. A polydisperse emulsion and a monodisperse emulsion may be used
in a mixture thereof, but the emulsion used herein is desirable to be a
monodisperse emulsion.
In this invention, the monodisperse emulsion is desirable to be one in
which the weight of the silver halide thereof whose grain sizes are within
the size range of the average grain size r.+-.20% accounts for not less
than 60% of the weight of the whole silver halide, more preferably not
less than 70%, and most preferably not less than 80%.
The average grain size r is defined as the grain size ri when the
ni.times.ri.sup.3, the product of the frequency ni of the grain having a
grain diameter ri with ri.sup.3, becomes maxium. (Effective number of
three figures, the minimum figure is rounded to the nearest whole number).
The grain size herein, in the case of a spherical silver halide grain, is
defined as the diameter thereof and, where the grain is in the
non-spherical form, is the diameter of a circular image into which is
converted the projection image of the grain image of the same area.
The grain diameter can be obtained, for example, in the manner that the
grain's image is magnified by an electron microscope to a 10,000 to 50,000
times-enlarged photo and the diameter or the projected area of the grain's
image of the obtained print is actually measured. (The number of the
grains to be measured should be not less than 1000 taken at random.)
The particularly preferred highly monodisperse emulsion in this invention,
when the width of the grain size distribution thereof is defined by
##EQU1##
is one whose distribution width is not more than 20%, and more preferably
not more than 15%, wherein the average grain size and the standard
deviation are found from the ri as defined previously.
The monodisperse emulsion can be obtained by adding an aqueous silver salt
solution and an aqueous halide solution to a gelatin solution containing
seed grains by the double-jet method under the control of pAg and pH.
Reference can be made to Japanese Patent O.P.I. Publication Nos.
48521/1979 and 49938/1983 for determining the adding speed of the above
solutions.
In order to obtain a further highly monodisperse emulsion, the growing
method in the presence of tetrazaindene as disclosed in Japanese Patent
O.P.I. Publication No. 122935/1985 may be used.
The silver halide emulsion may be used in a mixture of two or more
separately formed silver halide emulsions.
The siler halide emulsion may be chemically sensitized in usual manner;
i.e., by using alone or in combination the sulfur sensitization method,
selenium sensitization method, reduction sensitization method, noble-metal
sensitization method which uses gold or other noble-metallic compounds,
and the like.
The silver halide emulsion may be optically sensitized to desired
wavelength regions by using dyes known as sensitizing dyes to the
photographic field. Those sensitizing dyes may be used either alone or in
combination of two or more of them. A supersensitizer, a dye which itself
has no spectrally sensitizing function or a compound which does
substantially not absorb visible rays but enhances the sensitization
function of sensitizing dyes, may be incorporated along with such
sensitizing dyes into the silver halide emulsion.
Those usable as the sensitizing dye for the emulsion include cyanine dyes,
merocyanine dyes, complex cyanine dyes, complex merocyanine dyes,
holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes.
The particularly useful dyes are cyanine dyes, merocyanine dyes, and
complex merocyanine dyes.
To these dyes may be applied any of those nuclei usually utilized as the
basic heterocyclic nucleus in cyanine dyes, the said nuclei including
pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus,
oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus,
tetrazole nucleus, pyridine nucleus, and nuclei formed by fusing alicyclic
hydrocarbon rings to these nuclei, and nuclei formed by fusing aromatic
hydrocarbon rings to these nuclei; i.e., indolenine nucleus,
benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole
nucleus, benzothiazole nucleus, benzoselenazole nucleus, benzimidazole
nucleus, quinoline nucleus, and the like. These nuclei each may have a
substituent on the carbon thereof.
To the merocyanine dye or complex cyanine dye may be applied a 5- or
6-member heterocyclic nucleus, as one having a ketomethylene structure,
such as pyrazoline-5-one nucleus, thiohydantoin nucleus,
2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
rhodanine nucleus, thiobarbituric acid nucleus, or the like.
Useful sensitizing dyes for a blue-sensitive silver halide emulsion layer
are those as described in, e.g., West German Patent No. 929,080, U.S. Pat.
Nos. 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,959,
3,672,897, 3,694,217, 4,025,349 and 4,046,572, British Pat. No. 1,242,588,
Japanese Patent Examined Publication No. 14030/1969 and 24844/1977, and
the like. Useful sensitizing dyes for a green-sensitive silver halide
emulsion are those typical cyanine dyes, merocyanine dyes or complex
cyanine dyes as described in, e.g., U.S. Pat. Nos. 1,939,201, 2,072,908,
2,739,149, 2,945,763, and the like. And useful sensitizing dyes for a
red-sensitive silver halide emulsion are those typical cyanine dyes,
merocyanine dyes or complex cyanine dyes as described in, e.g., U.S. Pat.
Nos. 2,269,234, 2,270,378, 2,442,710, 2,454,629, 2,776,280, and the like.
Further, those cyanine dyes, merocyanine dyes or complex cyanine dyes as
described in U.S. Pat. Nos. 2,213,995, 2,493,748 and 2,519,001, and West
German Pat. No. 929,080, and the like, may be advantageously used for a
green-sensitive or red-sensitive silver halide emulsion.
These sensitizing dyes may be used either alone or in combination. The
combination of these sensitizing dyes is often used particularly for the
purpose of supersensitization. Examples representative of it are described
in Japanese Patent Examined Publication Nos. 4932/1968, 4933/1968,
4936/1968, 32753/1969, 25831/1970, 26474/1970, 11627/1971, 18107/1971,
8741/1972, 11114/1972, 25379/1972, 37443/1972, 28293/1973, 38406/1973,
38407/1973, 38408/1973, 41203/1973, 41204/1973, 6207/1974, 40662/1975,
12375/1978, 34535/1979 and 1569/1980, Japanese Patent O.P.I. Publication
Nos. 33220/1975, 33828/1975, 38526/1975, 107127/1975, 115820/1976,
135528/1976, 151527/1976, 23931/1977, 51932/1977, 104916/1977,
104917/1977, 109925/1977, 110618/1977, 80118/1979, 25728/1981, 1438/1982,
10753/1983, 91445/1983, 153926/1983, 114533/1984, 116645/1984 and
116647/1984, and U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060,
3,506,443, 3,578,447, 3,672,898, 3,679,428, 3,769,301, 3,814,609 and
3,837,862.
Those dyes which in themselves have no spectral sensitization function or
materials which do substantially not absorb visible rays but show
supersensitization effects and which are usable along with the above
sensitizing dyes are, for example, those aromatic organic
acid-formaldehyde condensates (as described in, e.g., U.S. Pat. No.
3,473,510), those cadmium salts, azaindene compounds, nitrogen-containing
heterocyclic group-substituted aminostilbene compounds (as described in,
e.g., U.S. Pat. Nos. 2,933,390 and 3,635,721), and the like. The combined
use described in U.S. Pat. Nos. 3,615,613, 3,615,641, 3,617,295 and
3,635,721 are particularly useful.
In the silver halide emulsion, for the purpose of preventing the production
of a fog or of keeping the photographic characteristics stable during the
manufacture, storage or photographic processing of the light-sensitive
material, any of those compounds known as antifoggants or stabilizers to
those skilled in the art may be used along with the foregoing compound [I]
or [II] during, upon completion of and/or after completion of the chemical
ripening prior to the coating of the silver halide emulsion.
Examples of the usable antifoggant or stabilizer include azoles such as
benzothiazole, nitroindazole, benzotriazole, nitrobenzimidazole, etc.,
mercapto-substituted heterocyclic compounds such as mercaptobenzothiazole,
mercaptobenzimidazole, mercaptobenzoxazole, mercaptooxadiazole,
mercaptothiadiazole, mercaptotriazole, mercaptotriazine,
mercaptotetrazoles (such as 1-phenyl-5-mercaptotetrazole), those wherein
sulfonic acid group or carboxy group is introduced to the above
mercaptoheterocyclic compouns, and further azaindenes such as
4-hydroxy-1,3,3a,7-tetrazaindene; those thiazolium salts as described in
U.S. Pat. Nos. 2,131,038, 3,342,569, 3,954,478, those pyrilium salts as
described in U.S. Pat. No. 3,148,067, and those quaternary onium salts as
described in Japanese Patent Examined Publication No. 40665/1975; those
catechols as described in U.S. Pat. No. 3,236,652 and Japanese Patent
Examined Publication No. 10256/1968, those resorcinols as described in
Japanese Patent Examined Publication No. 44413/1981, and those
polyhydroxybenzenes such as gallic acid esters as described in Japanese
Patent Examined Publication No. 4133/1968; those tetrazoles as described
in West German Pat. No. 1,189,380, those triazoles as described in U.S.
Pat. No. 3,157,509, those benzotriazoles as described in U.S. Pat. No.
2,704,721, those urazoles as described in U.S. Pat. No. 3,287,135, those
pyrazoles as described in U.S. Pat. No. 3,106,467, those indazoles as
described in U.S. Pat. No. 2,271,229, and those azoles such as polymerized
benzotriazoles as described in Japanese Patent O.P.I. Publication No.
90844/1984, those pyrimidines as described in U.S. Pat. No. 3,161,515,
those 3-pyrazolidones as described in U.S. Pat. No. 2,751,297, and those
polymerized pyrrolidones, i.e., heterocyclic compounds such as
polyvinyl-pyrrolidones as described in U.S. Pat. No. 3,021,213; those
various inhibitor precursors as described in Japanese Patent O.P.I.
Publication Nos. 130929/1979, 137945/1984, 140445/1984, British Pat. No.
1,356,124, U.S. Pat. Nos. 3,575,699 and 3,649,267, and the like; those
sulfinic acid and sulfonic acid derivatives as described in U.S. Pat. No.
3,047,393; and those inorganic salts as described in U.S. Pat. Nos.
2,556,263, 2,839,405, 2,488,709 and 2,728,663; and the like.
Gelatin is advantageously usable as the binder (or protective colloid) for
the silver halide emulsion, and gelatin derivatives, graft polymers of
gelatin with other high-molecular materials, other proteins, sugar
derivatives, cellulose derivatives, hydrophilic colloid materials such as
synthetic hydrophilic high-molecular homo- or co-polymer materials may
also be used.
Photographic emulsion layers and other hydrophilic colloid layers of the
light-sensitive material of this invention may be hardened by using alone
or in combination hardening agents that cross-link the binder (or
protective colloid) molecular to enhance the strength thereof. The
hardening agent may be added in a quantity so enough to harden the
light-sensitive material that the hardening agent need not be added to the
processing solution, but the hardening agent is also allowed to be added
to the processing solution.
To silver halide emulsion layers and/or other hydrophilic colloid layers of
the light-sensitive material may be added a plasticizer for the purpose of
increasing the elasticity. The preferred plasticizers are those compounds
described in RD 17643 XII A.
Into photographic emulsion layers and other hydrophilic colloid layers of
the light-sensitive material may be incorporated water-insoluble or
less-soluble synthetic polymer-dispersed product (latex) for the purpose
of improving the dimensional stabilization thereof.
The emulsion layer of the light-sensitive material may contain a
dye-forming coupler which, in the color developing process, forms a dye by
the coupling reaction thereof with the oxidized product of an aromatic
primary amine developing agent (such as a p-phenylenediamine drivative,
aminophenol derivative, etc.). The dye-forming coupler is usually selected
so as to form a dye to absorb an appropriate spectral light which each
individual emulsion is sensitive to; an yellow dye-forming coupler is used
for the blue-sensitive emulsion layer, a magenta dye-forming coupler is
used for the green-sensitive emulsion layer, and a cyan dye-forming
coupler is used for the red-sensitive emulsion layer. However, a silver
halide color photographic light-sensitive material is allowed to be
prepared otherwise, using a different combination than the above according
to purposes.
These dye-forming couplers are desirable to have in the molecule thereof a
group called `ballasting group` having not less than 8 carbon atoms to
make them nondiffusible. These dye-forming couplers each may be either of
the four-equivalent type, which requires 4 molecules of silver ions to be
reduced for the formation of one molecule of the dye, or of the
two-equivalent type, which requires only two molecules of silver ions to
be reduced. These dye-forming couplers include those compounds which, as a
result of coupling with the oxidized product of a developing agent,
release photographically useful fragments such as development inhibitors,
development accelerators, bleaching accelerators, developing agents,
silver halide solvents, color control agents, hardening agents, fogging
agents, antifoggants, chemical sensitizers, spectral sensitizers and
desensitizing agents.
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