FIELD OF THE INVENTION
[0001] The present invention relates to a method for producing a spectrally sensitized silver
halide emulsion and, more particularly, to a method of making a silver halide emulsion,
in which a cyanine dye of the kind which forms a J-aggregate and a supersensitizer
are used during the formation of silver halide grains.
BACKGROUND OF THE INVENTION
[0002] In making spectrally sensitized silver halide emulsions, sensitizing dyes are usually
added to emulsions after formation of silver halide grains. Methods of adding sensitizing
dyes to emulsions prior to completion of grain formation of silver halide are disclosed
in U.S. Patents 2, 735,766, 3,628,960, 4,183,756 and 4,225,666 and JP-A-196749/85
(U.S. Patent 4,683,193), JP-A-103149/86, JP-A-249053/86, and JP-A-210345/86 (the term
"JP-A" as used herein means an "unexamined published Japanese patent application").
[0003] Particularly in U.S. Patents 4,183,756 and 4,225,666, it is disclosed that advantages
such as an increase in sensitivity and a strengthening of adsorption of sensitizing
dyes to silver halide grains are obtained by adding sensitizing dyes to emulsions
after the stable nucleation, and during the course of the formation of silver halide
grains.
[0004] However, frequently silver halide emulsions made in accordance with the methods disclosed
in the above-cited patents, which involve adding a J-aggregated cyanine dye prior
to the grain formation of silver halide, are spectrally sensitized with markedly low
efficiency, or cannot provide a high spectral sensitizing effect.
[0005] The efficiency of spectral sensitization can be determined by measuring a relative
quantum yield Φr in spectral sensitization. The procedures for measuring Φr are well-known
to those skilled in the art, and are described in detail, e.g., in J. Spence & B.H.
Carroll,
Journal of Physical and Colloid Chemistry, vol. 52, p. 1090 (1948), and Tada-aki Tani & Hitoshi Urabe,
Nippon Shashin Gakkai-Shi, vol.41, p. 325 (1978).
SUMMARY OF THE INVENTION
[0006] A first object of the present invention is to provide an improved method for spectral
sensitization, in which adsorption of dyes is strengthened and thereby a high efficiency
of spectral sensitization can be obtained.
[0007] A second object of the present invention is to provide an improved method for spectral
sensitization, in which the desensitization of dyes is depressed and thereby a high
efficiency of spectral sensitization can be obtained.
[0008] A third object of the present invention is to provide an improved method for spectral
sensitization, in which a large amount of dyes are added to provide high efficiency
spectral sensitization.
[0009] We have found that an improved silver halide photographic emulsion, which has a high
spectral sensitizing effect, and in which adsorption of a sensitizing dye is strengthened,
can be made by forming silver halide grains in the presence of not only a J-aggregated
cyanine dye but also a sensitizing amount of a supersensitizer. Further, we have found
that in accordance with the above-described method, the desensitizing effect of dyes
can be depressed and the efficiency of spectral sensitization can be heightened, so
an improved silver halide photographic emulsion which has spectral sensitization of
high efficiency and chemical sensitization can be prepared. Furthermore, we have found
that in accordance with this method, the desensitizing effect of dyes can be depressed
to enable the preparation of an improved silver halide photographic emulsion with
a high spectral sensitizing efficiency by addition of a large amount of spectral sensitizing
dye.
[0010] Accordingly, the present invention relates to a method for producing a spectrally
sensitized silver halide photographic emulsion by the step of forming silver halide
grains in the presence of at least one J-aggregated cyanine dye and a supersensitizer.
DETAILED DESCRIPTION OF THE INVENTION
[0011] The term "supersensitizer" as used herein means any compound having a supersensitizing
effect conventionally used in the field of silver halide photographic emulsions,
and includes compounds capable of increasing the spectral sensitivity of an emulsion
when a cyanine dye is used in combination therewith, compared with the use of the
cyanine dyev alone.
[0012] A cyanine dye of the kind which forms the J-aggregate and a supersensitizer can
be added to a silver halide emulsion at any time, provided that it preceeds the completion
of the formation of silver halide grains. The addition time can be properly chosen
depending on the types of sensitizing dyes and emulsion used. Whole amounts of sensitizing
dye and supersensitizer may be added to the reaction system simultaneously with or
prior to the beginning of grain formation. On the other hand, the sensitizing dye
and the supersensitizer each may be divided into several portions, and added intermittently.
In the latter case, for instance, one portion is added at the beginning of the grain
formation, and the others can be added at regular time intervals during the course
of grain formation. On the other hand, the sensitizing dye and the supersensitizer
can be continuously added before completion of the grain formation. These ingredients
may be added together with a silver nitrate solution, a halide solution or independently
of these solutions. In the latter case, the addition may be initiated simultaneously
with or prior to the beginning of grain formation, or at a time after the beginning
of grain formation. When an emulsion-making method including a step of growing seed
crystals is employed, the dye and the supersensitizer may be continuously or intermittently
added during the growing step.
[0013] Even though the addition of the J-aggregated sensitizing dyes and the supersensitizer
is continued after the completion of grain formation of silver halide, some benefit
can be obtained, provided that the amounts added after the completion of grain formation
are below one-half the respective total amounts added. However, the continued addition
departing from the scope of the present invention causes the lowering of absorbance
in the spectrally sensitizable region, and further deterioration in keeping qualities
of the emulsion prepared and the sensitive material containing the emulsion.
[0014] A sensitizing dye and a supersensitizer can be added in various manners as described
above, provided that the addition thereof is finished prior to the completion of the
grain formation of silver halide. The sensitizing dye and the supersensitizer may
be added separately, or as a mixture thereof. They may be added simultaneously or
alternately with each other. When both are added simultaneously, each ingredient
may be added separately before or afterward. More specifically, it is preferred that
the addition of a first ingredient should be started before the quantity of the second
ingredient exceeds one-half the total amount to be added, and more than one-half of
the total amount of the first ingredient should be finished by the conclusion of the
addition of the second ingredient. More preferably, more than two-thirds of the respective
total amounts should be added simultaneously. In particular, the simultaneous addition
of the respective total amounts is favoured over other manners of addition.
[0015] The amounts of each of a sensitizing dye and a supersensitizer to be added to a silver
halide photographic emulsion in accordance with the present invention, though depending
on the shape and the size of silver halide grains to be supersensitized thereby, preferably
range from 1x10⁻⁶ to 5x10⁻³ mol, particularly from 1x10⁻⁵ to 2.5x10⁻³ mol, per mole
of silver halide.
[0016] In adding a sensitizing dye to be used in the present invention to a silver halide
photographic emulsion in accordance with the method of the present invention, the
dye may be directly dispersed into the emulsion, or dissolved in advance in a solvent,
such as water, acetone, methanol, ethanol, propanol, methyl cellosolve, 2,2,3,3-tetrafluoropropanol,
N,N-dimethylformamide or a mixture of two or more thereof, and then added to the emulsion.
[0017] Also, the dissolving a sensitizing dye can be performed with ultrasonic waves. Further,
various methods can be employed in adding the sensitizing dyes of the present invention,
including a method as described in U.S. Patent 3, 469,987, in which a sensitizing
dye is dissolved in a volatile organic solvent, the resulting solution is dispersed
into water or a hydrophilic colloid, and then the resulting dispersion is added to
an emulsion; a method as described in JP-B-46-24185 (the term "JP-B" as used herein
means an "examined published Japanese patent publication"), in which a water-insoluble
dye is dispersed into a water-soluble solvent without undergoing any dissolution treatment,
and the resulting dispersion is added to an emulsion; a method as described in JP-B-44-23389,
JP-B-44-27555, JP-B-57-22091, in which a sensitizing dye dissolved in an acid is added
to an emulsion, or a sensitizing dye which is dissolved in the presence of an acid
or a base is added to an emulsion; a method as described in U.S. Patents 3,822,135
and 4,006,025, in which a sensitizing dye is made an aqueous or collidal dispersion
in the presence of a surface active agent, and then added to an emulsion; a method
as described in JP-A-53-102733 and JP-A-58-105141, in which a sensitizing dye is dispersed
directly into a hydrophilic colloid, and then added to an emulsion; and a method as
described in JP-A-51-74624, in which a sensitizing dye is dissolved by the use of
a red-shift compound, and the resulting solution is added to an emulsion.
[0018] Cyanine dyes of the kind which form the J-aggregate, which are preferably used in
the present invention, are represented by the following general formulae (I), (II)
or (III). These dyes can also be employed as compounds referred to as the supersensitizers
in the present invention.

[0019] In the foregoing formula (I), Z¹ represents oxygen, sulfur, selenium, or -CH=CH-,
and Z² represents sulfur, selenium, or -CH=CH-.
[0020] R₁ and R₂, which may be the same or different, each represents an unsubstituted or
substituted alkyl group.
[0021] V¹ and V⁴, which may be the same or different, each represents hydrogen or an atomic
group necesary for forming a condensed benzene ring with V² and V⁵, respectively;
V², V³, V⁵ and V⁶, which may be the same or different, each represents a straight-
or branched-chain alkyl group containing at most 5 carbon atoms, an alkoxy group containing
at most 4 carbon atoms, a hydroxy group, an acylamino group containing at most 4 carbon
atoms, an unsubstituted or substituted phenyl group containing at most 8 carbon atoms,
a halogen atom, an alkoxycarbonyl group containing at most 5 carbon atoms, a carboxyl
group, or a hydrogen atom.
[0022] Provided that V³ may be linked with V² and V⁶ may be linked with V⁵, to form a condensed
benzene ring.
[0023] m₁ represents 0 or 1; and X₁ represents a counter ion residue necessary for charge
balance. Specific examples of a cationic counter ion residue represented by X₁ include
Na⁺, K⁺, a pyridinium cation, and an ammonium cation such as triethylammonium cation,
and anionic counter ion residue include Cl⁻, Br⁻, I⁻, SCN⁻, p-toluenesulfonium, benzenesulfonium,
ClO₄⁻, and ethylsulfate.

[0024] In the foregoing formula (II), Z²¹ represents an atomic group necessary for completing
a 4-thiazoline, thiazolidine, benzo-4-thiazoline, naphtho[1,2-d]-4-thiazoline, naphtho[2,3-d]-4-thiazoline,
selenazolidine, 4-selenazoline, benzo-4-selenazoline, naphtho[1,2-d] 4-selenazoline,
naphtho[2,3-d]-4-selenazoline, benzo-4-oxazoline, naphtho[1,2-d]-4-oxazoline, naphtho[2,3-d]-4-oxazoline
or benzo-4-imidazoline nucleus, each of which may be unsubstituted or substituted.
[0025] R₂₁, R₂₂ and R₂₃, which may be the same or different, each represents an unsubstituted
or substituted alkyl group.
[0026] R₂₄ represents a hydrogen atom or an atomic group necessary for completing a 5- or
6-membered ring in combination with R₂₃.
[0027] V²¹ represents an electron attracting group including fluorine, chlorine, a cyano
group, an alkoxycarbonyl group containing at most 4 carbon atoms, and an alkylsulfonyl
group containing at most 4 carbon atoms.
[0028] V²² can be a group represented by V²¹, and further may be hydrogen or an atomic group
necessary for completing a condensed benzene ring in combination with V²¹.
[0029] X₂₁ has the same meaning as X₁ in formula (I), and m₂₁ represents 0 or 1.

[0030] In the foregoing formula (III), Z³¹ represents oxygen, sulfur, or selenium.
[0031] Z³² represents an atomic group necessary for completing a thiazole, benzothiazole,
naphtho[1,2- d]thiazole, 8,9-dihydro-naphtho[1,2-d]thiazole, naphtho[2,3-d]thiazole,
selenazole, benzoselenazole, naphtho[1,2-d]selenazole, benzoxazole, naphtho[1,2-d]oxazole,
or naphtho[2,3-d]oxazole nucleus.
[0032] R₃₁ and R₃₂, which may be the same or different, each has the same definition as
R₁.
[0033] R₃₃ represents ethyl, propyl, butyl, phenyl or phenetyl and preferably is ethyl.
[0034] V³¹, V³² and V³³ have the same meanings as V¹, V² and V₃, respectively, and further,
V³² and V³³ may combine with each other to form a 5- or 6-membered ring, which can
contain oxygen atoms.
[0035] R₃₄ represents a hydrogen atom, or an atomic group necessary for completing a 5-
or 6-membered ring in combination with R₃₂.
[0036] X₃₁ has the same meaning as X₁ in (I), and m₃₁ represents 0 or 1.
[0037] Preferred examples of a substituent group by which alkyl groups represented by R₁,
R₂, R₂₁, R₂₂, R₂₃, R₃₁ and R₃₂ in the foregoing general formulae (I), (II) and (III)
can be substituted include a lower alkyl group, a halogen atom, a carbamoyl group,
a carboxyl group, an alkoxycarbonyl group, an acylamino group, a hydroxyl group,
a sulfo group, and a substituted phenyl group such as a sulfo-substituted phenyl,
a carboxy-substituted phenyl. Specific examples of unsubstituted and substituted alkyl
groups preferred as R₁, R₂, R₂₁, R₂₂, R₂₃, R₃₁ and R₃₂ include methyl, ethyl, propyl,
pentyl, methoxymethyl, ethoxyethyl, 2,2,2-trifluoroethyl, 2,2,3,3,-tetra-fluoropropyl,
carbamoylethyl, hydroxyethyl, carboxymethyl, carboxyethyl, 2-sulfoethyl, 3-sulfopropyl,
3-sulfobutyl, 4-sulfobutyl, p-sulfophenetyl, ethoxycarbonylethyl, 2-hydroxy-3-sulfopropyl,
2-acetylaminoethyl, 2-chloro-3-sulfopropyl and 2 [2-(3-sulfopropoxy)ethoxy]ethyl
group.
[0039] Preferred example of a supensitizer which can be used in the present invention include
sensitizing dyes described in U.S. Patents 3,703,377, 2,688,545, 3,397,060, 3,615,635
and 3,628,964, British Patents 1,242,588 and 1,293,862, JP-B-43-4936, JP-B-44-14030
and JP-B_43-10773, U.S. Patent 3,416,927, JP-B-43-4930, U.S. Patents 3,615,613, 3,615,
632, 3,617,295 and 3,635,721; holopolar cyanine dyes described in British Patent 1,153,343,
U.S. Patent 4,546,073, JP-A-59-148053; hemicyanines and hemicyanine bases described
in U.S.Patent 4,152, 163, JP-B-49-17525 and JP-B-48-38406; and aminostyryl compounds
described in British Patents 1,351,149, 1,230,449 and 1,310,994.
[0041] The heterocyclic group for Z may be a condensed ring, and preferably includes imidazole,
triazole, tetrazole, thiazole, oxazole, selenazole, benzimidazole, benzoxazole,
benzothiazole, thiadiazole, oxadiazole, benzoselenazole, pyrazole, pyrimidine, triazine,
pyridine, naphthothiazole, naphthoimidazole, naphthoxazole, azabenzimidazole, purine,
azaindene (e.g., triazaindene, tetraazaindene, pentaazaindene, etc.), and the like.
[0042] Further, these heterocyclic groups or condensed rings may be substituted with appropriate
substituents. Examples of the substituents are an alkyl group (e.g., methyl, ethyl,
hydroxyethyl, trifluoromethyl group, sulfopropyl, di-propylaminoehtyl, adamantane),
an alkenyl group (e.g., allyl), an aralkyl group (e.g., benzyl, p-chlorophenetyl),
an aryl group (e.g., phenyl, naphthyl, p-carboxyphenyl, 3,5-dicarboxyphenyl, m-sulfophenyl,
p-acetamidophenyl, 3-capramidophenyl, p-sulfamoylphenyl, m-hydroxyphenyl, p-nitrophenyl,
3,5-dichlorophenyl, 2-methoxyphenyl), a heterocyclic group (e.g., pyridyl), a halogen
atom (e.g., chlorine, bromine), a mercapto group, a cyano group, a carboxyl group,
a sulfo group, a hydroxyl group, a carbamoyl group, a sulfamoyl group, an amino group,
a nitro group, an alkoxy group (e.g., methoxy, ethoxy), an aryloxy group (e.g., phenoxy),
an acyl group (e.g., acetyl), an acylamino group (e.g., acetylamino, capramido, methylsulfonylamino),
a substituted amino group (e.g., diethylamino, hydroxyamino), an alkylthio or arylthio
group (e.g., methylthio, carboxyethylthio, sulfobutylthio), an alkoxycarbonyl group
(e.g., methoxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl), and the
like.
[0043] The mercapto-containing compounds may be disulfides (Z-S-S-Z) that can be easily
cleaved into the form of the formula (IV) in the emulsion.
[0044] Specific compounds represented by general formula (IV) include the compounds represented
by general formula (1) described in JP-A-222843/85.
[0045] In addition, materials which can exhibit a supersensitizing effect in combination
with sensitizing dyes although they themselves do not spectrally sensitize silver
halide emulsions or do not absorb light in the visible region, for example, aminostilbene
compounds substituted with nitrogen-containing heterocyclic groups (e.g., as described
in U.S. Patents 2,933,390 and 3,635,721), aromatic organic acid-formaldehyde condensates
(e.g., U.S. Patent 3,743,510), cadmium salts, azaindene compounds and so on, can be
employed as the supersensitizer of the present invention.
[0046] Sensitizing dyes and supersensitizers which can be used in the present invention
can be synthesized according to methods described in F.M. Hamer,
Heterocyclic Compounds - Cyanine Dyes and Related Compounds - (John Wiley & Sons, New York-London 1964), D.M. Sturmer,
Heterocyclic Compounds - Special Topics in Heterocyclic Chemistry-, chapter 8, paragraph 4, pages 482-515 (John Wiley & Sons, New York-London 1977),
and JP-A-60-78445.
[0047] The silver halide emulsion which can be used in the present invention is generally
made by mixing a solution of a water-soluble silver salt (e.g., silver nitrate) with
a solution of a water-soluble halide (e.g., potassium bromide) in the presence of
a solution of a water-soluble high polymer, such as gelatin. The silver halide formed
therein may be any of silver chloride, silver bromide, and mixed silver halides such
as silver chlorobromide, silver iodobromide, silver chloroiodobromide and so on.
The mean grain size thereof is preferably less than 4 microns. The term "mean grain
size "as used herein refers to the grain diameter in case of grains spherical or approximately
spherical in shape, while it refers to the edge length in case of cubic grains. In
both cases, it is represented by the mean based on the projected areas of grains.
The distribution of grain size may be narrow (monodisperse) or broad.
[0048] These silver halide grains may assume any crystal form, such as that of a cube, a
tetradecahedron, a rhombic dodecahedron or an octahedron, a composite form of two
or more thereof, a sphere, a plate, or so on.
[0049] Also, an emulsion in which silver halide grains having a tabular shape such that
the grain diameter is 5 or more times the grain thickness are contained in a fraction
of 50% or more, based on the total projected area, may be used. The preferred grain
size of these grains ranges from 0.5 to 10 µm. (The term "grain size "as used herein
refers to the diameter of a circle having the same area as the projected area of a
grain, and the term thickness refers to the distance between two parallel faces.)
Detailed descriptions are given, e.g., in JP-A 58-127921 and JP-A-58-113927.
[0050] The crystal structure of silver halide grains may be uniform throughout, or the silver
halide grains may have a multilayer structure in which the interior and the surface
of the grains differ in halide composition, or a conversion type structure described
in British Patent 635,841, and U.S. Patent 3,622,318. Either silver halide grains
of the kind which form latent image predominantly at the surface of the grains, or
those of the kind which mainly form latent image inside the grains may be used.
[0051] Photographic emulsions which can be used in the present invention can be prepared
using methods as described in P. Glafkides,
Chimie et Physique Photographique, (Paul Montel 1967), G.F. Duffin,
Photographic Emulsion Chemistry, (Focal Press 1966), and V.L. Zelikman et al.,
Making and Coating Photographic Emulsion, (Focal Press 1964).
[0052] More specifically, any of an acid process, a neutral process and an ammonia process
can be employed for preparation of photographic emulsions. Suitable methods for reacting
a water soluble silver salt with a water-soluble halide may be any of a single jet
method, a double jet method and a combination thereof. Also, a method in which silver
halide grains are produced in the presence of excess silver ion (the reverse mixing
method) can be employed in the present invention. The controlled double jet method,
in which the pAg of the liquid phase in which silver halide grains are precipitated
is maintained constant, can be also employed. According to this method, a silver halide
emulsion having a regular crystal form and grain sizes nearly uniform can be obtained.
[0053] In a process of the formation or physical ripening of silver halide grains, a cadmium
salt, a zinc salt, a lead salt, a thallium salt, a iridium salt or a complex salt
thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt
thereof, and the like may be present.
[0054] In order to control the crystal growth of silver halide grains in the step of forming
silver halide grains, silver halide solvents, such as ammonia, potassium thiocyanate,
ammonium thiocyanate, thioether compounds, thione compounds (e.g., those described
in JP-A-53-144319, JP-A-53-82408 and JP-A-55-77737), amine compounds (e.g., those
described in JP-A-54-100717) can be used.
[0055] While the silver halide emulsion can be employed without being chemically sensitized,
that is to say, without being subjected to after-ripening (in the form of a primitive
emulsion), it is preferably chemically sensitized. For the chemical sensitization,
methods described in. H. Frieser,
Die Grundlagen der Photographischen Prozesse mit Silberhalogeniden, pp. 675-734, (Akademische Verlagsgesellschaft 1968) can be employed.
[0056] More specifically, sulfur sensitization methods using active gelatin, and compounds
containing sulfur capable of reacting with silver ions (e.g., thiosulfates, thioureas,
mercapto compounds, rhodanines and so on), reduction sensitization methods using reducing
materials (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic
acid, silane compounds and so on), noble metal sensitization methods using noble metal
compounds (e.g., gold compounds, and complex salts of Group VIII metals such as platinum,
iridium, palladium, etc.), and so on can be employed independently or as a combination
thereof.
[0057] In addition, other sensitizers such as polyoxyethylene derivatives (as described
in British Patent 981,470, JP-B-31-6475, U.S. Patent 2,716,062), polyoxypropylene
derivatives, derivatives having a quaternary ammonium group, and so on may be employed.
[0058] The photographic emulsion employed in the present invention can contain a wide variety
of compounds for purposes of preventing fog or stabilizing photographic functions
during production, storage, or photographic processing, including azoles, such as
benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles,
benzotriazoles, aminotriazoles; mercapto compounds, such as mercaptothiazoles, mercaptobenzothiazoles,
mercaptobenzimidazoles, mercapto-thiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole),
mercaptopyrimidines, mercapto-triazines; thioketo compounds such as oxazolinethione;
azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted
(1,3,3a,7)-tetraazaindenes), pentaazaindenes; and compounds which have been known
as antifoggants or stabilizers, such as benzenethiosulfones, benzenesulfinic acid
and benzenesulfonic acid amide.
[0059] More specific examples and usages of the above-cited compounds are disclosed in
U.S. Patents 3,954,474 and 3,982,947, JP-B-52-28660.
[0060] As for the binder or the protective colloid which can be used in applying the silver
halide emulsion, which is spectrally sensitized in accordance with the present invention,
to a photosensitive material, gelatin can be used. Also, hydrophilic synthetic high
polymers and the like can be used. Gelatin which can be used includes lime-processed
gelatin, acid-processed gelatin, and derived gelatins. Such gelatins are described
in
Research Disclosure, Vol, 176, No. 17643, IX (Dec. 1976).
[0061] The spectrally sensitized silver halide emulsion of the present invention and the
photographic light-sensitive material using the same may contain color image-forming
couplers, that is to say, compounds capble of forming colors by color development
processing by oxidative coupling with aromatic primary amine developing agents (e.g.,
phenylenediamine derivatives, aminophenol derivatives, etc.). Nondiffusible couplers
which contain a hydrophobic group called a ballast group in a molecule, or polymeric
couplers are preferred over others. These couplers may be either four-equivalent or
two-equivalent to silver ion. In addition, the emulsion and the light-sensitive material
may contain colored couplers having a color compensating effect, couplers capable
of releasing a development inhibitor with the progress of development ("DIR couplers"),
and couplers capable of releasing a development accelerator or a fogging agent ("DAR
couplers" and "FR couplers"). Further, those may contain colorless DIR coupling compounds
which can yield a colorless compound by the coupling reaction, that release a development
inhibitor.
[0062] Suitable examples of magenta couplers include those of 5 pyrazolone type, pyrazolobenzimidazole
type, cyanoacetylcumarone type, open-chain acylacetonitrile type, and pyrazoloazole
type. Suitable examples of yellow couplers include those of acylacetamide type (such
as benzoylacetanilides, pivaloylacetanilides). Suitable examples of cyan couplers
include those of naphthol type, phenol type and the like.
[0063] In order to provide characteristics required of photosensitive materials, two or
more of the above-described couplers can be incorporated in the same layer, or one
of them can be added to two or more of different layers.
[0064] Compounds which can be additionally used in the silver halide emulsion prepared in
accordance with the present invention, and in the photographic light-sensitive material
using this emulsion include desensitizers, brightening agents, high boiling organic
solvents (coupler solvents), dye-image stabilizers, stain inhibitors, absorbers (dyes,
light absorbers and UV absorbers), hardeners, coating aids (surface active agents),
plasticizers, lubricants, antistatic agents, matting agents, development accelerators,
and so on. As for the additives described hereinbefore and these additives, those
described in
Research Disclosure, Vol. 176, No. 17643, I to XVI (pages 22 to 28) (Dec. 1978) can be used.
[0065] The finished emulsion is coated on an appropriate support such as baryta paper, resin-coated
paper, synthetic paper, a triacetate film, a polyethylene tere phthalate film, another
plastic base, or a glass plate. Various coating methods, including a dip coating method,
an air knife coating method, a curtain coating method and an extrusion coating method
utilizing a hopper as described in U.S. Patent 2,681,294, can be employed.
[0066] Such a support may be either transparent or opaque depending upon the intended use
of the light-sensitive material. When a support used is transparent, it can be colorless
or colored by addition of a dye or a pigment.
[0067] The exposure for obtaining a photographic image may be carried out in a conventional
manner. Any pf various known light sources including natural light (sunlight), a tungsten
lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, xenon
flash lamp, cathode ray flying spot and so on can be employed for the exposure. Suitable
exposure times which can be used include not only exposure times commonly used in
cameras ranging from about 1/1000 to about 1 sec., but also exposure times shorter
than 1/1000 sec., e.g., about 1/10⁴ to about 1/10⁶, as used with xenon flash lamps
and cathode-ray tubes. Exposure times longer than 1 second can also be used. The spectral
distribution of the light employed for the exposure can be controlled using color
filters, if desired. Laser beams can also be employed for the exposure. Moreover,
the emulsion of the present invention may also be exposed to light emitted from phosphors
excited by electron beams, X-rays, γ-rays, α-rays and the like.
[0068] Photographic light-sensitive materials to which the emulsion of the present invention
can be applied include various color and black-and-white photosensitive materials.
Specific examples of such materials include color negative films (for amateur use,
motion picture use, etc.), color reversal films (for slide use, motion picture use,
etc., which may be the coupler-in-emulsion type, or not), color photographic papers,
color positive films (for motion picture use, etc.), color reversal photographic papers,
heat-developable color photosensitive materials, color photosensitive materials for
a silver dye bleach process, photographic light-sensitive materials for a photomechanical
process (lith films, scanner films, etc.), X-ray photographic light-sensitive materials
(for medical use employing radiography or fluorography, for industrial use, etc.),
black and-white negative films, black-and-white photographic papers, microphotographic
light-sensitive materials (COM, microfilms, etc.), color diffusion transfer photosensitive
materials (DTR), silver salt diffusion transfer photosensitive materials, printout
photosensitive materials, and so on.
[0069] In the photographic processing of a photosensitive material to which the silver halide
emulsion prepared in accordance with the present invention is applied, any known processing
method and any known processing solution can be employed. The processing temperature
is generally in the range of about 18°C to about 50°C. Of course, temperatures lower
than about 18°C or higher than about 50°C may be employed. The photographic processing
may include either development processing for forming a silver image (black-and-white
photographic processing) or development processing for forming a dye image (color
photographic processing).
[0070] Specifically, the development processing can be performed using the methods described
in
Research Disclosure, Vol. 176, No. 17643, pages 28-29, and
idi, Vol. 187, No. 18716, page 651, left and right columns.
[0071] The present invention is illustrated in greater detail by reference to the following
examples. However, the invention is not to be construed as being limited to these
examples. Unless otherwise indicated, all parts, percents and ratios are by weight.
EXAMPLE 1
Method 1 (Comparative example)
[0072] In a reaction container, 1,000 ml of water, 30 g of deionized bone gelatin, 15 ml
of a 50 % NH₄NO₃ aqueous solution and 7.5 ml of a 25 % aqueous ammonia were placed,
and kept at 50°C with thoroughly stirring. Thereto, 750 ml of a 1N AgNO₃ aqueous solution
and a 1N KBr aqueous solution were added over a 40-minute period, and the silver potential
relative to a saturated calomel electrode was kept at +50 mV all through the reaction.
[0073] The silver bromide grains obtained had a cubic form, and their edge length was 0.62±0.06
µm. The foregoing emulsion was desalted, and thereto were added 140 g of deionized
bone gelatin and 700 ml of water. The resulting emulsion was adjusted to pH 6.5 and
pAg 8.3 at 50°C (which was called Emulsion (1)-1).
[0074] This emulsion was divided into 7 fractions, and each was allowed to stand for 20
minutes at 40°C with thorough stirring in order to effect ripening. During the ripening,
the sensitizing dye II-12 was added, in the form of 5x10⁻⁴, 1x10⁻³ and 2x10⁻³ mol/l
of methanol solutions, to three of these fractions in amounts of 8.6x10⁻⁵ mol, 1.72x10⁻⁴
mol and 3.44x10⁻⁴ mol, respectively, per mol of silver, while the sensitizing dye
II-12 and the sensitizing dye III-1 to function as a supersensitizer were added to
the other four fractions in equimolar amounts of 4.3x10⁻⁵ mol, 8.6x10⁻⁵ mol, 1.72x10⁻⁴
mol and 3.44x10⁻⁴ mol, respectively, per mole of silver. To all of these fractions
were further added 0.033 g of sodium 2-(N- methylstearoylamino)ethylsulfonate, 0.016
g of sodium dodecylbenzenesulfonate and 0.784 g of 1,3-bis(vinylsulfonyl)-2-propanol.
Each of the resulting emulsion fractions was coated on a cellulose triacetate film
base at a coverage of 7 g/m² based on the silver bromide. Each of the coated emulsions
was exposed to a tungsten lamp (color temperature: 2,854°K) through interference filters
transmitting light of 400 nm, 541 nm and 571 nm, respectively, and a continuous wedge.
The exposed emulsion coats were developed at 30°C for 10 minutes using the Developer
D19 (comprising 2.2 g of Metol, 96 g of sodium sulfite, 8.8 g of hydroquinone, 48
g of sodium carbonate, and 5 g of potassium bromide in 1 liter of water).
[0075] In addition to sensitometric evaluation, the relative quantum yields of the spectral
sensitization with the dye II-12 were determined as described in Tada-aki Tani & Hitoshi
Urabe,
Nippon Shashin Gakkai-Shi, volume 41, page 325 (1978). The results obtained are shown in Table 1.
Method 2 (comparative example)
[0076] Silver halide grains were formed in the same manner as in Method 1, except the methanol
solution of sensitizing dye II-12 was added continuously at an uniform rate over a
period from 4 minutes to 38 minutes after the start of the addition of the aqueous
solution of silver nitrate. Therein, the amounts of the sensitizing dye II-12 added
were 8.6x10⁻⁵ mol, 1.72x10⁻⁴ mol and 3.44x10⁻⁴ mol, respectively, per mol of silver.
The silver bromide grains formed had a cubic form in every case, and edge lengths
were 0.62±0.05 µm, 0.61±0.07 µm and 0.60±0.06 µm, respectively (These emulsions were
named (2)-1, (2)-2 and (2)-3, respectively).
[0077] To each of the foregoing emulsions, 140 g of deionized gelatin and 700 ml of water
were added after desalting and washing, and then each was adjusted to pH 6.5 and pAg
8.3. Thereafter, ripening was carried out at 40°C for 20 minutes with thorough stirring.
During the ripening, sodium 2-(N-methylstearoylamino)-ethylsulfonate, sodium dodecyl-benzenesulfonate
and 1,3-bis(vinylsulfonyl)-2-propanol were added to each emulsion. The resulting
emulsions were each coated on a cellulose triacetate base film, exposed and developed
in the same manner as used in Method 1.
[0078] The results obtained are also shown in Table 1.
Method 3 (Present invention)
[0079] The same experiments as in Method 2 were performed, except that the sensitizing
dye III-1 to function as a supersensitizer was added at an uniform rate in the form
of 2.5x10⁻⁴, 5x10⁻⁴ and 1x10⁻³ mol/l methanol solutions simultaneously with addition
of the sensitizing dye II-12 in equimolar amounts.
[0080] The thus obtained silver bromide grains were also cubic in all cases, and edge lengths
were 0.62±0.07 µm, 0.60±0.07 µmand 0.60±0.07 µm, respectively.
[0081] The results of the experiments are shown in Table 1.
Table 1
Experiment No. |
Emulsion |
Addn. Amt. of Dye II-12 mol/mol/ Ag |
Addn. Amt. of Dye III-1 mol/mol/ Ag |
Absorption Coefficient at 571 nm |
Relative Sensitivity at 571 nm |
Φr at 571 nm |
1 (Comparison) |
(1)-1 |
8.6×10⁻⁵ |
0 |
0.288 |
100 |
0.48 |
2 (Comparison) |
(1)-1 |
1.72×10⁻⁴ |
0 |
0.410 |
96 |
0.43 |
3 (Comparison) |
(1)-1 |
3.44×10⁻⁴ |
0 |
0.547 |
56 |
0.49 |
4 (Comparison) |
(1)-1 |
4.3×10⁻⁵ |
4.3×10⁻⁵ |
0.186 |
684 |
0.50 |
5 (Comparison) |
(1)-1 |
8.6×10⁻⁵ |
8.6×10⁻⁵ |
0.277 |
703 |
0.46 |
6 (Comparison) |
(1)-1 |
1.72×10⁻⁴ |
1.72×10⁻⁴ |
0.382 |
306 |
0.53 |
7 (Comparison) |
(1)-1 |
3.44×10⁻⁴ |
3.44×10⁻⁴ |
0.467 |
272 |
0.66 |
8 (Comparison) |
(2)-1 |
8.6×10⁻⁵ |
0 |
0.226 |
22 |
0.07 |
9 (Comparison) |
(2)-2 |
1.72×10⁻⁴ |
0 |
0.345 |
27 |
0.11 |
10 (Comparison) |
(2)-3 |
3.44×10⁻⁴ |
0 |
0.510 |
20 |
0.19 |
11 (Invention) |
(3)-1 |
4.3×10⁻⁵ |
4.3×10⁻⁵ |
0.211 |
765 |
0.50 |
12 (Invention) |
(3)-2 |
8.6×10⁻⁵ |
8.6×10⁻⁵ |
0.328 |
1238 |
0.72 |
13 (Invention) |
(3)-3 |
1.72×10⁻⁴ |
1.72×10⁻⁴ |
0.477 |
945 |
0.68 |
14 (Invention) |
(29)-4 |
3.44×10⁻⁴ |
3.44×10⁻⁴ |
0.531 |
754 |
0.71 |
(The sensitivity was expressed as a reciprocal of the amount of exposure for the density
of fog+0.2 with the value of the emulsion of Experiment 1 being taken as 100) |
[0082] As can be seen from the data set forth in Table 1, the values of sensitivity and
Φr when where the exposure was carried out with light of 571 nm, at which the sensitizing
dye II-12 exhibits its absorption maximum, were extremely low when the sensitizing
dye II-12 forming the J-aggregate was added to an emulsion prior to completion of
the formation of the silver halide grains (experiments 8 to 10), as compared with
the case where the sensitizing dye was added after the completion of the grain formation
(experiments 1 to 3). On the other hand, although the simultaneous addition of the
sensitizing dye II-12 and the dye III-1 after the grain formation produced a supersensitizing
effect (experiments 4 to 7), the simultaneous addition of these dyes prior to the
completion of the grain formation in accordance with the present invention (experiments
11 to 14) achieved much higher sensitivities and/or higher Φr values.
[0083] That is, the method of the present invention has proved excellent, since not only
was the supersensitizing efficiency higher when the supersensitization was effected
prior to the completion of the grain formation than when the supersensitization was
carried out after the grain formation, but also very high sensitivity was attained
in the former case.
EXAMPLE 2
Method 4 (Comparative example)
[0084] To an aqueous 3% gelatin solution which contained 1.6x10⁻⁴ mol/mol silver of the
following compound (compound A);

and was kept at 75°C, a 750 ml of 1N aqueous solution of silver nitrate and an aqueous
solution containing a mixture of 0.98 mol of potassium bromide and 0.02 mol of potassium
iodide in 1 liter of water were simultaneously added with thorough stirring at a constant
rate over a period of 60 minutes as the silver potential in the reaction system was
maintained constant (-90 mV vs a standard calomel electrode SCE). Thus, octahedral
silver iodobromide grains having an iodide content of 2 mol% were formed. The resulting
emulsion was desalted according to a conventional flocculation process, to prepare
a photographic emulsion.
[0085] Therein, a methyl cellosolve 2.5x10⁻³ mol/l solution of the sensitizing dye 1-18
was further added in an amount of 7.2x10⁻⁴ mol per mol of silver over a period from
10 minutes after the start of the addition of the aqueous solution of silver nitrate
to 5 minutes before the conclusion of the addition of the aqueous solution of silver
nitrate. The mean grain size of the thus obtained silver halide grains was about 1.03
µm, and the variation coefficient was 8.9 %.
[0086] To the above emulsion, a water solution of Na₃Au(S₂O₃)₃ was added in an optimal amount,
and aged at 50°C for 60 minutes to effect gold-sulfur sensitization. This emulsion
was named (4)-1.
Method 5 (Present invention)
[0087] Two kinds of silver iodobromide grains were formed in the same manner as in Method
4, except a methyl cellosolve solution containing a mixture of the sensitizing dye
I-18 and the following compound B,

instead of the sensitizing dye I-18 alone were added at a constant rate so that the
total amount of the sensitizing dye I-18 added was 7.2x10⁻⁴ mol/mol Ag, and those
of the compound B 7.2x10⁻⁵ mol/mol Ag and 2.1x10⁻⁴ mol/mol Ag, respectively. Then,
in the same manner as Method 4, the resulting emulsions were desalted by a flocculation
process, and subjected to gold-sulfur sensitization at 50°C by adding an optimal amount
of a water solution of Na₂Au(S₂O₃)₃. These emulsions were named (5)-1 and (5)-2, respectively.
[0088] The mean grain size of each of the two kinds of octahedral silver iodobromide grains
formed was about 1.04 µm (and the variation coefficients were 13.5% and 13.9%, respectively).
[0089] After addition of 100 g of 10% gelatin gel, the emulsion (4)-1 obtained according
to Method 4 was divided into three fractions, and thereto compound B was added at
40°C in amounts of 0, 7.2x10⁻⁵ mol and 2.1x10⁻⁴ mol, respectively, per mole of silver.
To these emulsions, and to those obtained by further adding 100 g of 10% gelatin gel
to the emulsions (5)-1 and (5)-2, respectively, were added successively 4-hydroxy-6-methyl-(1,3,3a,7)-tetraazaindene
in an amount of 0.2 g per Kg of emulsion, sodium 2-hydroxy-4,6-dichloro-l,3,5-triazine
in an amount of 1.0 g per Kg of emulsion, and sodium dodecylbenzenesulfonate in an
amount of 0.1 g per Kg of emulsion. Each of the resulting emulsions was coated in
an amount of 3.7 g (as Ag)/m² on a polyethylene terephthalate film base to prepare
a photographic light-sensitive material.
[0090] In coating the above-described emulsion, an aqueous solution containing 5.0 wt% of
gelatin as a main component and 0.02 wt% of sodium dodecylbenzenesulfonate (a surface
active agent), and 0.057 wt% of sulfostyrene potassium homopolymer (a viscosity-increasing
agent) as additives was coated simultaneously on top of the emulsion layer. The gelatin
coverage of the thus-formed protective layer was about 1.0 g/m².
[0091] Each of the coated samples was exposed to a tungsten lamp (color temperature: 2854°K)
through interference filters capable of transmitting light of 545 nm and 400 nm,
respectively, which corresponded to the absorption maxima of main absorption peaks
in the distribution of spectral sensitization, and a continuous wedge. The exposed
samples were developed at 20°C for 7 minutes using a developer prepared by diluting
the following concentrated liquid developer with an equal volume of water.
Composition of Concentrated Liquid Developer
[0092] Water 700 ml
Metol (p-methylaminophenol sulfate) 3.1 g
Anhydrous Sodium Sulfite 45 g
Hydroquinone 12 g
Sodium carbonate (monohydrate) 79 g
Potassium Bromide 1.9 g
Water to make 1ℓ
[0093] The results obtained are shown in Table 2 together with relative quantum yields,
Φr, of the spectral sensitization with the dye I-18. The relative quantum yields Φr
were determined by the same method in Example 1.
Table 2
Experiment Number |
Emulsion |
Addition Amount of Compound B mol/mol Ag |
Absorption Coefficient at 545 nm |
Relative Sensitivity at 545 nm |
at Φr 545 nm |
1 (Comparison) |
(4)-1 |
- |
0.573 |
100 |
0.32 |
2 (Comparison) |
(4)-1 |
7.2×10⁻⁵ |
0.565 |
214 |
0.68 |
3 (Comparison) |
(4)-1 |
2.1×10⁻⁴ |
0.462 |
151 |
0.72 |
4 (Invention) |
(5)-1 |
7.2×10⁻⁵ |
0.608 |
265 |
0.80 |
5 (Invention) |
(5)-2 |
2.1×10⁻⁴ |
0.532 |
201 |
0.85 |
[0094] Though compound B had a supersensitizing effect on the sensitizing dye I-18 in all
the experiments, the spectrally sensitizing effect was enhanced to a greater extent
by adding both compounds before the completion of the grain formation of silver halide
in accordance with the present invention.
[0095] In another experiment where the emulsion was prepared in the same manner as in Method-4,
except the sensitizing dye I-18 was not added during the grain formation of silver
halide, but it was added in the same amount during a period after the gold-sulfur
sensitization and before the coating, was employed, Φr was 0.36 and the relative sensitivity
to light of 545 nm was 112.
[0096] According to the method of the present invention, not only can the relative quantum
yield of spectral sensitization Φr be heightened, but also high spectral sensitivities
can be achieved over the main portion of the spectral sensitization range, which is
important in practical use. The present method is unexpectedly superior to a spectral
sensitization method in which a sensitizing dye is added to an emulsion during a period
after the grain formation and before the coating, or a spectral sensitization method
in which a sensitizing dye forming the J-aggregate is added during the grain formation,
while another supersensitizing sensitizing dye is added after the grain formation
and before the coating.
[0097] While the invention has been described in detail and with reference to specific embodiments
thereof, it will be apparent to one skilled in the art that various changes and modifications
can be made therein without departing from the spirit and scope thereof.
1. A method for producing a spectrally sensitized silver halide photographic emulsion
comprising the step of forming silver halide grains in the presence of at least one
J-aggregated cyanine dye and at least one supersensitizer
2. The method as claimed in claim 1, wherein said J-aggregated cyanine is represented
by formula (I):

wherein Z¹ represents oxygen, sulfur, selenium, or -CH=CH-; Z² represents sulfur,
selenium, or -CH=CH-; R₁ and R₂, which may be the same or different, each represents
an unsubstituted or substituted alkyl group; V¹ represents hydrogen or an atomic group
necessary for forming a condensed benzene ring with V²; V⁴ represents hydrogen or
an atomic group necessary for forming a condensed benzene ring with V⁵; V², V³, V⁵
and V⁶, which may be the same or different, each represents a straight-chain or branched
chain alkyl group containing at most 5 carbon atoms, an alkoxy group containing at
most 4 carbon atoms, a hydroxyl group, an acylamino group containing at most 4 carbon
atoms, an unsubstituted or substituted phenyl group containing at most 8 carbon atoms,
a halogen atom, an alkoxycarbonyl group containing at most 5 carbon atoms, a carboxyl
group or hydrogen, provided that V³ may be linked with V² to form a condensed benzene
ring and V⁶ may be linked with V⁵ to form a condensed benzene ring; m₁ is 0 or 1;
and X₁ represents a counter ion necessary for charge balance.
3. The method as claimed in claim 1, wherein said J-aggregated cyanine dye is represented
by formula (II):

wherein Z²¹ represents an atomic group necessary for forming an unsubstituted nucleus
selected from 4-thiazoline, thiazolidine, benzo-4-thiazoline, naphtho[1,2-d]-4-thiazoline,
naphtho[2,3-d]-4-thiazoline, selenazolidine, 4-selenazoline, benzo-4-selenazoline,
naphtho[1,2,-d]-4-selenazoline, naphtho[2,3-d]-4-selenazoline, benzo-4-oxazoline,
naphtho[1,2-d]-4-oxazoline, naphtho[2,3-d]-4- oxazoline and benzo-4-imidazoline nucleus;
R₂₁, R₂₂ and R₂₃, which may be the same or different, each represents an unsubstituted
or substituted alkyl group; R₂₄ represents hydrogen or atomic group necessary for
forming a 5-membered or 6-membered ring in combination with R₂₃; V²¹ represents an
electron attracting group; V²² represents an electron attracting group, hydrogen or
an atomic group necessary for forming a condensed benzene ring in combination with
V²¹; m₂₁ is 0 or 1: X₂₁ is a counter ion necessary for charge balance.
4. The method as claimed in claim 1, wherein said J-aggregated cyanine dye is represented
by formula (III):

wherein Z³¹ represents oxygen, sulfur or selenium ; Z³² represents an atomic group
necessary for forming a nucleus selected from thiazole, benzothiazole, naphtho[1,2-d]thiazole,
8,9-dihydronaphtho[1,2-d]thiazole, naphtho[2,3-d]-thiazole, selenazole, benzoselenazole,
naphtho[1,2-d]-selenazole, benzoxazole, naphtho[1,2-d]oxazole, or naphtho[2,3-d]oxazole;
R₃₁ and R₃₂, which may be the same or different, each represents ethyl, propyl, butyl,
phenyl or phenetyl;' R₃₃ represents ethyl, propyl, butyl, phenyl, or phenetyl; V³¹
represents a hydrogen atom or an atomic group necessary for forming a condensed benzene
ring with V³²; V ³² and V³³, which may be the same of different, each represents a
straight-chain or branched-chain alkyl group containing at most 5 carbon atoms, an
alkoxy group containing at most 4 carbon atoms, a hydroxyl group, an acylamino group
containing at most 4 carbon atoms, an unsubstituted or substituted phenyl group containing
at most 8 carbon atoms, a halogen atom, an alkoxycarbonyl group containing at most
5 carbon atoms, a carboxyl group or hydrogen; provided that V³² and V³³ may be linked
to form a 5-membered or 6 membered ring; R₃₄ represents a hydrogen atom, or an atomic
group necessary for completing a 5- or 6-membered ring in combination with R₃₂; m₃₁
is 0 or 1 and X₃₁ represents a counter ion necessary for charge balance.
5. The method as claimed in claim 3, wherein said electron attracting group represented
by V²¹ and V²² is selected from fluorine, chlorine, a cyano group, an alkoxycarbonyl
group containing at most 4 carbon atoms and an alkylsulfonyl group containing at
most 4 carbon atoms.
6. The method as claimed in claim 4, wherein R₃₃ represents ethyl.
7. The method as claimed in claim 2, wherein said substituted alkyl group represented
by R₁, and R₂ is substituted with a substituent selected from a lower alkyl group,
a halogen atom, a carbamoyl group, a carboxyl group, an alkoxycarbonyl group, an acylamino
group, a hydroxyl group, a sulfo group and a substituted phenyl group.
8. The method as claimed in claim 3, wherein said substituted alkyl group represented
by R₂₁, R₂₂ and R₂₃ is substituted with a substituent selected from a lower alkyl
group, a halogen atom, a carbamoyl group, a carboxyl group, an alkoxycarbonyl group,
an acylamino group, a hydroxyl group, a sulfo group and a substituted phenyl group.
9. The method as claimed in claim 4, wherein said substituted alkyl group represented
by R₃₁, and R₃₂ is substituted with a substituent selected from a lower alkyl group,
a halogen atom, a carbamoyl group, a carboxyl group, an alkoxycarbonyl group, an acylamino
group, a hydroxyl group, a sulfo group and a substituted phenyl group.
10. The method as claimed in claim 1, wherein said silver halide grains comprise from
about 1x10⁻⁶ to 5x10⁻³ mol of each of said sensitizing dye and said supersensitizer
per mol of said silver halide.
11. The method as claimed in claim 1, wherein said silver halide grains comprise from
about 1x10⁻⁵ to 2.5x10⁻³ mol of each of said sensitizing dye and said supersensitizer
per mol of said silver halide.
12. The method as claimed in claim 1, wherein said J-aggregated cyanine dye and said
supersensitizer are present at the beginning of grain formation.
13. The method as claimed in claim 1, wherein said J-aggregated cyanine dye and said
supersensitizer are each added to an aqueous solution containing at least one water-soluble
silver salt and at least one water-soluble halide salt during grain formation.
14. The method as claimed in claim 13, wherein at least one-half of said J-aggregated
cyanine dye and at least one-half of said supersensitizer are simultaneously added
during grain formation.
15. The method as claimed in claim 13, wherein at least two-thirds of said J-aggregated
cyanine dye and at least two-thirds of said supersensitizer are simultaneously added
during grain formation.
16. The method as claimed in claim 15, wherein the total amounts of said J-aggregated
cyanine dye and said supersensitizer are simultaneously added during grain formation.