FIELD OF THE INVENTION
[0001] This invention relates to a silver halide photographic light-sensitive material and,
particularly, to a method for preparing a silver halide photographic emulsion which
is improved upon illuminance intensity reciprocity law failure and is high in sensitivity.
BACKGROUND OF THE INVENTION
[0002] In the field of silver halide photographic light-sensitive materials, there are
demands for the light-sensitive materials which are improved upon reciprocity law
failures such as a low intensity reciprocity law failure and a high intensity reciprocity
law failure.
[0003] It has been known so far to add an iridium compound into a silver halide emulsion
so as to improve such an illuminance intensity reciprocity law failure as mentioned
above. For example, there has been a known means of improving an illuminance intensity
reciprocity law failure in such a manner that an iridium compound is added into an
emulsion in the course of growing the crystals of silver halide grains.
[0004] In the conventional techniques, however, a silver halide emulsion is desensitized
or not so sensitized as to be expected even if an iridium compound is added to the
silver halide emulsion, though the illuminance intensity reciprocity law failure may
be improved. Therefore, these techniques do not answer to the demands for increasing
the speed of light-sensitive materials.
SUMMARY OF THE INVENTION
[0005] It is an object of the invention to provide a silver halide photographic light-sensitive
material in which the speed is made higher and the illuminance intensity reciprocity
law failure is improved upon, by solving the problems of the above-described conventional
techniques so that a high-speed sensitization and an illuminance intensity reciprocity
law failure improvement can be made compatible, thereby satisfying not only the demand
for restraining fog production but the demand for preventing any desensitization produced
by a dye adsorption.
[0006] This invention relates to a method of preparing a silver halide photographic emulsion,
which contains silver halide grains having different silver halide compositions mingled
therein; wherein the grains are characterized in that the silver halide grains are
grown in the presence of silver halide fine-grains having a solubility product smaller
than that of the silver halide grains contained in the emulsion for at least one period
in the course of growing the silver halide grains of the emulsion and iridium ions
are made present at the time when or after starting the growth of the silver halide
grains. (Such emulsion grains as described above is hereinafter sometimes referred
to as 'the emulsion of the invention'.) The above described object of the invention
can be achieved in the above-described constitution.
[0007] To be more concrete, when an iridium compound is added into the emulsions having
been used conventionally so as to improve the illuminance intensity reciprocity law
failure, a desensitization is thereby produced. On the other hand, when using such
a specific silver halide emulsion as described above in the invention, the reciprocity
law failure can be improved and a sensitization can further be attained in effects
due to iridium ions present.
[0008] In addition to the above, according to the invention, a light-sensitive material
having low fog level can be obtained and any desensitization produced by a dye adsorption
can be prevented.
DETAILED DESCRIPTION OF THE INVENTION
[0009] First, the emulsion of the invention will be detailed.
[0010] The emulsion of the invention contains silver halide grains each having different
compositions mingled together therein.
The expression, the cases, where silver halide grains each having different compositions
are mingled together include a case where silver halide grains each having different
compositions are mingled together, for example, where those grains each have one silver
halide composition in the inner portion thereof and another different silver halide
composition in the outer portion thereof. In the invention, it is permitted to mingle
the silver halide compositions together in any embodiments.
[0011] In the emulsion of the invention, the silver halide grains thereof are grown up in
at least one period in the course of growing the silver halide grains contained in
the emulsion in the presence of the silver halide fine grains <hereinafter referred
to as AgX grains (2), for convenience' sake> having a solubility product equivalent
to or less than that of the silver halide grains contained in the emulsion <hereinafter
referred to as AgX grains (1), for convenience' sake>.
[0012] The term, 'a solubility product', expressed in this patent specification are synonymous
with that in the ordinary chemical expression.
[0013] As described above, AgX grains (1) are allowed to have themselves two or more silver
halide compositions in the grains. In the case where the different silver halide compositions
are mingled in grains, the two or more kinds of silver halides mingled therein are
allowed to be distributed in the grains either uniformly or ununiformly. In the invention,
for example, the ununiform distributions such as those of the core/shell and epitaxial
types are preferable and, among the types, the core/shell type is particularly preferable.
[0014] There is no special limitation to the silver halide compositions of AgX grains (1),
and any AgX grains (1) may be used, provided the grains have phases different in silver
halide compositions. Among these silver halides, silver iodobromide, silver chlorobromide
and silver chloroiodobromide are preferable and, inter alia, silver iodobromide is
particularly preferable. To be more concrete, for example, any ones such as mixedly
crystallized silver iodobromide or silver chlorobromde can be used. It is, however,
preferable to use silver iodobromide having a core/shell structure in which the cores
each have a silver iodide content within the range of not less than 15 mol% to not
more than 40 mol%.
[0015] The grain-sizes of AgX grains (1) are preferable to be not more than 3.0 µm in terms
of a sphere-equivalent diameter.
[0016] AgX grains (1) may be either of the poly- and mono-disperse type and the mono-disperse
type is more preferable.
[0017] The term, 'mono-disperse', expressed herein means that not less than 95% of all the
grains have the grain-sizes within the range of ±40% of an average grain-size.
[0018] There is no special limitation to the grain configurations. For example, they may
be in any configurations such as a cube, an octahedron, a tetradecahedron, a tabular-shape,
a potato-shape, and so forth.
[0019] Emulsion of the invention containing the above-described AgX grains (1) can be used
in at least one of the silver halide emulsion layers of a light-sensitive material
and, in the case of two or more emulsion layers, it is preferable to use the emulsion
of the invention in every emulsion layer.
[0020] Among all the silver halide grains contained in an emulsion layer, it is preferable
that AgX grains (1) amount to at least not less than 30 mol% of all the grains and,
particularly, to not less than 60 mol% thereof.
[0021] In the emulsion of the invention, AgX grains (1) are grown up under the presence
of AgX grains (2), provided that AgX grains (2) having a solubility product smaller
than those of AgX grains (1) are made present at least for a period in the course
of growing AgX grains (1). In this case, AgX grains (2) may be so used as to grow
up AgX grains (1), upon making AgX grains (2) present until a water-soluble halide
solution and a water-soluble silver salt solution (hereinafter refered to as grain-growing
elements) are completely supplied.
[0022] Generally, the average grain-sizes of AgX grains (2) are smaller than those of AgX
grains (1). However, there may also be some instances where the average grain-sizes
of AgX grains (2) are larger than those of AgX grains (1). The average grain-sizes
of AgX grains (2) are within the range of, preferably, 0.001 to 0.7 µm, more preferably,
0.01 to 0.3 µm and, further preferably, 00.1 to 0.1 µm.
[0023] The embodiments of making AgX grains (2) present will be detailed and, at the same
time, the processes of growing AgX grains (1) will also be explained below.
[0024] In the first method of growing AgX grains (1), seed silver halide grains are grown
up by making use of both of a solution of water-soluble silver salts and a water-soluble
halide solution which are the grain growing elements so that AgX grains (1) can be
prepared. In the second method, silver halide nuclei are produced without making use
of any seed grains but by making use of the above-described two the grain growing
elements and the grains are then grown up so that AgX grains (1) can be prepared.
From the viewpoint of the reproducibility of the grain-sizes of AgX grains (1), the
first method may advantageously be used.
[0025] AgX grains (2) are required to make them present in a suspension system (hereinafter
referred to as a mother liquor) in which AgX grains (1) are prepared, for at least
one period of time in the course of growing AgX grains (1), or until the time at latest
when AgX grains (1) are grown up completely.
[0026] In the case of using seed grains, AgX grains (2) may be made present in a mother
liquor before making the seed grains present therein; and, AgX grains (2) may also
be added into a mother liquor containing seed grains, prior to the addition of a grain
growing element also, AgX grains (2) may be added into a mother liquor in the course
of adding the grain growing elements; further, AgX grains (2) may be added separately
two or more times selected from the above-described points of time of addition.
[0027] In the case of growing the grains after producing silver halide nuclei without using
any seed grains, it is preferable to add AgX grains (2) after producing the nuclei.
AgX grains (2) may be added before adding the grain growing elements or in the course
of adding the elements, and further they may be added separately two or more times.
[0028] Also, AgX grains (2) and the grain growing elements may be added collectively, continuously
or intermittently.
[0029] It is preferable to add AgX grains (2) and seed silver halide grains into a mother
liquor with a multi-jet precipitation method such as a double-jet precipitation method,
at an adding rate suitable for growing grains under the conditions where pH, pAg,
temperatures and so forth are controlled.
[0030] AgX grains (2) and seed silver halide grains may be prepared in a mother liquor or
may be added into the mother liquor after they are prepared outside the mother liquor.
[0031] As for the water-soluble silver salt solution applicable to prepare AgX grains (2),
an ammoniacal silver salt solution may preferably be used.
[0032] As for the silver halide compositions of AgX grains (2), it is preferable to use
silver iodide or silver iodobromide having a iodide content higher than that of silver
iodobromide being grown, in the case, for example, that AgX grains (1) is silver iodobromide;
and it is preferable to use silver bromide or silver chlorobromide having a bromide
content higher than that of silver chlorobromide grains being grown, in the case,
for example, that AgX grains (1) is silver chlorobromide. When AgX grains (1) is silver
iodobromide, it is particularly preferable to use silver iodide as AgX grains (2).
[0033] In the case where AgX grains (1) is silver iodobromide or silver chloroiodobromide,
it is preferable to supply all the iodide applicable for growing up grains so as to
serve as AgX grains (2). It is, however, permitted to supply a part of the iodide
in the form of an aqueous halide solution, provided, the effects of the invention
may not be affected.
[0034] AgX grains (2) are preferable to be excellent in mono-dispersibility.
[0035] As for the compositions of seed silver halide grains, a variety of silver halides
such as silver chloride, silver bromide, silver chlorobromide, silver chloroiodide,
silver iodobromide, and silver chloroiodobromide may freely be used as desired.
[0036] In the preparation processes for the above-described AgX grains (1), the temperatures
of the mother liquor are within the range of, preferably, 10 to 70°C and, more preferably,
20 to 60°C; and the pAg values thereof are within the range of, preferably, 6 to 11
and, more preferably, 7.5 to 10.5; and the pH values thereof are within the range
of, preferably, 5 to 11 and, more preferably, 7 to 10.
[0037] The emulsions of the invention are those in which iridium ions are made present therein
at least at the time when or after starting the growth of AgX grains (1).
[0038] The iridium ions may be made present by adding a water-soluble iridium salt.
[0039] There is no special limitation to the water-soluble iridium salts applicable to the
invention, and they include, for example, Na₃IrCℓ₆, K₃IrCℓ₆, K₂IrCℓ₆, (NH₄)₂IrCℓ₆
and Na₂IrCℓ₆.
[0040] These compounds may also be used in any combination.
[0041] These iridium compounds may be used upon dissolving them in water or in a suitable
solvent. As the common methods of stabilizing the iridium compound solution, it is
allowed to use a method in which an aqueous hydrogen halide solution such as that
of HCℓ, HBr or HF, or an alkali halide solution such as that of KCℓ, NaCℓ, KBr or
NaBr is added into the iridium compound solution.
[0042] The iridium ions applicable to the invention may be added in an amount of, preferably,
not more than 1x10⁻⁴ mols per mol of the whole silver halide ultimately produced,
more preferably, not more than 1x10⁻⁵ mols and, further preferably, not more than
1x10⁻⁷ mols.
[0043] Iridium ions may be made present at the time when or after starting the growth of
grains. In other words, they are also allowed to be made present at the point of time
when starting the growth of grains, in the course of growing them, or after grains
are grown up. Iridium ions may be added in such a manner that the whole amount of
the ions are added at any points of time when forming AgX grains (1), they are added
separately several times, or they are added successively.
[0044] Iridium ions are also allowed to add in the mixture with an aqueous halide solution
that is a silver halide grain growing element.
[0045] In this instance, it is preferable to add the iridium ions either at the time when
or after 70% of the ultimate grain-size thereof are formed or prior to a chemical
ripening treatment.
[0046] It may be considered that the positions in AgX grains (1) where iridium is contained
may depend upon the various points of time when adding iridium ions in the course
of growing grains. It is allowed that iridium may be contained in any positions of
grains, namely, in the center thereof concentrically, on the surfaces thereof, or
in all the portions thereof. It is particularly preferable that an iridium-containing
layer is made present in about several hundreds Å from each of the grain surfaces.
To be more concrete, it is most preferable to make iridium present in a layer about
several hundreds Å apart from the surface of each grain. To make them present in this
way, it will do that iridium is added immediately before completing the crystal grain
growth and the grains are then grown for about several hundreds Å.
[0047] When preparing the emulsion of the invention or the other emulsions which are used
in combination, if required, it is also permitted to add thereto a substance other
than gelatin, such as those adsorptive to silver halide grains.
As for the adsorptive substances, the compounds including, for example, a sensitizing
dye, an antifoggant and a stabilizer which are commonly used in the art, or heavy
metal ions may advantageously be used. The typical examples of these adsorptive substances
are given in Japanese Patent Publication Open to Public Inspection (hereinafter referred
to as Japanese Patent O.P.I. Publication) No. 62-7040/1987.
[0048] From the viewpoints of restraining fog production and improving the storage stability,
it is preferable to add at least one kind each of the antifoggants and stabilizers
selected from among the adsorptive substances when preparing a seed emulsion.
[0049] Among the antifoggants and stabilizers, heterocyclic mercapto compounds and/or azaindene
compounds are particularly preferable to be used. More preferable examples of the
heterocyclic mercapto compounds and azaindene compounds are detailed in, for example,
Japanese Patent O.P.I. Publication No. 63-41848/1988 and they may be used in the invention.
[0050] The amounts of the above-described heterocyclic mercapto compounds and azaindene
compounds to be added shall not be limitative. However, they may be added in an amount
within the range of, preferably, 1x10⁻⁵ to 3x10⁻² mols per mol of silver halides used
and, more preferably, 5x10⁻⁵ to 3x10⁻³ mols. The above given amounts may suitably
be selected according to the variations of the preparation conditions of silver halide
grains, an average grain-sizes of silver halide grains and the kinds of the above-described
compounds.
[0051] When an emulsion is completed to form silver halide grains, it is then desalted in
a well-known method. As the desalting methods applicable thereto, a method described
in Japanese Patent Application Nos. 62-81373/1987 and 63-9047/1988 may be used, in
which a gelatin coagulant for desalting the grains serving as seed grains may be used;
a noodle-washing method may also be used, in which gelatin is gelated to desalt an
emulsion; and a coagulation methos may further be used, in which inorganic salts comprising
a polyvalent anion, including, for example, sodium sulfate, an anionic surfactant
and anionic polymers (such as polystyrenesulfonic acid) are utilized.
[0052] Thus desalted silver halide grains are redispersed in gelatin, so that an emulsion
may be prepared.
[0053] The emulsions applicable to the invention may be chemically sensitized in any ordinary
methods including, namely, a sulfur sensitizing method in which a sulfur-containing
compound capable of reacting with silver ions or active gelatin is used; a selenium
sensitizing method in which a selenium compound is used; and a noble-metal sensitizing
method in which a gold or other noble metal compound is used; independently or in
combination.
[0054] As for the chemical sensitizers, chalcogens sensitizers, for example, may be used.
Among them, a sulfur sensitizer and a selenium sensitizer are preferably used.
[0055] The sulfur sensitizers include, for example, a thiosulfate, allylthiocarbazide,
thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate and rhodanine. Besides
the above, the sulfur sensitizers described in U.S. Patent Nos. 1,574,944, 2,410,689,
2,278,947, 2,728,668, 3,501,313 and 3,656,955, West German (OLS) Patent No. 1,422,869,
and Japanese Patent O.P.I. Publication Nos. 56-24937/1981 and 55-45016/1980 each
may be used.
[0056] The amounts of the sulfur sensitizer to be added are varied to a considerable extent
according to the various conditions such as pH values, temperatures and the sizes
of silver halide grains. As a rough standard, an amount thereof to be added is preferably
within the extent of the order of 10⁻⁷ to 10⁻¹ mols per mol of silver halides used.
[0057] The selenium sensitizers applicable thereto include, for example, aliphatic isoselenocyanates
such as allylisoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylates
and the esters thereof, selenophosphates, and selenides such as diethylselenide and
diethyldiselenide. The typical examples thereof are given in U.S. Patent Nos. 1,574,944,
1,602,592 and 1,623,499.
[0058] Also, a reduction sensitizer may be used in combination. The reduction sensitizers
include, for example, stannous chloride, thiourea dioxide, hydrazine and polyazine.
[0059] Further, the noble-metal compounds other than those of gold, such as a palladium
compound, may be used in combination.
[0060] In the invention, it is preferable that AgX grains (1) contain a gold compound. The
gold compounds preferably applicable to the invention include, for example, various
kinds of gold compounds which may have the oxidation number of either +1 or +3 valency.
The typical examples thereof include a chloroaurate, potassium chloroaurate, auric
trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric azide,
ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide and gold selenide.
[0061] The gold compounds may be so used as not only to sensitize grains, but not to substantially
contribute to any sensitization.
[0062] The amounts of the gold compounds to be added are varied according to the various
requirements. As a rough standard, they are added in an amount within the range of
10⁻⁸ to 10⁻¹ mols per mol of silver halides used and, preferably, 10-7 to 10⁻² mols.
These compounds may be added at any points of time when forming AgX grains, when physically
or chemically ripening, and when completing the chemical ripening treatment.
[0063] The emulsions may be spectrally sensitized to any desired wavelength regions by making
use of sensitizing dyes.
The sensitizing dyes are allowed to use either independently or in combination.
[0064] It is also allowed to contain, together with the sensitizing dyes, a supersensitizer
for enhancing the sensitizing functions of the sensitizer, that is, a dye having no
spectrally sensitizing function in itself or a compound incapable of substantially
absorbing any visible rays of light.
[0065] The silver halide photographic light-sensitive materials relating to the invention
can be used for any light-sensitive materials including, for example, black-and-white
silver halide photographic light-sensitive materials (such as an X-ray or lithographic
light-sensitive materials and black-and-white photographing negative films), and
color photographic light-sensitive materials (such as color negative films, color
reversal films and color print papers).
[0066] They may further be used for diffusion-transfer type light-sensitive materials (such
as color diffusion-transfer elements and silver salt diffusion-transfer elements),
and thermal-development type light-sensitive materials (such as those for black-and-white
or color use).
[0067] In the case of multicolor photographic light-sensitive materials, they are each comprised
of a support multilayered thereonto with the suitable numbers of blue-, green- and
red-sensitive AgX emulsion layers in suitable order which contain usually yellow,
magenta and cyan couplers, respetively, as the photographic couplers and, if required,
with the suitable numbers of non-light-sensitive layers so that a color reproduction
may be performed in a substractive color process. The numbers of the layers and the
multilaying order thereof may suitably be changed to meet the priority characteristics
and the purpose of application.
[0068] The photographic light-sensitive materials of the invention are permitted to use
therein any desirable additives including, for example, an antifoggant, a hardener,
a plasticizer, a latex, a surfactant, an antistain agent, a matting agent, a lubricant
and an antistatic agent.
[0069] The photographic light-sensitive materials of the invention may be subjected to a
variety of black-and-white or color developing treatments so that images may be formed.
[0070] The color developing agents applicable to the color developing treatmented are allowed
to use the derivatives of the aminophenol and p-phenylenediamine types, which are
widely used in a variety of color photographic processes.
[0071] The color developers applicable to treat the photographic light-sensitive materials
are allowed to contain the known compounds for the components of the developers, as
well as an aromatic primary amine type color developing agent.
Such treatments may also be performed in a system in which any benzyl alcohol having
the problem of pollution load is not contained.
[0072] The pH values of such a developer as mentioned above are usually not less than 7
and, most generally, within the range of about 10 to 13.
[0073] The color developing temperatures are usually not lower than 15°C and, more usually,
within the range of 20 to 50°C. It is preferable to develop at a temperature of not
lower than 30°C in a rapid developing treatment. Meanwhile, it takes 3 to 4 minutes
to perform a conventional treatment. However, when using an emulsion prepared for
a rapid treatment, the color developing time may be generally saved to be 20 to 60
seconds and, further, within 30 to 50 seconds.
[0074] In the case of color-developing the photographic light-sensitive materials of the
invention, a bleaching treatment and a fixing treatments are carried out, generally,
after they are color developed. The bleaching and fixing treatments are also allowed
to perform at the same time.
[0075] Usually, a washing treatment follows after the fixing treatment. A stabilizing treatment
may be made in place of the washing treatment, or the both treatments may be made
together.
[Examples]
[0076] Next, the invention will be detailed with reference to the examples given below.
It is, however, the matter of course that the invention shall not be limited to the
following examples.
[0077] First, the preparation of each emulsion applicable to the examples will now be detailed.
Preparation of Seed Emulsion N-1 (Preparation Example 1)
[0078] According to the procedures detailed in Japanese Patent O.P.I. Publication No. 50-45437/1975,
250 mℓ of an aqueous solution of 4M-AgNO₃ (in which M represents molarity) and 250
mℓ of 4M-KBr-KI solution having a ratio of KBr:KI=98:2 (mol ratio) were each added
into 500 mℓ of an aqueous 2.0% gelatin solution warmed up to 40°C, over a period for
35 minutes while controlling the pAg to be 9.0 and pH to be 2.0, in a controlled double-jet
precipitation. The aqueous gelatin solution of thus obtained silver halide grains
containing the whole amount of silver added was adjusted to be pH 5.5 with the use
of an aqueous potassium carbonate solution. Thereto, 364 mℓ of an aqueous solution
of 5% Demol N, manufactured by Kao-Atlas Company, as a precipitant and 244 mℓ of an
aqueous 20% magnesium sulfate solution as polyvalent ions were then added so as to
produce a coagulation. The resulting coagulation were precipitated by allowing them
to stand and the supernatant liquid was then decanted. Further, 1,400 mℓ of distilled
water were added and dispersed again. The resulting redispersion was again coagulated
and precipitated by adding 36.4 mℓ of an aqueous 20% magnesium sulfate solution and
the resulting supernatant liquid was decanted. The whole amount was made to be 425
mℓ by adding an aqueous solution containing 28 g of ossein gelatin, and the resulting
solution was dispersed at 40°C for 40 minutes, so that a seed emulsion was prepared.
[0079] The resulting emulsion was named N-1. As the results of the electron-microscopic
observations, N-1 was proved to be a monodisperse type emulsion having an average
grain-size of 0.093 µm.
Preparation of Seed Emulsion N-2 (Preparation Example 2)
[0080] In the same way as in Preparation Example 1, AgBrI seed emulsion N-1 having an average
grain-size of 0.27 µm and a silver iodide content of 2 mol% was prepared.
Manufacturing Example 1 of Emulsion
[0081] By making use of the following 6 kinds of solutions, 4 kinds of emulsions, EM-1 through
EM-4, were prepared. In Emulsion EM-1, the grains thereof were of the core/shell type
silver iodobromide having an average grain-size of 0.38 µm and an average AgI content
of 8.46 mol%.

[0082] By making use of a mixing stirrer appeared in Japanese Patent O.P.I. Publication
Nos. 57-92523/1082 and 57-92524/1982, 252 mℓ of Solution C-1 was added into Solution
A-1 by taking one minute at 40°C so as to produce AgI grains. As the results obtained
through the electron-microscopic observation, the resulting AgI grains were proved
to have an average grain-size of about 0.05 µm. The very AgI grains corresponded
to the silver halide fine grains <the foregoing AgX (2)> embodied in this Example.
Following after the production of the AgI grains, Solution B-1 was added thereinto.
[0083] Next, Solutions C-1 and D-1 were added with a double jet precipitation method while
controlling the pAg, pH of the mixture and the flow rates of Solutions C-1 and D-1,
as shown in Table-1. When making a double jet precipitation of Solutions C-1 and D-1
only, silver bromide was produced. However, as the result from the growth of the grains
in the presence of the AgI grains, silver iodobromide was grown up, because AgI grains
had already been made present at this stage. When AgI grains were consumed by keeping
the additions of the both solutions on, silver bromide was produced successively.
Therefore, the resulting grains each had the silver halide compositions different
from each other, that is, they were comprised of silver iodobromide to serve as the
cores thereof and silver bromide as the shells.
[0084] In the course of the double jet precipitation, the pAg and pH were adjusted by the
flow rates of Solutions E-1 and F-1 by means of a variable flow-rate roller tube
pump. Two minutes after completing the addition of Solution C-1, the pAg was adjusted
to be 10.4 with Solution E-1 and then two minutes after, the pH was adjusted to be
6.0 with Solution F-1.
[0085] Next, a desalting and washing treatments were carried out in ordinary methods and
a dispersion was then carried out in an aqueous solution containing 197.4 g of ossein
gelatin. After then, the whole amount was adjusted to be 3000 mℓ with distilled water,
so that Emulsion EM-1 was obtained.
[0086] Emulsions EM-2 through EM-4 were prepared in the procedures described below.
[0087] EM-2 was prepared in the procedures that the grains were grown up in quite the same
manner as in EM-1 and silver was added in an amount of 98.5% of the whole amount of
silver to be added until the crystal growth is to be completed and, at the point where
the silver was so added, K₂IrCℓ₆ was added in an amount of 6.5x10⁻⁶ mols per mol of
AgX.
[0088] EM-3 was prepared in the procedures that the grains were grown up in quite the same
manner as in EM-2 and silver was added in an amount of 98.5% of the whole amount of
silver to be added until the crystal growth is to be completed and, at the point where
the silver was so added, K₂IrCℓ₆ was added in an amount of 6.5x10⁻⁸ mols per mol of
AgX.
[0089] EM-4 was prepared in the procedures that the grains were grown up in quite the same
manner as in EM-3 and silver was added in an amount of 90.0% of the whole amount of
silver to be added until the crystal growth is to be completed and, at the point where
the silver was so added, K₂IrCℓ₆ was added in an amount of 6.5x10⁻⁸ mols per mol of
AgX.
Table-1
Grain Growth Conditions (EM-1) |
Time (min.) |
pAg |
pH |
Rate of Addition (mℓ/min.) |
|
|
|
Solution C-1 |
Solution D-1 |
0 |
8.55 |
9.00 |
9.8 |
9.3 |
7.85 |
8.55 |
8.81 |
30.7 |
29.2 |
11.80 |
8.55 |
8.60 |
44.9 |
42.7 |
17.33 |
8.55 |
8.25 |
61.4 |
58.4 |
19.23 |
8.55 |
8.10 |
63.5 |
60.4 |
22.19 |
8.55 |
7.88 |
56.6 |
53.8 |
28.33 |
8.55 |
7.50 |
41.2 |
39.8 |
36.61 |
9.38 |
7.50 |
31.9 |
34.1 |
40.44 |
9.71 |
7.50 |
30.6 |
37.1 |
45.14 |
10.12 |
7.50 |
34.6 |
57.8 |
45.97 |
10.20 |
7.50 |
37.3 |
36.3 |
57.61 |
10.20 |
7.50 |
57.3 |
55.8 |
63.08 |
10.20 |
7.50 |
75.1 |
73.1 |
66.63 |
10.20 |
7.50 |
94.0 |
91.4 |
Manufacturing Example 2 of Emuldions (Comparative Emulsion)
[0090] A core/shell type silver iodobromide emulsion was so prepared as to have the AgI
contents of 15 mol%, 5 mol% and 3 mol% in order from the inside of the grains, an
average grain-size of 0.38 µm and an average AgI content of 8.46 mol%, by making
use of the 7 kinds of solutions given below.
Each part inside the grain had a different silver iodide content and aqueous gelatin
solutions were used in every part of the grains. The emulsion could therefore be used
for the purpose of the comparison.

[0091] By making use of the same mixing stirrer as used in Manufacturing Example 1 at a
temperature of 40°C, Solutions E-5 and B-5 were added into Solution A-5 with the
double jet precipitation method. At the same time when completing the addition of
B-5, C-5 was added and, at the same time when completing the addition of C-5, D-5
was added. In the course of the double jet precipitation, the controls of the pAg
and pH values and the adding rates of Solutions E-5, B-5, C-5 and D-5 are each shown
in Table-2.
[0092] The pAg and pH values were controlled by changing the flow-rates of Solutions F-5
and G-5 by means of a variable flow-rate roller tube pump.
[0093] After completing the addition of Solution E-5, the adjustments of pAg and pH, the
desalting and washing treatments and the dispersing treatments were carried out in
the same manner as in Manufacturing Example 1.
[0094] The resulting emulsion is called EM-5.
Table-2
Grain Growth Conditions (EM-5) |
Time (min.) |
pAg |
pH |
Rate of Addition of Solution (mℓ/min.) |
|
|
|
Solution E-5 |
Solution B-5 |
Solution C-5 |
Solution D-5 |
0 |
9.00 |
8.55 |
9.8 |
9.3 |
|
|
7.85 |
8.81 |
8.55 |
30.7 |
29.2 |
|
|
11.80 |
8.63 |
8.55 |
44.9 |
42.7 |
|
|
17.33 |
8.25 |
8.55 |
61.4 |
58.4 |
|
|
19.23 |
8.10 |
8.55 |
63.5 |
60.4 |
|
|
22.19 |
7.88 |
8.55 |
56.6 |
53.8 |
|
|
28.33 |
7.50 |
8.55 |
41.2 |
39.8 |
39.8 |
|
36.61 |
7.50 |
9.38 |
31.9 |
|
34.1 |
|
40.44 |
7.50 |
9.71 |
30.6 |
|
37.1 |
|
45.14 |
7.50 |
10.12 |
34.6 |
|
57.8 |
|
45.97 |
7.50 |
10.20 |
37.3 |
|
36.3 |
|
57.61 |
7.50 |
10.20 |
57.3 |
|
55.8 |
55.8 |
63.08 |
7.50 |
10.20 |
75.1 |
|
|
73.1 |
66.63 |
7.50 |
10.20 |
94.0 |
|
|
91.4 |
[0095] Further, Emulsion EM-6 was prepared in the following procedures. EM-6 was prepared
in the manner that grains were grown up under quite the same conditions as in EM-5
and then by adding K₂IrCℓ₆ in an amount of 6.5x10⁻⁸ mols per mol of AgX when an amount
of 98.5 % of the whole silver was added.
Manufacturing Example 3 of Emulsion
[0096] In the same procedures as in Manufacturing Example 1, AgX grains (those of the core/shell
type AgBrI) were so prepared as to have an average grain-size of 0.65 µm and an average
AgI content of 7.16 mol%.

[0097] The preparation was carried out in the same procedures as in Manufacturing Example
1, except that 201 mℓ of Solution C-3 was added into Solution A-3 by taking one minute
at a temperature of 40°C. The pAg, pH and flow-rate thereof are shown in Table-3.
The resulting emulsion is called EM-7. The grains contained in this emulsion were
mixedly comprised of silver iodobromide in the cores thereof and silver bromide in
the shells thereof.
Table-3
Grain Growth Conditions (EM-7) |
Time (min.) |
pAg |
pH |
Rate of Addition (mℓ/min.) |
|
|
|
Solution C-3 |
Solution D-1 |
0 |
9.00 |
8.55 |
22.1 |
22.1 |
7.01 |
8.93 |
8.55 |
18.8 |
18.8 |
18.45 |
8.77 |
8.55 |
30.4 |
30.4 |
30.22 |
8.55 |
8.55 |
41.5 |
41.5 |
33.98 |
8.46 |
8.55 |
51.5 |
51.5 |
35.92 |
8.40 |
8.55 |
65.7 |
67.6 |
38.19 |
8.31 |
9.04 |
77.4 |
84.3 |
39.60 |
8.25 |
9.38 |
83.7 |
97.2 |
41.64 |
8.18 |
9.79 |
55.8 |
82.7 |
44.07 |
8.11 |
10.12 |
38.7 |
79.5 |
44.83 |
8.10 |
10.20 |
35.6 |
36.4 |
61.76 |
7.80 |
10.20 |
30.4 |
31.1 |
82.4 |
7.50 |
10.20 |
24.5 |
25.1 |
[0098] The resulting grains were grown up under quite the same conditions as in EM-7 and
then by adding K₂IrCℓ₆ in an amount of 6.5x10⁻⁸ mols per mol of AgX when an amount
of 98.5 % of the whole silver was added. The resulting emulsion is called EM-8.
Manufacturing Example 4 of Emulsions (Comparative Emulsion)
[0099] With reference to Manufacturing Example 2, a silver iodobromide emulsion (for comparative
use) was so prepared as to have the AgI contents of 15 mol%, 5 mol% and 3 mol% in
order from the inside of the grains thereof, an average grain-size of 0.65 µm and
an average AgI content of 7.16 mol%. The resulting emulsion is hereinafter called
EM-9.
[0100] Further, another emulsion was prepared by growing the grains thereof in quite the
same manner as in EM-9 and by adding K₂IrCℓ₆ in an amount of 6.5x10⁻⁸ mols per mol
of AgX at which 98.5% of the whole silver to be added. The resulting emulsion is hereinafter
called EM-10.
Manufacturing Example 5 of Emulsions (Comparative Emulsion)
[0101] With reference to Manufacturing Example 4, an octahedral monodisperse type emulsion,
EM-11, for comparative use was so prepared as to have a silver iodide content of 2
mol% and an average grain-size of 0.65 µm.
[0102] Further, another emulsion was prepared by growing the grains thereof in quite the
same manner as in EM-11 and by adding K₂IrCℓ₆ in an amount of 6.5x10⁻⁸ mols per mol
of AgX at which 98.5% of the whole silver to be added. The resulting emulsion is hereinafter
called EM-12.
Example 1
[0103] Each of EM-1 through EM-6 described in Manufacturing Examples 1 and 2 was subjected
to an optimum gold-sulfur sensitization, so that six kinds of chemically sensitized
emulsions were obtained. Using the two kinds of emulsions, EM-1 and -5, separate from
the above emulsions, two kinds of emulsion were obtained of EM-1 by adding K₂IrCℓ₆
in an amount of 6.5x10⁻⁶ mols per mol of AgX and K₂IrCℓ₆ in an amount of 6.5x10⁻⁸
mols per mol of AgX, respectively, and the other two kinds of emulsion were obtained
of EM-5 in the same manner.
[0104] The resulting emulsions were ripened for 30 minutes and then subjected to gold-sulfur
sensitizations, respectively, so that four kinds in total of sensitized emulsions
were obtained. Each of these emulsions was spectrally sensitized to blue rays of light
by adding the following Sensitizing Dyes (I) and (II) in an amount of 350 mg per mol
of AgI, respectively.
[0105] Next, the emulsions were each stabilized by adding TAI and 1-phenyl-5-mercaptotetrazole.
To each of the resulting 10 kinds of emulsions, the photographic additives such as
a spreading agent and a layer hardener so as to prepare the coating solutions. The
coating solutions were coated over to the sublayered film bases and were then dried
up in an ordinary method, respectively, so that Samples No. 1 through No. 10 were
prepared.
[0106] Further, the yellow coupler (Y-1) was dissolved in ethyl acetate and dioctyl phthalate
in an amount by weight equivalent to that of the coupler. The resulting solution
was emulsified by dispersing it and, after adding it into each of the emulsions, the
resulting coating solutions were coated and dried in the same manner as in Sample
No. 1 through No. 10, so that Sample No. 11 through No. 20, respectively.

[0107] Each of Sample No. 1 through No. 20 was exposed to light through an wedge by using
a blue filter under the 3 kinds of exposure conditions of 8 seconds, 1/12.5 seconds
and 1x10⁻⁴ seconds. Among the samples already exposed to light, Sample No. 1 through
No. 10 were treated in a 90-second process with the following processing solutions
in the processing steps (I) given below by making use of a KX-500 automatic processor
manufactured by Konica Corp, thereby determining the photographic sensitivities of
the processed samples.
Processing steps (I) (35°C) |
Developing |
25 seconds |
Fixing |
25 seconds |
Washing |
25 seconds |
Drying |
15 seconds |
[0108] The composition of each processing solution used in the above processing steps will
be given below:
<Developer> |
Potassium sulfite |
55.0 g |
Hydroquinone |
25.0 g |
1-phenyl-3-pyrazolidone |
1.2 g |
Boric acid |
10.0 g |
Sodium hydroxide |
21.0 g |
Triethylene glycol |
17.5 g |
5-methylbenzotriazole |
0.06 g |
5-nitroindazole |
0.14 g |
1-phenyl-5-mercaptotetrazole |
0.015 g |
Glutaraldehyde bisulfite |
15.0 g |
Glacial acetic acid |
16..0 g |
Potassium bromide |
4.0 g |
Triethylenetetraminehexaacetate |
2.5 g |
Add water to make |
1 liter |
Adjust pH to be pH=10.20 |
<Fixer> |
Disodium ethylenediaminetetraacetate |
5.0 g |
Tartaric acid |
3.0 g |
Ammonium thiosulfate |
130.9 g |
Sodium sulfite, anhydrous |
7.3 g |
Boric acid |
7.0 g |
Acetic acid, in a 90wt% solution |
5.5 g |
Sodium acetate, 3-hydroxide |
25.8 g |
Aluminium sulfate, 18-hydroxide |
14.6 g |
Sulfuric acid, in a 50wt% solution |
6.77 g |
Add water to make |
1 liter |
Adjust pH to be pH=4.20 |
[0109] Sample No. 11 through No. 20 were exposed to light in the same way as in Sample No.
1 through No. 10 and were then treated in the processing steps (II) given below:
Processing steps (II) (38°C) |
|
Color developing |
3min.15sec. |
Bleaching |
6min.30sec. |
Washing |
3min.15sec. |
Fixing |
6min.30sec. |
Washing |
3min.15sec. |
Stabilizing |
1min.30sec. |
Drying |
|
[0110] The composition of each processing solution used in the above processing steps will
be given below:
<Color developer> |
4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate |
4.75 g |
Sodium sulfite, anhydrous |
4.25 g |
Hydroxylamine 1/2 sulfate |
2.0 g |
Potassium carbonate, anhydrous |
37.5 g |
Potassium bromide |
1.3 g |
Trisodium nitrilotriacetate (monohydrate) |
2.5 g |
Potassium hydroxide |
1.0 g |
Add water to make |
1 liter |
<Bleaching solution> |
Iron ammonium ethylenediaminetetraacetate |
100.0 g |
Diammonium ethylenediaminetetraacetate |
10.0 g |
Potassium bromide |
150.0 g |
Glacial acetic acid |
10.0 g |
Add water to make |
1 liter |
Adjust pH with aqueous ammonia to be pH=6.0 |
<Fixer> |
Ammonium thiosulfate |
175.0 g |
Ammonium sulfite, anhydrous |
8.6 g |
Sodium metasulfite |
2.3 g |
Add water to make |
1 liter |
Adjust pH with acetic acid to be pH=6.0 |
<Stabilizer> |
Formalin (in a 37% solution) |
1.5 mℓ |
Konidux (manufactured by Konica Corp.) |
7.5 mℓ |
Add water to make |
1 liter |
[0111] Table-4 shows the results of fog (Dmin) and the sensitivities obtained by exposing
each sample to light.
Table-4
No. |
Emulsion |
Ir content of surface (mol/molAgX) |
Dmin |
Sensitivity |
Distinction between Invention and Out of Invention |
|
|
|
|
8-sec. exposure |
1/12.5-sec. exposure |
1x10⁻⁴-sec. exposure |
|
1 |
EM-1 |
- |
0.19 |
80 |
100 |
80 |
Out of Invention* |
2 |
EM-2 |
- |
0.15 |
135 |
150 |
145 |
Invention* |
3 |
EM-3 |
- |
0.16 |
210 |
250 |
230 |
Invention* |
4 |
EM-4 |
- |
0.15 |
135 |
165 |
155 |
Invention* |
5 |
EM-5 |
- |
0.20 |
65 |
80 |
65 |
Out of Invention |
6 |
EM-6 |
- |
0.19 |
40 |
50 |
45 |
Out of Invention |
7 |
EM-1 |
6.5x10⁻⁶ |
0.16 |
140 |
160 |
150 |
Invention* |
8 |
EM-1 |
6.5x10⁻⁸ |
0.16 |
195 |
230 |
215 |
Invention* |
9 |
EM-5 |
6.5x10⁻⁶ |
0.18 |
35 |
50 |
45 |
Out of Invention |
10 |
EM-5 |
6.5x10⁻⁸ |
0.19 |
55 |
70 |
60 |
Out of Invention |
11 |
EM-1 |
- |
0.22 |
75 |
100 |
85 |
Out of Invention* |
12 |
EM-2 |
- |
0.18 |
130 |
140 |
145 |
Invention* |
13 |
EM-3 |
- |
0.18 |
205 |
230 |
215 |
Invention* |
14 |
EM-4 |
- |
0.17 |
140 |
160 |
150 |
Invention* |
15 |
EM-5 |
- |
0.24 |
70 |
80 |
70 |
Out of Invention |
16 |
EM-6 |
- |
0.22 |
45 |
55 |
50 |
Out of Invention |
17 |
EM-1 |
6.5x10⁻⁶ |
0.18 |
130 |
155 |
140 |
Invention* |
18 |
EM-1 |
6.5x10⁻⁸ |
0.19 |
190 |
220 |
205 |
Invention* |
19 |
EM-5 |
6.5x10⁻⁶ |
0.22 |
45 |
60 |
50 |
Out of Invention |
20 |
EM-5 |
6.5x10⁻⁸ |
0.22 |
55 |
65 |
60 |
Out of Invention |
* Fine grains of AgI were present during growing emulsion grains. |
[0112] In Table-4, the sensitivities are shown in such a manner that, taking the reciprocal
number of the exposure required to give a density of fog +0.1 in each of the cases
where the couplers were added and not added, the sensitivies of Samples No. 1 through
No. 10 are each indicated by a value relative to the sensitivity of Sample No. 1,
which is set at a value of 100, obtained by exposing it to light for 1/12.5 seconds
and the sensitivies of Samples No. 11 through No. 20 are each indicated by a value
relative to the sensitivity of Sample No. 11, which is set at a value of 100, obtained
by exposing it to light for 1/12.5 seconds.
[0113] As shown in Table-4, in the samples each not containing any coupler, among Samples
No. 1 through No. 10, Samples No. 2 through No. 4 of the invention each using the
grain doped with iridium inside the crystals thereof were proved to be lower in fog
and higher in sensitivity than Comparative Samples No. 1 and No. 5 each not doped
with any iridium inside the crystals thereof. Further, as is obvious from the results
from Samples No. 7 through No. 10, Inventive Samples No. 7 and No. 8 to each of which
iridium was added after the crystals thereof were completely grown up were proved
to be lower in fog and higher in sensitivity than Sample No. 1 and Comparative Samples
No. 9 and No. 10 to each of which iridium was added after the crystals thereof were
completely grown up, and they were also proved to be able to obtain the same effects
as in the case that iridium was doped inside the crystals.
[0114] When an illuminance is either low or high, the samples using the emulsions of the
invention are higher in sensitivity than any Comparative Sample. It can be understood
that the invention can be effectual in improving an illuminance reciprocity law failure.
[0115] Samples No. 11 through No. 20 to each of which couplers were added can display the
same effects as in the case where no coupler was added. It was proved that the samples
of the invention are low in fogginess and high in sensitivity.
Example 2
[0116] Samples No. 21 through No. 26 were prepared in the manner that the emulsions EM-7
through EM-12 each described in Manufacturing Examples 3 and 4 were each subjected
to the chemical and spectral sensitization in the same way as in Example 1 and magenta
couplers were then added thereto as shown in Table-5, provided, as for the spectral
sensitization, the following sensitizing dyes (III) and (IV) were used in the amounts
of 300 mg and 30 mg per mol of AgI, respectively.
[0117] Each of the resulting Samples No. 21 through No. 26 was exposed to light and then
processed in the same procedures as in Example 1, provided, the exposure were made
for 1/12.5 seconds through a blue or yellow filter and were then treated in Processing
Steps (II) given in Example 1.

[0118] The results thereof as shown in Table-5. Wherein, each resulting sensitivity is represented
by the reciprocal number of an exposure required to give a density of fog +0.1, the
resulting blue sensitivity is represented by a value relative to the blue sensitivity
value set at a value of 100 of Sample No. 21 not yet added thereto any spectral sensitizing
dye, and the resulting minus-blue sensitivity is represented by a value relative to
the minus-blue sensitivity set at a value of 100 of Sample No. 21.
Table-5
Sample No. |
Emulsion |
Dmin |
Before spectrally sensitized |
After spectrally sensitized |
Subject to Invention or out of Invention |
|
|
|
to blue |
to blue |
to yellow |
|
21 |
EM-7 |
0.26 |
100 |
70 |
110 |
Out of Invention* |
22 |
EM-8 |
0.24 |
170 |
160 |
265 |
Invention* |
23 |
EM-9 |
0.26 |
90 |
60 |
95 |
Out of Invention |
24 |
EM-10 |
0.25 |
75 |
50 |
85 |
-ditto- |
25 |
EM-11 |
0.30 |
60 |
30 |
65 |
-ditto- |
26 |
EM-12 |
0.30 |
65 |
35 |
70 |
-ditto- |
* Fine grains of AgI were present during growing emulsion grains. |
[0119] As shown in Table-5, it can be understood that Sample No. 22 of the invention which
used the emulsion grain doped therein with iridium inside the crystals thereof is
characterized in that a decrease in the intrinsic sensitivity by dyes is less extent
than that in Comparative Samples and that not only the sensitivity is higher in the
spectrally sensitized regions but the fog is lower.
[0120] It is further understood from Samples No. 25 and No. 26 that the silver iodobromide
emulsion grains having a uniform halide compositions can little display the effect
of the invention that is contributed by an iridium compound.
[0121] The effects of the invention could be obtained as in Sample No. 22, even when making
use of either emulsion grains doped uniformly therein with iridium or the other emulsion
added thereto with iridium at a time before 98.5% of the whole silver amount was added,
under the same grain growing conditions as in EM-8.
Example 3
[0122] A multilayered color light-sensitive material No. 27 was so prepared as to be coated
over a subbed cellulose acetate support and to comprise the layers having the following
corresponding compositions.
[0123] In the following compositions, the amounts of silver halide and colloidal silver
each coated are expressed in terms of the g/m² unit of silver contained therein; the
amounts of additives and gelatin each used are expressed in terms of the g/m² unit
thereof; and the amounts of sensitizing dyes and couplers each used are expressed
in terms of the mol numbers thereof in one and the same layer per mol of silver halides
used.
[0125] Further, Samples No. 28 through No. 30 were prepared in the following procedures:
[0126] Sample No. 28 was a sample prepared in quite the same manner as in Sample No. 27,
except that EM-1 and EM-7 of Sample No. 27 were replaced by EM-3 and EM-8, respectively.
[0127] Sample No. 29 was a sample prepared in quite the same manner as in Sample No. 27,
except that EM-1 and EM-7 of Sample No. 27 were replaced by EM-5 and EM-9, respectively.
[0128] Sample No. 30 was a sample prepared in quite the same manner as in Sample No. 27,
except that EM-1 and EM-7 of Sample No. 27 were replaced by EM-6 and EM-10, respectively.
[0129] Each of the resulting samples was exposed to white light and was then processed.
After then, each of the relative sensitivities thereof was measured.
[0130] The relative sensitivities were measured of the cyan, magenta and cyan densities
in the ordinary method, respectively. The results thereof are shown in Table-6.
Table-6
No. |
B |
G |
R |
|
27 |
100 |
100 |
100 |
(comparative) |
28 |
220 |
190 |
150 |
(inventive) |
29 |
70 |
75 |
80 |
(comparative) |
30 |
55 |
65 |
70 |
(comparative) |
In the table, |
B : Blue-sensitivity, |
G : Green-sensitivity, and |
R : Red-sensitivity |
[0131] The sensitivities of B, G and R are indicated each by a value relative to the sensitivity
value set at a value of 100 of Sample No. 27.
[0132] As is obvious from Table-6, it was proved that Sample No. 28 used therein the silver
halide emulsions relating to the invention are higher in sensitivity than in Comparative
Samples No. 27, No. 29 and No. 30 and that the multilayered samples are also able
to display the same effects as in the single-layered samples.