FIELD OF THE INVENTION
[0001] This invention relates to a silver halide emulsion useful in the photographic field
and to a silver halide color photographic light sensitive material applied with the
above-mentioned emulsion and, particularly, to the silver halide emulsion remarkably
improved in image-sharpness and pressure characteristics and to the silver halide
color photographic light sensitive material applied with the above-mentioned emulsion,
which is excellent in image-sharpness, pressure, color reproduction characteristics
and gradation.
BACKGROUND OF THE INVENTION
[0002] Recently, in the field of silver halide color photographic light sensitive materials,
the progress of super high-sensitization typified by ISO 1600 to 3200 and a small
format typified by disk-films have been made and a high image-quality has therefore
been required. For satisfying the requirement, a lot of studies have been made mainly
on the improvements of silver halide emulsions.
[0003] For example, U.S. Patent No. 4,439,520 and Japanese Patent Publication Open to Public
Inspection (hereinafter referred to as JP OPI Publication) Nos. 62-99751(1987) and
62-115435(1987) disclose the multilayered color photographic light sensitive materials
having a high speed and an excellent dye-image sharpness in which the high speed layer
thereof contains a tabular-grained silver halide emulsion having a grain thickness
of less then 0.3 µm and an aspect ratio of not less than 8 : 1. Besides, JP OPI Publication
Nos. 57-93344(1982), 54-145135(1979) and 57-151944(1982) disclose the techniques for
improving image-sharpness by making use of the diffusible DIR.
[0004] Therein the techniques of the tabular-shaped grains may be classified into those
for improving an image-sharpness upon utilizing an optical effect, and the techniques
of the DIR compounds may be classified into those for improving an image-sharpness
upon utilizing a development effect. In particular, a light scattering produced of
silver halide grains will seriously affect an image-sharpness and, as pointed out
in each of the foregoing patent publications, an image-sharpness is remarkably improved
when the silver halide grains are each tabular-shaped and have a thickness of less
than 3 µm. Besides the above-given disclosures, there have been the disclosures of
many other techniques on the above-mentioned tabular-shaped silver halide grains.
For example, JP OPI Publication Nos. 58-113926(1983), 58-113927(1983) and 58-113926(1983)
disclose each the emulsion grains having an aspect ratio of not less than 8.
[0005] The term, an 'aspect ratio', mentioned herein means a ratio of the thickness of a
tabular-shaped silver halide grain to the diameter thereof. The term, 'the diameter
of a grain', mentioned herein means the diameter of a circle having the same area
as the projective area of the grain when an emulsion is observed through a microscope
or an electron microscope. The term, a 'grain thickness', means the distance between
the two parallel surfaces constituting a tabular-shaped silver halide grain.
[0006] The above-mentioned tabular-shaped silver halide grains are characterized in hardly
monodispersing themselves as compared to any nontabular-shaped silver halide grains
(which are regularly crystallized). There have been various attempts for monodispersing
the tabular-shaped silver halide grains and some of the patents on the attempts have
been disclosed so far.
[0007] JP OPI Publication Nos. 52-153428(1977), 55-142329(1980), 61-112142(1986) and 51-39027(1976)
and French Patent No. 253,406 disclose each the techniques for monodispersing tabular-shaped
silver halide grains. In every one of the techniques, the silver halide grains used
therein have a low aspect ratio of less than 3 or they are the mixture of hexagonal
and triangular tabular grains. Therefore, they are still not satisfactory for the
monodisperse type tabular-shaped grains. As for the tabular-shaped grains uniform
in both configuration and grain-size, the monodisperse type tabular-shaped grains
mainly having a hexagonal configuration have been disclosed in JP OPI Publication
Nos. 63-151618(1988, 1-213637(1989) and 2-838(1990).
[0008] However, the tabular-shaped silver halide grains such as those mentioned above are
seriously poor in pressure characteristics and it has been difficult to improve any
image-sharpness without deteriorating the pressure characteristics in any conventional
techniques. The term, 'pressure characteristics', has the two meanings; one meaning
is that an unexposed portion is developed, that is so-called a pressure fog and the
other meaning is that a photosensitive speed is lowered when making an exposure, that
is so-called a pressure desensitization, each when a pressure is applied to a silver
halide photographic light sensitive material. If the above-mentioned characteristics
are poor, the silver halide photographic light sensitive material will have a serious
defect.
[0009] It is the matter of course that the more the thickness of a tabular-shaped grain
is thinner, the more the pressure characteristics are mechanically weaker and, therefore,
the pressure characteristics will tend to be deteriorated. However, the pressure characteristics
of the grain will be more seriously deteriorated when the grain has a higher aspect
ratio even if the grain thickness remains the same. It may be interpreted that the
tabular-shaped grain is liable to receive a greater moment as compared to a globular-shaped
grain even if the materials of both of the grains have the same mechanical strength.
The above-mentioned pressure characteristics are varied by the distributions of the
halogen compositions of silver halide grains, the conditions for a chemical sensitization
and the silver halide configurations.
[0010] Generally speaking, when a chemical sensitization level is insufficient, (in other
words, when a chemical ripening is made insufficiently), a pressure desensitization
will be deteriorated. When a chemical sensitization level is excessive, a pressure
fog production will be deteriorated, though the pressure desensitization may be reduced.
[0011] When a highly iodide containing portion is made present in silver halide grains,
a pressure fog production tend to be deteriorated, though the pressure fog production
tend to be improved.
[0012] In the silver halide compositions, silver chloride, silver chlorobromide, silver
chloroiodobromide, silver iodide or silver iodobromide may selectively be used so
as to meet the purposes and applications of light sensitive materials. However, silver
iodobromide may often be used in color photographic films for general use. The distribution
of the grain compositions inside silver halide grains is optimized for controlling
the gradations, color reproducibility and photosensitive speeds, as well as for controlling
the pressure characteristics thereof. Therefore, when the color reproducibility and
gradations are improved, there may often raise such an antinomic problem that the
pressure characteristics may be deteriorated.
[0013] For example, when a silver halide has a higher iodine content, the silver halide
will be sensitized higher. However, the light absorption wavelength region inhering
in silver halide will affect the long-wavelength side and color reproducibility. Therefore,
a high image-quality color film can be improved in color reproducibility by making
use of silver iodobromide having a low iodine content. When silver halide is made
to have a low iodine content, however, there raises such a problem that the developability
(that is, the developing speed) of silver halide grains may be increased so that the
gradation may be hardened. On the other hand, tabular-shaped silver halide grains
will have a developing speed higher than those of the other-shaped grains even if
the halogen composition thereof are the same with each other. In this case, the above-mentioned
hard gradation problem may, therefore, become remarkable.
[0014] From the viewpoints of photosensitivity and pressure characteristics, it is generally
desired that silver halide grains are to have a higher monodispersibility. When making
use of monodisperse type silver halide grains, however, the gradation thereof is hardened.
When making use of tabular-shaped silver halide grains having a low iodine content
for the purposes of improving color reproducibility and image-sharpness, it cannot
prepare nothing but a strikingly hard light sensitive material. Particularly in the
case of a color negative film which requires a wide exposure latitude and a soft gradation,
the above-mentioned gradation problem is essential and, it has, therefore, been demanded
to provide an emulsion excellent in color reproduction characteristics, that is, an
emulsion low in iodine content, excellent in both image-sharpness and pressure characteristics,
but without spoiling the gradation thereof.
OBJECTS OF THE INVENTION
[0015] It is an object of the invention to provide a silver halide emulsion remarkably improved
in image-sharpness and pressure characteristics and, at the same time, to provide
a silver halide photographic light sensitive material applied with the above-mentioned
emulsion.
[0016] Another object of the invention is to provide a silver halide emulsion without spoiling
any gradation, but excellent in image-sharpness, color reproducibility and pressure
characteristics and, at the same time, to provide a silver halide photographic light
sensitive material applied with the above-mentioned emulsion.
SUMMARY OF THE INVENTION
[0017] The present inventors have discovered that the above-mentioned objects of the invention
can be achieved in each of the inventions applied in the following patent application.
[0018] To be more concrete, the invention can be achieved with a silver halide emulsion
characterized in satisfying the following requirements:
(A) At least 50% of the whole projective area of the silver halide grains contained
in an emulsion is to be occupied by tabular-shaped silver halide grains having an
aspect ratio within the range of 3.0 to 7.0;
(B) At least 70% of the whole projective area of the silver halide grains contained
in an emulsion is to be occupied by tabular-shaped silver halide grains each bearing
even numbers of the twinned crystal faces parallel to the principal face formed in
a hexagon having a maximum adjacent side ratio within the range of 2.0 to 1.0; and
(C) The silver halide grains mentioned in the above-given requirement (B) are to have
a grain-size variation coefficient within the range of 21 to 29% and a thickness variation
coefficient of not more than 20%.
[0019] The invention can also be achieved with a silver halide photographic light sensitive
material characterized in the following requirements:
The light sensitive material is to comprise a support bearing thereon at least
one of light sensitive silver halide emulsion layers and at least one of non-light
sensitive hydrophilic colloidal layers;
At least either one of the light sensitive silver halide emulsion layers is to
contain the silver halide emulsion claimed in claim 1; and
In all the non-light sensitive hydrophilic colloidal layers each apart from the
support farther than the light sensitive silver halide emulsion layer farthest from
the support, the total dried layer thickness thereof is to be not thicker than 2.0µm.
[0020] The invention can further be achieved with a silver halide photographic light sensitive
material claimed in claim 2, which is characterized in the following requirements:
The light sensitive material is to comprise a support bearing thereon at least
one each of red-sensitive silver halide emulsion layers containing each a cyan coupler,
green-sensitive silver halide emulsion layers containing each a magenta coupler and
blue-sensitive silver halide emulsion layers containing each a yellow coupler;
At least either one of the green-sensitive silver halide emulsion layers and/or
the blue-sensitive silver halide emulsion layers is to contain the silver halide emulsion
claimed in claim 1.
DETAILED DESCRIPTION OF THE INVENTION
[0021] In tabular-shaped silver halide grains contained in the silver halide emulsions of
the invention (hereinafter sometimes abbreviated to 'the tabular grains of the invention'),
the term, an 'aspect ratio', herein means the diameter/thickness ratio of a subject
grain; the term, a 'diameter of a silver halide grain', herein means the diameter
of a circle having the same area with the projective area of a subject grain; and
the term, a 'grain thickness', herein means a distance between two parallel faces
constituting a subject tabular-shaped silver halide grain.
[0022] In the invention, the expression, 'a hexagonal tabular-shaped grain', herein means
that a subject grain has a hexagonal (111) face and a maximum adjacent side ratio
within the range of 1.0 to 2.0. The term, 'a maximum adjacent side ratio', herein
means a ratio of the length of the shortest side of a hexagon to the length of the
longest side thereof. The hexagonal tabular-shaped grains of the invention may also
have rounded corners to some extent, provided, the maximum adjacent side ratio thereof
is to be within the range of 1.0 to 2.0. When the corners of the hexagon is rounded
to some extent, the length of a hexagonal side is to be expressed by the distance
between the two points intersecting a line extended from the straight portion of a
subject side and each of the lines extended from the straight portions of the adjacent
sides each other.
[0023] In the hexagonal tabular-shaped grains of the invention, each of the sides thereof
substantially comprises a straight line having a length of, desirably, not shorter
than one half of the side length and, preferably, not shorter than four-fifths of
the side length. In the invention, an adjacent side ratio is preferable to be within
the range of 1.0 to 1.5.
[0024] The silver halide emulsions of the invention are generally comprised of a dispersion
medium and silver halide grains. In not less than 70%, desirably not less than 80%
and preferably not less than 90% of the silver halide grain projective areas, the
grains are each shaped in a hexagon having an adjacent side ratio within the range
of 1.0 to 2.0. And, the grains are occupied by tabular-shaped silver halide grains
each having two parallel twinned-crystal faces.
[0025] The hexagonal tabular-shaped grains stated in the invention are characterized in
having a plurality of (e.g., a couple of) parallel twinned-crystal faces. This fact
can be confirmed by observing the cross section of the thin layer cut piece of an
emulsion-coated film at a low temperature (i.e., at a liquid nitrogen temperature)
through a transmission type electron microscope.
[0026] The term, 'the variation coefficient of grain sizes', stated in the invention, herein
means the degrees of a grain size scattering, and it is expressed by a percentage
obtained when the standard deviation of the projective areas (converted into the circular
diameter) of hexagonal tabular-shaped grains of the invention having a maximum adjacent
side ratio within the range of 1.0 to 2.0 is divided by the average grain size.
[0027] The term, 'the variation coefficient of grain thickness', stated in the invention,
herein means the degrees of a grain thickness scattering, and it is expressed by a
percentage obtained when the standard deviation of the thickness of hexagonal tabular-shaped
grains of the invention having a maximum adjacent side ratio within the range of 1.0
to 2.0 is divided by the average thickness.
[0028] In at least 50% of the whole projective area of the silver halide grains of the invention,
they are comprised of tabular-shaped grains having an aspect ratio within the range
of 3.0 to 7.0. It is preferred that the tabular-shaped grains are to have an aspect
ratio within the range of 3.0 to 7.0 in at least 70% of the whole projective area.
[0029] The aspect ratio thereof is to be within the range of 3.0 to 4.9, desirably, in at
least 50% of the whole projective area and, preferably, in at least 70% of the whole
projective area.
[0030] If the aspect ratio is too high, pressure characteristics (such as a pressure desensitization
and a pressure fog production) will be deteriorated, because the maximum moment is
increasingly applied to silver halide grains when a pressure is applied to a light
sensitive material. On the contrary, if the aspect ratio is too low, an image-sharpness
will undesirably be deteriorated by a light scattering, because grains are thickened
to shorten the projective diameter so as to become closer to the length scattering
visible rays of light.
[0031] The above-mentioned aspect ratio has an optimum value from the viewpoints of pressure
characteristics and image-sharpness. It is, therefore, the matter of course that the
proportions of the grains out of the desirable aspect ratio range are preferred to
be the less, the better in the distribution of silver halide grains.
[0032] At least 70% of the whole projective area of the silver halide grains contained in
an emulsion is to be occupied by the silver halide grains of the invention each bearing
even numbers of the twinned crystal faces parallel to the principal face formed in
a hexagon having a maximum adjacent side ratio within the range of 2.0 to 1.0; and
at least 90% of the whole projective area is preferably occupied by the hexagonal
tabular-shaped silver halide grains such as those mentioned above.
[0033] It is also desirable that at least 70% of the whole projective area is occupied by
hexagonal tabular-shaped grains having a maximum adjacent side ratio within the range
of 0.1 to 1.5 and it is further preferable that at least 90% of the whole projective
area is occupied by hexagonal tabular-shaped grains having a maximum adjacent side
ratio within the range of 0.1 to 1.5. If the percentage of the hexagonal tabular-shaped
grains is relatively low, it makes higher the percentage of the mixture of various
other-shaped silver halide grains such as those having regular-crystals, triangular
twinned crystals and various multiple twinned crystals.
[0034] When mixing the above-mentioned grains having the different configurations, the grains
are chemically sensitized on different levels according to the configurations of the
grains, because the chemical sensitization is seriously affected by the configurations,
surface indexes, compositions and defects each of silver halide grains. It is, therefore,
not only unable to satisfy the optimum chemical sensitization requirements because
of the relation between a sensitivity and a fog production, but also unable to make
the pressure characteristics satisfactory as the whole, because the grains worse in
pressure fog production and excessive in chemical ripening are mixed with the grains
worse in pressure desensitization and insufficient in chemical ripening. In the conditions
where a large number of hexagonal tabular-shaped grains having a high maximum adjacent
side ratio (i.e., triangular grains having rounded corners) are produced, the maximum
adjacent side ratios of each grain are liable to be scattered, that is, a group consisting
of grains each different in configurations is liable to be produced. Therefore, the
chemical sensitization can hardly be optimized and the resulting emulsion is also
deteriorated in pressure characteristics. It is, therefore, not desirable.
[0035] In the silver halide emulsions of the invention, pure silver bromide and silver iodobromide
can preferably be used. From the viewpoint of color reproducibility aptitude, the
average silver iodide content of silver iodobromide is desirably not more than 10
mol%, more desirably not more than 8 mol% and preferably not more than 6 mol%. From
the viewpoint of color reproducibility aptitude, pure silver bromide having a silver
iodide content of less than 0.5 mol% is preferably used. From the viewpoint of the
emulsion stability, those having a slight silver iodide content is desirably used.
From the overall viewpoints, the optimum silver iodide content is within the range
of 0.1 to 6 mol%, desirably 0.5 to 4 mol% and preferably 1 to 3.5 mol%.
[0036] From the viewpoints of color reproducibility aptitude and gradation, the average
silver iodide content is preferably within the above-mentioned range. From the viewpoint
of pressure characteristics, the silver iodide contents of individual silver halide
grains of an emulsion are preferable to be uniform among the grains, because a chemical
sensitization is affected by the silver iodide content thereof as well as by the aforementioned
grain configurations. The silver iodide contents of individual grains can be measured
by making use of an XMA (standing for an X-ray microanalyzer). When defining the percentage
of the standard deviation of the silver iodide contents of individual grains measured
by an XMA to an average silver iodide content as a relative standard deviation, (refer
to JP OPI Publication No. 60-254032/1985), such a relative standard deviation is desirably
not more than 20% and preferably not more than 15%, from the viewpoint of pressure
characteristics.
[0037] In the hexagonal tabular-shaped grains of the invention, the grain sizes thereof
are desirably not smaller than 0.4 µm, more desirably within the range of 0.5 to 3.0
µm and preferably within the range of 0.5 to 1.7 µm.
[0038] In the tabular-shaped grains of the invention, the average grain thickness thereof
is within the range of desirably 0.05 to 0.3 Mm, more desirably 0.05 to 0.25 µm and
preferably 0.05 to 0.20 µm. The grain sizes and grain thicknesses thereof can be optimized
so as to make the sensitivity, image-sharpness and pressure characteristics most excellent.
The optimum grain size and the optimum grain thickness may be varied by other factors
exerting an influence on sensitivity, image-sharpness and pressure characteristics,
(such as the thicknesses of hydrophilic colloidal layers, layer hardening degrees,
chemical ripening conditions, the amounts and kinds of DIR compounds used, the ISO
speeds and silver-coating weights of a subject light sensitive material) which constitute
a light sensitive material. The image-sharpness is more deteriorated when an average
grain size and average grain thickness are more closer to a scattering length (within
the range of 0.3 µm to 0.5 µm). The thicker the grain thickness is, the better the
pressure characteristics are. Even when the grain thicknesses are the same, the higher
the aspect ratio is, the more the pressure characteristics are deteriorated. The larger
the grain size is, the more the sensitivity is increased, but the graininess is deteriorated.
It is, therefore, preferable as same as in the cases of the conventional emulsions
to select the minimum grain size so as to provide a necessary sensitivity.
[0039] From the viewpoint of the pressure characteristics, it is preferable as mentioned
above that a grain size scattering is to be as small as possible, that is, a monodispersibility
is to be as higher as possible. However, the emulsions of the invention have a problem
that the gradation is hardened, because the emulsions of the invention comprise each
tabular-shaped grains having a higher developing rate and low iodine-containing grains,
and the gradation is accelerated to be hardened by the grain sizes are monodispersed,
so that the emulsions cannot be used. For the reason mentioned above, an optimum grain
size distribution is selected out of the range within which the pressure characteristics
and gradation can both be compatible. The optimum grain size variation coefficient
is to be within the range of 21 to 29% and the hexagonal tabular-shaped grains of
the invention have the variation coefficient within the above-specified range that
is preferably between 21% to 26%. When the variation coefficient is too large, a chemical
sensitization aptitude becomes unsatisfactory and the pressure characteristics are
deteriorated by the above-mentioned presumptive reasons. When the variation coefficient
is less than 21%, the gradation is unfavorably hardened, but the pressure characteristics
become better. From this fact, an antinomic requirement is raised for the variation
coefficient. On the silver halide grains of the invention, that is, on the hexagonally
configurated tabular-shaped silver halide grains each having an aspect ratio within
the range of 3.0 to 7.0 in at least 50% of the whole projective area and a maximum
adjacent side ratio within the range of 1.0 to 2.0 in at least 70% of the whole projective
area, the present inventors have discovered through their studies that the pressure
characteristics are improved as mentioned above and the excellent pressure characteristics
can be displayed up to the region where the grain size variation coefficient is relatively
larger. In other words, an excellent gradation can be displayed without spoiling any
pressure characteristics within the variation coefficient range of 21 to 29%. The
above-mentioned facts indicate that the optimum chemical sensitization is seriously
affected more by the configuration scattering than by the grain size scattering and
that a satisfactorily uniform chemical sensitization can be performed among the grains
by making the grain configurations uniform, even if there are slight grain size scattering.
In the case of a polydisperse type emulsion having a variation coefficient of not
less than 30%, the pressure characteristics are seriously deteriorated even if the
emulsion comprises hexagonal tabular-shaped grains having an aspect ratio within the
range of 3.0 to 7.0, because the chemical sensitization is not uniformly made.
[0040] As described above, the optimum thickness of the silver halide grains applicable
to the invention is selected so as to balance the pressure characteristics with the
image-sharpness. Even when an average grain thickness is the same, the smaller the
grain thickness scattering is, the better. In other words, it may be considered that,
even if the grains have a preferable average grain thickness from the viewpoints of
pressure characteristics and image-sharpness, some parts of the too thick grains produce
a light scattering and an image-sharpness deterioration and some parts of too thin
grains produce a pressure fog and a pressure desensitization, so that these grains
produce the defects of an emulsion. The grain thickness distribution, that is the
grain thickness variation coefficient, is expressed by a percentage of the standard
deviation of individual grain thickness to the average thickness thereof. On the hexagonal
tabular-shaped grains of the invention, the thickness variation coefficient thereof
is to be not more than 20% and preferably not more than 15%.
[0041] The emulsions of the invention are useful when they are used in various types of
light sensitive materials. The emulsions of the invention are remarkably effective
particularly when they are used in a silver halide photographic light sensitive material
comprising a support bearing thereon at least one of light-sensitive silver halide
emulsion layers and at least one of non-light sensitive hydrophilic colloidal layers
and containing the silver halide emulsion of the invention in at least one of the
light-sensitive silver halide emulsion layers and, further, having not thicker than
2.0 µm of the total dried thickness of the whole non-light sensitive hydrophilic colloidal
layer apart from the support farther than the light sensitive silver halide emulsion
layer apart farthest from the support. The above-mentioned effects may be presumably
displayed because the hydrophilic colloidal layer is made present as the outermost
layer of the light sensitive material (hereinafter referred to as a protective layer)
so as to play a role of protecting the silver halide emulsion layers from both of
a pressure desensitization and a pressure fog production, and because the thinner
the protective layer is in a light sensitive material, the worse the pressure characteristics
are and the pressure characteristics of an emulsion may remarkably reflect on the
characteristics of the light sensitive material.
[0042] When the protective layer of a light sensitive material is made thicker, the pressure
characteristics are improved. However, the image-sharpness is deteriorated in the
silver halide emulsion layers coated underneath the protective layer (i.e., close
to the support side). Therefore, a thinner protective layer is preferable for making
higher the image-quality of a light sensitive material. The silver halide emulsions
of the invention excellent in pressure characteristics are useful because the effects
thereof can be displayed particularly when they are used in a light sensitive material
having such a thinner protective layer as mentioned above and an excellent image-sharpness.
The image-sharpness of a light sensitive material having a thin protective layer are
not so much deteriorated by the presence of a protective layer and, therefore, the
light scattering of silver halide grains becomes dominant. Also regarding the image-sharpness,
the effects of the tabular-shaped silver halide grains of the invention can remarkably
be displayed particularly in a light sensitive material having such a thin protective
layer as mentioned above..
[0043] The thickness of a protective layer means the total dried layer thicknesses of the
whole non-light sensitive hydrophilic colloidal layer apart from a support farther
than the silver halide emulsion layer apart farthest from the support. The thickness
thereof can be measured by cutting a light sensitive material into pieces by making
use of a microtome and then by measuring the cut pieces through an optical or electron
microscope. The pressure characteristic and image-sharpness effects of the emulsions
of the invention can be remarkably displayed in a light sensitive material provided
with a thin protective layer having a layer thickness of not more than 2.0 µm and
particularly not more than 1.5 µm.
[0044] The effects of the invention can be displayed in a light sensitive material provided
with the above-mentioned thin protective layer and the invention is useful in a variety
of light sensitive materials such as a monochromatic light sensitive material, a color
reversal film and a color negative film and, the invention is particularly useful
in a multilayered color light sensitive material. To be more concrete, it is particularly
useful for making the image-sharpness and pressure characteristics excellent to use
the tabular-shaped silver halide emulsions of the invention in the green-sensitive
and/or blue-sensitive silver halide emulsions of a silver halide color photographic
light sensitive material comprising a support bearing thereon at least one each of
red-sensitive silver halide emulsion layers containing cyan color developing couplers,
green-sensitive silver halide emulsion layers containing magenta color developing
couplers and blue-sensitive silver halide emulsion layers containing yellow color
developing couplers. The above-mentioned usefulness may be presumed because the blue-sensitive
and green-sensitive layers are provided relatively far from the support that is provided
closer to a protective layer so that the layers are liable to be affected by a pressure
and the image-sharpness is liable to be affected by a light scattering in the silver
halide emulsion layer provided closer to the support.
[0045] When making use of the silver halide emulsions of the invention in the blue-sensitive
and/or green-sensitive layers, each of the color-sensitive layers may be comprised
of a single silver halide emulsion layer or may be comprised of a plurality of layers
each having the different speeds. When the layer containing the silver halide emulsion
of the invention is comprised of a plurality of layers, the effects can be displayed
when at least one of the component layers contains the silver halide emulsion of the
invention. It is, however, preferable to contain the silver halide emulsion of the
invention in two or more of the component layers.
[0046] In the invention, the hexagonal tabular-shaped grains may be comprised of any one
of silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide
and, among them, silver bromide and silver iodobromide are preferably used. Silver
iodide may preferably be contained in an amount within the foregoing range. The crystal
structures thereof are allowed to have a uniform structure, the compositions heterogeneous
between the inside and the outside or a layered structure. It is also preferable to
contain reduction-sensitization silver nuclei in the grains. It can readily be judged
whether the reduction-sensitization silver nuclei are contained in the grains or not
when making an exposure, internally developing in an ordinary method and then making
out an H-D curve, because the reversal image of an internal fog made present therein
can be observed.
[0047] In the invention, the emulsions may be of the core/shell type. The core/shell type
emulsion mentioned herein means an emulsion comprising the grains each having at least
an inner part (a core) and at least one outer layer (a shell), such as the double
layer structured grains given in JP OPI Publication No. 61-148442/1986 and the multilayer
structured grains given in JP OPI Publication No. 61-245151/1986. For example, the
core/shell type emulsions may be comprised of the grains having a high iodine-containing
phase, that is, a silver iodobromide or silver chloroiodobromide phase having a silver
iodide content of not less than 10 mol%, desirably not less than 20 mol% and preferably
not less than 25 mol%.
[0048] When preparing the silver halide emulsion of the invention, it is allowed to apply
an ordinary single-jet method, double-jet method or controlled double-jet method,
provided the requirements for the invention can be satisfied. Among these methods,
a controlled double-jet method is particularly desirable from the viewpoint that a
pH and a pAg can readily be controlled.
[0049] In the controlled double-jet method, iodine ions can usually be supplied either from
an aqueous alkaline iodide solution or from the mixture of the above-mentioned aqueous
solution and an aqueous solution of other alkali halides. Iodine ions may more desirably
be supplied in a method in which silver iodide is supplied in the form of a solid
as mentioned in JP OPI Publication No. 1-323215/1989.
[0050] According to the above-mentioned method, the materials for growing the crystals can
be supplied in a triple-jet method of making use of an aqueous ammoniacal silver salt
or an aqueous solution of a water-soluble silver salt, an aqueous alkaline bromide
solution and a suspension containing silver iodide grains. The pH and pAg thereof
can be controlled in the same manner as in an ordinary controlled double-jet method.
According to the above-mentioned method, a high iodine containing phase can effectively
and uniformly be formed, and a silver halide emulsion excellent in image-sharpness
and pressure characteristics, which is objective of the invention, can effectively
be prepared by making combination use of the silver halide emulsion of the invention.
Besides, for preparing a silver halide emulsion having the same uniformity as above-mentioned,
it is useful to use a method for growing silver iodobromide grains on seed grains
in an Ostwald ripening treatment, such as the method described in JP OPI Publication
No. 1-183417/1989.
[0051] When preparing a silver halide emulsion in the invention, a variety of the means
applicable to the field of the art can be used. For example, it is allowed to use
the techniques such as a technique for doping various kinds of heavy metal salts and
the complexes thereof into silver halide grains, a desalting technique (for removing
dissolved residuals) and a technique for chemical sensitization, a physical ripening
or a spectral sensitization.
[0052] In an emulsion, the silver halide grains may be of the core/shell types having various
structures. The silver halide emulsions are also allowed to contain an azole or other
various compounds for the purposes of preventing a fog production or stabilizing the
photographic characteristics in the courses of carrying out the emulsion preparation
steps, preserving the emulsion or processing the development thereof.
[0053] The above-mentioned emulsions are further allowed to contain various kinds of binders
such as gelatin as a dispersion medium.
[0054] When forming an emulsion layer, a gelatin layer hardener may be used.
[0055] Particularly when forming an emulsion layer, a silver halide emulsion is further
allowed to contain, besides the above, a variety of well-known surfactants with the
various purposes of serving as a coating aid or of preventing an staticity, improving
a slidability, making an dispersive emulsification, preventing an adhesion and improving
photographic characteristics (such as a development acceleration, a layer hardening
and a sensitization).
[0056] When applying an emulsion prepared in the invention to a color light sensitive material,
it is allowed to use the techniques and materials applicable to light sensitive materials;
for example, cyan, magenta and yellow couplers are contained, in combination, in red-sensitive,
green-sensitive and blue-sensitive silver halide emulsion layers, respectively. In
this case, the couplers are desirable to have a hydrophobic group that is so-called
a ballast group in the molecules thereof so that the couplers can be non-diffusible.
The couplers may have either a 4-equivalency or a 2-equivalency to a silver ion. Each
of the couplers is also allowed to contain a colored coupler having a color correction
effect or a coupler capable of releasing a development inhibitor (that is so-called
a DIR coupler) as a development is being progressed. Further, the couplers may also
be those producing a colorless product upon coupling reaction.
[0057] As for the yellow couplers, any well-known closed-chain ketomethylene type couplers
can be used. Among these couplers, a benzoyl acetanilide type and pivaloyl acetanilide
type compounds may advantageously be used. The typical examples of the yellow color-developing
couplers applicable thereto include those given in U.S. Patent Nos. 2,875,057, 3,265,506,
3,408,194, 3,551,155, 3,582,322, 3,725,072 and 3,891,445; West German Patent No. 1,547,868;
and West German Patent (OLS) Publication Nos. 2,213,461, 2,219,917, 2,261,361, 2,414,006
and 2,263,875.
[0058] As for the magenta color developing couplers, a pyrazolone type compound, an indazolone
type compound and a cyanoacetyl compound can be used. Among the compounds, the pyrazolone
type compounds are particularly advantageous. The typical examples of the magenta
color developing couplers applicable thereto include those given in U.S. Patent Nos.
2,600,788, 2,983,608, 3,062,653, 3,127,269, 3,314,476, 3,419,391, 3,519,429, 3,558,319,
3,582,322, 3,615,506, 3,834,908 and 3,891,445; West German Patent No. 1,810,464; West
German Patent (OLS) Publication Nos. 2,468,865, 2,417,945, 2,418,959 and 2,424,467;
and JP Examined Publication No. 40-6031/1965.
[0059] As for the cyan color developing couplers, a phenol type compound and a naphthol
type compound can be used. The typical examples thereof include those given in U.S.
Patent Nos. 2,369,929, 2,434,272, 2,474,293, 2,521,908, 2,895,826, 3,034,892, 3,311,476,
3,458,315, 3,476,563, 3,583,971, 3,591,383 and 3,767,411; West German Patent (OLS)
Publication Nos. 2,414,830 and 2,454,329; and JP OPI Publication No. 48-59838/1973.
[0060] As for the colored couplers, it is allowed to use those given in, for example, U.S.
Patent nos. 3,476,560, 2,521,908 and 3,034,892; JP Examined Publication Nos. 44-2016/1969,
38-22335/1963, 42-11304/1967 and 44-32461/1969; JP Application Nos. 49-98469/1974
and 50-118029/1975; and West German Patent (OLS) Publication No. 2,418,959.
[0061] As for the DIR couplers, it is allowed to use those given in, for example, U.S. Patent
Nos. 3,227,554, 3,617,291, 3,701,783, 3,790,384 and 3,632,345; West German Patent
(OLS) Publication Nos. 2,414,006, 2,454,301 and 2,454,329; British Patent No. 953,454;
and JP Application No. 50-146570/1975.
[0062] A light sensitive material is also allowed to contain, besides the above-mentioned
DIR compounds, a compound capable of releasing a development inhibitor as a development
is being progressed. The compounds applicable thereto include those given in, for
example, U.S. Patent Nos. 3,297,445 and 3,379,529; and West German Patent (OLS) Publication
No. 2,417,914. Besides the above, it is further allowed to use the couplers given
in, for example, JP OPI Publication Nos. 55-85549/1980, 57-94752/1982, 56-65134/1981,
56-135841/1981, 54-130716/1979, 56-133734/1981 and 56-135841/1981; U.S. Patent No.
4,310,618; British Patent No. 2,083,640; and Research Disclosure Nos. 18360(1979),
14850(1980), 19033(1980), 19146(1980), 20525(1981) and 21728(1982).
[0063] The above-given couplers may be contained in one and the same layer, independently
or in combination, and one and the same compound may also be contained in two or more
layers.
[0064] The coupler is introduced into a silver halide emulsion layer in such a well-known
method as mentioned in U.S. Patent No. 2,322,027. For example, the coupler is dissolved
in an alkyl phthalic acid ester (such as dibutyl phthalate and dioctyl phthalate),
a phosphoric acid ester (such as diphenyl phosphate, triphenyl phosphate, tricresyl
phosphate and dioctylbutyl phosphate) a citric acid ester (such as acetyltributyl
citrate), a benzoic acid ester (such as octyl benzoate) and an alkylamide (such as
dimethyllauryl amide) or an organic solvent having a boiling point within the range
of about 30°C to 150°C including, for example, a lower alkyl acetate such as ethyl
acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methylisobutyl
ketone, β-ethoxyethyl alkylene acetate and methyl cellosolve acetate, and the resulting
solution is then dispersed in a hydrophilic colloid. It is also allowed to mix the
above-given high boiling organic solvent with a low boiling organic solvent.
[0065] When the coupler has an acid group such as those of carboxylic acid or sulfonic acid,.the
coupler may be introduced in the form of an aqueous alkaline solution into a hydrophilic
colloid.
[0066] Generally, a silver halide emulsion layer may be added with these couplers in an
amount within the range of, desirably, 2x10⁻³ mols to 5x10⁻¹ mols and, preferably,
1x10⁻² mols to 5x10⁻¹ mols per mol of silver.
[0067] As for the color-fog inhibitors, a hydroquinone derivative and so forth may be used.
As for the supports for forming a light sensitive material, they include those made
of baryta paper, polyethylene-coated paper, synthetic polypropylene paper, glass plate,
cellulose acetate, cellulose nitrate, polyvinyl acetal and polypropylene, including,
for example, a polyester film such as those made of polyethylene terephthalate, and
a polystyrene film. The above-mentioned supports may be suitably selected so as to
meet the application purposes of light sensitive materials and the support may be
sublayered if required.
[0068] After exposing a light sensitive material to light, it is developed in any well-known
methods having usually been applied.
[0069] The light sensitive materials used therein the emulsions of the invention can be
fit for various uses including, for example, a variety of application such as general
black-and-white photography, X-ray photography, color photography, infra-red photography,
microphotography, a silver dye bleaching treatment, reversal photography and a diffusion
transfer process.
[0070] When applying to a multilayered color light sensitive material, it is allowed to
apply to various layer structures such as a regular layer structure, an inverted layer
structure and so forth, of which have been well-known in the field of the art.
[0071] For making a high speed and a high image quality compatible, various inventions have
been made on the order of layer arrangements. These techniques are desirable to be
combined. The inventions made on the order of layer arrangements are disclosed in,
for example, U.S. Patent Nos. 4,184,876, 4,129,446 and 4,186,016; British Patent No.
1,560,955; U.S. Patent Nos. 4,186,011, 4,267,264, 4,173,479, 4,157,917 and 4,165,236;
British Patent No. 2,138,962; JP OPI Publication No. 59-177552/1984; British Patent
No. 2,137,372; and JP OPI Publication Nos. 59-180556/1984 and 59-204038/1984.
[0072] It is allowed particularly to make a non-light sensitive layer present among two
or more emulsion layers each having the same color sensitive speed.
[0073] The speeds may also be improved by providing a reflective layer containing fine-grained
silver halide grains underneath a high speed layer including particularly a high-speed
blue sensitive layer. This technique is detailed in, for example, JP OPI Publication
No. 59-160135/1984.
[0074] Generally, the multilayered color photographic light sensitive materials containing
the emulsions of the invention contain each a cyan forming coupler in the red-sensitive
emulsion layer, a magenta forming coupler in the green-sensitive emulsion layer and
a yellow forming coupler in the blue-sensitive emulsion layer thereof, respectively.
It is allowed to have other different combinations if occasion demands. For example,
it is also allowed to combine some infrared-sensitive layers for making a pseudocolor
photography or a semiconductive laser exposure.
[0075] As disclosed in U.S. Patent No. 3,497,350 and JP OPI Publication No. 59-214853/1984,
it is further allowed to use such a method that a color sensitivity and a color-image
forming coupler of an emulsion layer are suitably combined together and the emulsion
layer is arranged to the position farthest from a support.
[0076] The emulsions of the invention are useful for multilayered type color photographic
light sensitive materials. In this case, the light sensitive materials of the invention
generally have each ar least one of red-sensitive silver halide emulsion layers, one
of green-sensitive silver halide emulsion layers and one of blue-sensitive silver
halide emulsion layers. It is desirable that each of the same color-sensitive layers
thereof is to have not less than two emulsion layers each having the different color-sensitivities.
It is preferable that each of the layers is to have a three-layer structure and also
that a method for improving the graininess is to be used. The above-mentioned techniques
are described in, for example, British Patent No. 923,045 and JP Examined Publication
No. 49-15495/1974.
EXAMPLES
[0077] Now, the examples of the invention will be detailed below. It is, however, to be
understood that the invention shall not be limited thereto.
EXAMPLE-1
(Preparation of a seed emulsion)
[0078] There prepared 0.6215 mols of a hexagonal tabular-shaped emulsion in the following
manner.

[0079] Solutions B and C of 9.08 ml each were added into Solution A at 35°C by making use
of the mixing stirrer detailed in JP Examined Publication No. 58-58288/1983 and 58-58289/1983
in a double-jet precipitation method by taking 2 minutes, so that the nuclei were
produced.
[0080] After stopping the above-mentioned addition of Solutions B and C, the temperature
of Solution A was raised up to 60°C by taking 30 minutes and Solutions B and C were
each added again in a flow rate of 19.5 ml/min. in a double-jet precipitation method
by taking 25 minutes. In the course of adding the solutions again, the silver potential
was controlled to be +6 mv with Solution D (wherein the silver potential was measured
at the silver ion selection electrode while serving a saturated silver-silver chloride
electrode as the reference electrode.) After completing the addition of the solutions,
the pH was kept at 6 with a 3% KOH solution and an aqueous solution containing 21.3
g of ossein gelatin was added, so that seed emulsion EM-0 was prepared. The resulting
seed emulsion EM-0 was proved to be the hexagonal tabular-shaped grains having the
maximum adjacent side ratio within the range of 1.0 to 2.0 in not less than 90% of
the whole projective area of the silver halide grains and also proved through an electron
microscopic observation to be that the tabular-shaped grains had an average grain
thickness of 0.07 µm and an average grain size (converted into an average circular
diameter) of 0.5 µm. Seed grain EM-0 contained 0.6215 mols in 4612 ml thereof.
(Preparation of a tabular-shaped emulsion of the Invention)
[0081] A tabular-shaped silver iodobromide emulsion EM-1 containing 2.46 mol% of AgI was
prepared by making use of 4 kinds of the following solutions.

[0082] The whole amount of Solutions B and C were added into Solution A at 60°C by making
use of the mixing stirrer detailed in JP Examined Publication No. 58-58288/1983 and
58-58289/1983 in a double-jet precipitation method at a flow rate of 15.45 ml/min.
by taking 14 minutes, so that the addition and the growth were carried out.
[0083] In the course mentioned above, the silver potential was controlled to be +28.0 mV
by making use of Solution D.
[0084] After completing the addition, a washing treatment was carried out in an ordinary
manner in a precipitation method (in which phenyl carbamoyl type gelatin was used)
so as to remove the excessive salts. After that, an aqueous gelatin solution containing
47.57 g of ossein gelatin was added thereto and was then so stirred as to be dispersed
again.
[0085] The resulting emulsion EM-1 contained 5.756 mols of silver halide in 2445 ml thereof
and the pH and pAg thereof were controlled to be 5.8 and 8.06 at 40°C, respectively.
[0086] The configurations of about 3000 grains of EM-1 were analyzed by observing and measuring
them through an electron microscope. The results thereof are shown in Table-1. In
EM-1, the proportion of the grains having an aspect ratio within the range of 3.0
to 7.0 was proved to be 81.1%. In this emulsion, 50% of the whole projective area
of the silver halide grains was occupied by the grains having an aspect ratio of not
less than 4.34, and 70% of the whole projective area thereof was occupied by the tabular-shaped
grains having an aspect ratio of not less than 3.86. The whole silver halide grain
projective area of 93%, that was not less than 90% thereof, were also proved to be
occupied by the hexagonal tabular-shaped grains having a maximum adjacent side ratio
within the range of 1.0 to 2.0. Further, in the hexagonal tabular-shaped grains, the
average grain size was 0.92 µ (converted into the average circle diameter thereof);
the grain size distribution thereof was 21.8% in terms of the variation coefficient;
the average grain thickness was 0.218 µm; and the thickness variation coefficient
was 15%.
[0087] The results of the emulsion analyses
| Emulsion |
Em-1 |
EM-2 |
| Aspect ratio of grains in 50% of the projective area |
≧4.34 |
≧4.07 |
| Aspect ratio of grains in 70% of the projective area |
≧3.86 |
≧3.33 |
| Grain proportion within an aspect ratio of 3.0∼7.0 |
81.1% |
76% |
| Hexagonal tabular grain proportion within a maximum adjacent side ratio of 1.0∼2.0 |
93% |
94% |
| Average grain size of the hexagonal tabular grains (converted into the average circle
diameter) |
0.92µm |
0.62µm |
| Grain size variation coefficient of the hexagonal tabular grains |
21.8% |
24.2% |
| Average grain thickness of the hexagonal tabular grains |
0.218µm |
0.163µm |
| Grain thickness variation coefficient of the hexagonal tabular grains |
15% |
9% |
EXAMPLE-2
(Preparation of a tabular-shaped emulsion of the Invention)
[0088] Tabular-shaped silver iodobromide emulsion EM-2 of the invention containing 3.18
mol% of AgI was prepared by making use of the 4 kinds of the following solutions.

[0089] The whole amount of Solutions B and C were added into Solution A at 60°C by making
use of the mixing stirrer detailed in JP Examined Publication No. 58-58288/1983 and
58-58289/1983 in a double-jet precipitation method at a flow rate of 15.6 ml/min.
by taking 54.52 minutes, so that the addition and the growth were carried out.
[0090] In the course mentioned above, the silver potential was controlled to be +38.0 mV
by making use of Solution D.
[0091] After completing the addition, a washing treatment was carried out in an ordinary
manner in a precipitation method (in which phenyl carbamoyl type gelatin was used)
so as to remove the excessive salts. After that, an aqueous gelatin solution containing
29.3 g of ossein gelatin was added thereto and was then so stirred as to be dispersed
again.
[0092] The resulting EM-2 contained 4.94 mols of silver halide in 2660 ml thereof. The pH
and pAg of the emulsion solution were controlled to be 5.8 and 8.06 at 40°C, respectively.
The configurations of about 3000 grains of EM-2 were analyzed by observing and measuring
them through an electron microscope. The results thereof are shown in Table-1. In
EM-2, the proportion of the grains having an aspect ratio within the range of 3.0
to 7.0 was proved to be 76%. In this emulsion, 50% of the whole projective area of
the silver halide grains was occupied by the grains having an aspect ratio of not
less than 4.07, and 70% of the whole projective area thereof was occupied by the tabular-shaped
grains having an aspect ratio of not less than 3.33. The whole silver halide grain
projective area of 94%, that was not less than 90% thereof, was also proved to be
occupied by the hexagonal tabular-shaped grains having a maximum adjacent side ratio
within the range of 1.0 to 2.0. Further, in the hexagonal tabular-shaped grains, the
average grain size was 0.62 µ (converted into the average circle diameter thereof);
the grain size distribution thereof was 24.2% in terms of the variation coefficient;
the average grain thickness was 0.163 µm; and the thickness variation coefficient
was 9%.
EXAMPLE-3
EXAMPLE-4
[0094] Silver halide photographic light sensitive materials were prepared by chemically
and spectrally sensitizing the emulsions EM-1 through EM-19 (to be blue- and green-sensitive)
in the ordinary methods, respectively, and the effects of the emulsions of the invention
were compared to each other.
[0095] Multilayered color photographic light sensitive materials were prepared in quite
the same conditions as in those given in JP Application No. 2-10971/1989, except that
the other blue-sensitive emulsions were used therein. To be more concrete, Samples
No.1 through No.19 were each prepared by replacing the silver halide emulsions contained
in the high-speed blue-sensitive layers and the low-speed blue-sensitive layers thereof
by the same amounts of chemically sensitized emulsions EM-1 through EM-19.
[0096] For each of Samples No. 1 through No. 19, the sum total of thicknesses of dried coatings
on all nonsensitive hydrophilic colloidal layers which are located to be farther from
the support than the photosensitive silver halide emulsion layer farthest from the
support was set to 1.98 µ.
[0097] The evaluations were made in the ordinary methods on the sensitometric characteristics
(of the blue-sensitive layers), pressure resistance (of the same layers) and image-sharpness
(of the green-sensitive layers) each of the resulting samples. The results of the
evaluations are shown in Table-3.
[0098] From the results thereof, it was proved that, when making use of the emulsions of
the invention, color photographic light sensitive materials can be so prepared as
to have an excellent image-sharpness, to reduce the deterioration caused by a pressure
desensitization and a pressure fog production and to have an excellent gradation.
[0099] Besides the above samples, Sample No.20 was so prepared as to contain the emulsion
of the invention, EM-2, in the low-speed blue-sensitive layer thereof. The same evaluations
as in the above-mentioned were made on Sample No.20. The resulting Sample No.20 proves
that the image-sharpness of the green-sensitive layers can be improved and that the
image-sharpness of the green-sensitive layers can preferably be improved especially
when making use of the emulsions of the invention in both of the high-speed and low-speed
blue-sensitive layers thereof.
[0100] The image-sharpness of the red-sensitive layers can desirably be improved similar
to the above-mentioned case, when making use of the emulsions of the invention in
the green-sensitive layers.
