FIELD OF THE INVENTION
[0001] The present invention relates to a process for the preparation of a silver halide
photographic element. In particular, the present invention relates to the use of an
aryl derivative in a process for preparing a silver halide emulsion to improve the
speed to Dmin ratio of the resulting photographic material.
BACKGROUND OF THE INVENTION
[0002] Silver halide emulsions are usually prepared by precipitating silver halide (silver
bromide, silver iodide, silver chloride or mixture thereof) in the presence of a hydrophilic
colloid (normally gelatin).
[0003] Afterwards, the silver halide emulsions are subjected to a sensitization process
for increasing their sensitivity to light. There are two primary types of sensitization
processes: spectral sensitization and chemical sensitization.
[0004] Spectral sensitization comprises the addition of spectral sensitizing dyes which
are adsorbed on the silver halide grain surface to make the emulsion sensitive to
the imaging radiation or emitted radiation (i.e., visible or infrared radiation).
[0005] Chemical sensitization involves the addition of various chemical substances to obtain
a prescribed value of sensitivity and contrast. Typical methods for chemical sensitizing
a silver halide photographic emulsion include sulfur sensitization, noble metal sensitization,
and reduction sensitization. It is also common in the art to have combination methods,
such as sulfur-noble metal sensitization, reduction-noble metal sensitization, and
the like.
[0006] A number of patents and patent applications, as well as literature references disclose
specific methods to improve chemical sensitization. See i.e.,
Research Disclosure, September 1994, Item 36544, Paragraph IV, pp. 510-511, which gives a wide array
of references for each of the above-mentioned methods.
[0007] Additionally, a wide range of metals have been used as doping agents during emulsion
making of silver halide emulsions to modify grain structure and properties. A general
review of the use of these doping agents can be found in
Research Disclosure, September 1994, Item 36544, Paragraph II.D.3, pp. 504-505.
[0008] Some recent patents and patent applications teach the use of some metals during chemical
sensitization alone or in combination with the above mentioned conventional method.
[0009] For example, EP 467,106 discloses a silver halide photographic element chemically
sensitized by gold and sulfur compounds and further by a mercury compound.
[0010] JP 04-009,034 discloses silver halide photographic element chemically sensitized
by gold in the presence of an iridium or a platinum complex salt.
[0011] JP 04-009,837 discloses silver halide photographic element chemically sensitized
by reduction sensitization and further by a palladium compound.
[0012] EP 476,345 discloses silver halide photographic element chemically sensitized in
the presence of a noble metal, a sulfur sensitizer, a selenium compound and a silver
halide solvent.
[0013] JP 04-051,232 discloses silver halide photographic element chemically sensitized
in the presence of a gold compound, an iridium compound, and a Group VIII metal compound.
[0014] JP 05-045,768 discloses silver halide photographic element chemically sensitized
in the presence of a tellurium organic compound and a gold compound. JP 05-053,234
further discloses the possibility of an additional reduction sensitization.
[0015] JP 05-045,769 discloses silver halide photographic element chemically sensitized
in the presence of tellurium, sulfur and noble metal organic compounds.
[0016] JP 04-335640, 05-027,360, 05-027,388, EP 563,708 and EP 638,840 disclose silver halide
photographic element chemically sensitized in the presence of selenium, gold and sulfur
sensitizer.
[0017] EP 568,092 discloses silver halide photographic element chemically sensitized in
the presence of a heavy metal and a thiourea compound.
[0018] JP 06-051,418 discloses silver halide photographic element chemically sensitized
in the presence of a mercuric chloride organic derivative, sodium thiocyanate, sodium
thiosulfate, and potassium chloroaurate.
[0019] However, all sensitization methods that provide substantial increase of sensitivity
are disadvantageous in that although high sensitivity is obtained, fog is also increased,
particularly with tabular emulsions.
[0020] Additionally, photographic properties are generally altered when the material is
subjected to different stressed conditions like rapid drying during manufacture, elevated
temperature during storage, high temperature or roller pressure during processing
in automatic machines.
[0021] After the sensitization process, the silver halide emulsion is coated on a support
together with coating additives. A wide description of useful coating aids can be
found in
Research Disclosure No. 38597, September 1996, "Photographic Silver Halide Emulsions, Preparations, Addenda,
Systems and Processing", Item IX.
[0022] US 5,028,520 discloses the use of hydroquinone sulfonic acid potassium salt on tabular
silver halide emulsion in an amount of from 0.03 to 0.5 moles per mole of silver to
decrease the surface glossiness. The reference also states that no effect is obtained
with an amount lower than 0.03 mole per mole of silver.
[0023] JP 54-040729, JP 56-001936 and JP 62-021143 disclose the use of polyhydroxybenzene
derivatives on cubic silver halide emulsions to decrease pressure sensitivity in graphic
art films.
[0024] EP 452772, EP 476521, EP 482599 and EP 488029 disclose the use of polyhydroxybenzene
derivatives with functional groups that allow better silver halide grain adsorption
to decrease pressure sensitivity of final film.
[0025] EP 339870 discloses a silver halide photographic emulsion having in reactive association
a sensitizing amount of polyalkylene glycol compound and a fog reducing amount of
an arylhydroxy compound.
[0026] The object of the invention is to prevent the above mentioned drawback and provide
a silver halide emulsion with higher speed to Dmin ratio and enhanced film storability.
SUMMARY OF THE INVENTION
DETAILED DESCRIPTION OF THE INVENTION
[0029] In the manufacturing of silver halide elements, the following process steps are typically
employed: an emulsion-making step, a chemical and optical sensitization step, and
a coating step.
[0030] The silver halide emulsion-making step generally includes (i) a nucleation step,
where silver halide grain seeds are formed, (ii) one or more growing steps, where
the grain seeds achieve their final dimension, and (iii) a washing step, where all
soluble salts are removed from the final emulsion. In addition, a ripening step is
performed between the nucleation and growing step and/or between the growing and the
washing steps.
[0031] Silver halide emulsions can be prepared using a single-jet method, a double-jet method,
or a combination of these methods and can be ripened using, for example, an ammonia
method, a neutralization method, or an acid method. Various parameters may be adjusted
to control grain growth such as, pH, pAg, temperature, shape and size of reaction
vessel, and the reaction method (e.g., accelerated or constant flow rate precipitation,
interrupted precipitation, ultrafiltration during precipitation, reverse mixing processes
and combinations thereof). A silver halide solvent, such as ammonia, thioethers, thioureas,
etc., may be used, if desired, for controlling grain size, grain structure, particle
size distribution of the grains, and the grain-growth rate. The following references
provide useful guidance: Trivelli and Smith,
The Photographic Journal, Vol. LXXIX, May 1939, pp. 330-338; T.H. James,
The Theory of The Photographic Process, 4
th Edition, Chapter 3;
Chimie et Physique Photographique, P. Glafkides, Paul Montel (1967);
Photographic Emulsion Chemistry, G. F. Duffin, The Focal Press (1966);
Making and Coating Photographic Emulsions, V. L. Zelikman, The Focal Press (1966); U.S. Pat. Nos. 2,222,264; 2,592,250; 3,650,757;
3,917,485; 3,790,387; 3,716,276; and 3,979,213; and
Research Disclosure, Sept. 1994, Item 36544 "Photographic Silver Halide Emulsions, Preparations, Addenda,
Systems and Processing."
[0032] In the preparation of silver halide emulsions, commonly used halogen compositions
of the silver halide grains can be used. Suitable silver halides include silver chloride,
silver bromide, silver iodide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide
and the like. However, silver bromide and silver bromoiodide are preferred silver
halide compositions with silver bromoiodide compositions containing from 0 to 10 mol%
silver iodide, preferably, from 0.2 to 5 mol% silver iodide, and more preferably,
from 0.5 to 1.5mol% silver iodide. The halogen composition of individual grains may
be homogeneous or heterogeneous.
[0033] As a binder for silver halide emulsions, gelatin is preferred, but other hydrophilic
colloids can be used, alone or in combination, such as, dextran, cellulose derivatives
(e.g., hydroxyethylcellulose, carboxymethyl cellulose), collagen derivatives, colloidal
albumin or casein, polysaccharides, synthetic hydrophilic polymers (e.g., polyvinylpyrrolidone,
polyacrylamide, polyvinylalcohol, polyvinylpyrazole) and the like. Gelatin derivatives,
such as, highly deionized gelatin, acetylated gelatin and phthalated gelatin can also
be used. It is also common to employ the hydrophilic colloids in combination with
synthetic polymeric binders and peptizers such as acrylamide and methacrylamide polymers,
polymers of alkyl and sulfoalkyl acrylates and methacrylates, polyvinyl alcohol and
its derivatives, polyvinyl lactams, polyamides, polyamines, polyvinyl acetates, and
the like.
[0034] The grains of these silver halide emulsions may be coarse or fine, and the grain
size distribution may be narrow or broad. In addition, the silver halide grains may
be regular grains having a regular crystal structure such as cube, octahedron, and
tetradecahedron, or the spherical or irregular crystal structure, or those having
crystal defects such as twin planes, or those having a tabular form, or combinations
thereof. Furthermore, the grain structure of the silver halides may be uniform from
the interior to exterior thereof, or be multilayer. In a simple embodiment, the grains
may comprise a core and a shell, which may have different halide compositions and/or
may have undergone different modifications such as the addition of doping agents.
Besides having a differently composed core and shell, the silver halide grains may
also comprise different phases in-between. Additionally, the silver halides may be
of the type that allows a latent image to be formed mainly on the surface thereof
or the type that allows it to be formed inside the grains thereof.
[0035] Preferably, tabular silver halide emulsions are used having an aspect ratio of at
least 2:1, preferably, 2:1 to 20:1, more preferably, 2:1 to 14:1, and most preferably,
2:1 to 8:1. As used herein, aspect ratio refers to the average diameter:thickness
ratio of silver halide grains. Average diameters of the tabular silver halide grains
range from about 0.3 to about 5 µm, preferably, from about 0.5 to about 3 µm, more
preferably, from about 0.8 to about 1.5 µm. Suitable tabular silver halide grains
have a thickness of less than 0.4 µm, preferably, less than 0.3 µm, and more preferably,
within 0.1 to 0.3 µm. The projected area of the tabular silver halide grains should
account for at least 50%, preferably, at least 80%, and more preferably, at least
90% of the projected area of all the silver halide grains of the emulsion.
[0036] The tabular silver halide grain dimensions and characteristics described above can
be readily ascertained by procedures well known to those skilled in the art. As used
herein, the term "diameter" is defined as the diameter of a circle having an area
equal to the projected area of the grain. The term "thickness" refers to the distance
between two substantially parallel main planes constituting the tabular silver halide
grains. From the measure of diameter and thickness of each grain the diameter:thickness
ratio of each grain can be calculated, and the diameter:thickness ratios of all tabular
grains can be averaged to obtain their average diameter:thickness ratio. By this definition,
the average diameter:thickness ratio is the average of individual tabular grain diameter:thickness
ratios. In practice, it is simpler to obtain an average diameter and an average thickness
of the tabular grains and to calculate the average diameter:thickness ratio as the
ratio of these two averages. Whatever the method used, the average diameter:thickness
ratios obtained do not greatly differ.
[0037] Silver halide emulsions containing tabular silver halide grains can be prepared by
various processes known to those of ordinary skill in the art for the preparation
of photographic elements.
[0038] Preparation of silver halide emulsions containing tabular silver halide grains is
described in, for example, de Cugnac and Chateau, "Evolution of the Morphology of
Silver Bromide Crystals During Physical Ripening",
Science and Industries Photographiques, Vol. 33, No.2 (1962), pp.121-125; Gutoff, "Nucleation and Growth Rates During the
Precipitation of Silver Halide Photographic Emulsions",
Photographic Science and Engineering, Vol. 14, No. 4 (1970), pp. 248-257; Berry et al., "Effects of Environment on the
Growth of Silver Bromide Microcrystals", Vol.5, No.6 (1961), pp. 332-336;
Research Disclosure, Sept. 1994, Item 36544 "Photographic Silver Halide Emulsions, Preparations, Addenda,
Systems and Processing"; U.S. Pat. Nos. 4,063,951; 4,067,739; 4,184,878; 4,434,226;
4,414,310; 4,386,156; and 4,414,306; and EP Pat. Appln. No. 263,508.
[0039] At the end of the silver halide grain formation, water soluble salts are removed
from the emulsion by procedures known in the art. Suitable washing processes are those
wherein the dispersing medium and soluble salts dissolved therein can be removed from
the silver halide emulsion on a continuous basis, such as, for example, a combination
of dialysis or electrodialysis for the removal of soluble salts or a combination of
osmosis or reverse osmosis for the removal of the dispersing medium.
[0040] Among the known techniques for removing the dispersing medium and soluble salts while
retaining silver halide grains in the remaining dispersion, ultrafiltration is a particularly
advantageous washing processes for the practice of this process. Typically, an ultrafiltration
unit comprising membranes of inert, non-ionic polymers is used as a washing process.
Since silver halide grains are large in comparison with the dispersing medium and
the soluble salts or ions, silver halide grains are retained by the membranes while
the dispersing medium and the soluble salts dissolved therein are removed.
[0041] Prior to use, silver halide grain emulsions are generally fully dispersed and bulked
up with gelatin or other dispersion of peptizer and subjected to any of the known
methods for achieving optimum sensitivity. A wide description of methods and compounds
useful in chemical and optical sensitization can be found in
Research Disclosure No. 38597, September 1996, "Photographic Silver Halide Emulsions, Preparations, Addenda,
Systems and Processing", Items IV and 5.
[0042] Chemical sensitization is performed by adding chemical sensitizers and other additional
compounds to the silver halide emulsion, followed by the so-called chemical ripening
at high temperature for a predetermined period of time. Chemical sensitization can
be performed by various chemical sensitizers such as gold, sulfur, reducing agents,
platinum, selenium, sulfur plus gold, and the like. Tabular silver halide grains,
after grain formation and desalting, are preferably chemically sensitized by at least
one gold sensitizer and at least one sulfur sensitizer. During chemical sensitization
other compounds can be added to improve the photographic performances of the resulting
silver halide emulsion, such as, for example, antifoggants, stabilizers, optical sensitizers,
supersensitizers, and the like.
[0043] Gold sensitization is performed by adding a gold sensitizer to the emulsion and stirring
the emulsion at high temperature of preferably 40°C or more for a predetermined period
of time. As a gold sensitizer, any gold compound which has an oxidation number of
+1 or +3 and is normally used as gold sensitizer can be used. Preferred examples of
gold sensitizers are chloroauric acid, the salts thereof and gold complexes, such
as those described in US 2,399,083. Specific examples of gold sensitizers include
chloroauric acid, potassium chloroaurate, auric trichloride, sodium aurithiosulfate,
potassium aurithiocyanate, potassium iodoaurate, tetracyanoauric acid, 2-aurosulfobenzothiazole
methochloride and ammonium aurothiocyanate.
[0044] Sulfur sensitization is performed by adding a sulfur sensitizer to the silver halide
emulsion and stirring the emulsion at a high temperature of 40°C or more for a predetermined
period of time. Useful examples of sulfur sensitizer include thiosulfonates, thiocyanates,
sulfinates, thioethers, and elemental sulfur.
[0045] The amounts of the gold sensitizer and the sulfur sensitizer change in accordance
with the various conditions, such as activity of the gold and sulfur sensitizer, type
and size of silver halide grains, temperature, pH and time of chemical ripening. These
amounts, however, are preferably from 1 to 20 mg of gold sensitizer per mole of silver,
and from 1 to 100 mg of sulfur sensitizer per mole of silver. The temperature of chemical
ripening is preferably 45°C or more, and more preferably 50°C to 80°C. The pAg and
pH may take arbitrary values.
[0046] During chemical sensitization, times and order of addition of the gold sensitizer
and sulfur sensitizer are not particularly limiting. For example, gold and sulfur
sensitizers can be added at the initial stage of chemical sensitization or at a later
stage either simultaneously or at different times. Usually, gold and sulfur sensitizers
are added to the silver halide emulsion by their solutions in water, in a water-miscible
organic solvent, such as methanol, ethanol and acetone, or as a mixture thereof.
[0047] A stabilizer is preferably added at any time before the addition of the sulfur sensitizer.
Even if the action of the stabilizer is not yet fully understood, it is believed that
it acts as a digest stabilizer and a site director for the sulfur sensitizer. Preferably,
the stabilizer is added before the addition of sulfur chemical sensitizer in an amount
of from 1 to 500 milligrams per mole of silver, preferably, from 10 to 300 milligrams
per mole of silver.
[0048] Specific examples of useful stabilizers include thiazole derivatives; benzothiazole
derivatives; mercapto-substituted heterocyclic compounds, such as, for example, mercaptotetrazoles,
mercaptotriazoles, mercaptodiazoles, mercaptopyrimidines, mercaptoazoles; azaindenes,
such as triazaindenes and tetrazaindenes; triazoles; tetrazoles; and sulfonic and
sulfinic benzene derivatives. Azaindenes are preferably used, more preferably, tetraazaindenes.
[0049] Moreover, the silver halide grain emulsion may be optically sensitized to a desired
region of the visible spectrum. The method for spectral sensitization is not particularly
limited. For example, optical sensitization may be possible by using an optical sensitizer,
including a cyanine dye, a merocyanine dye, complex cyanine and merocyanine dyes,
oxonol dyes, hemioxonol dyes, styryl dyes and streptocyanine dyes, either alone or
in combination. Useful optical sensitizers include cyanines derived from quinoline,
pyridine, isoquinoline, benzindole, oxazole, thiazole, selenazole, imidazole. Particularly
useful optical sensitizers are the dyes of the benzoxazole-, benzimidazole- and benzothiazole-carbocyanine
type. Usually, the addition of the spectral sensitizer is performed after the completion
of chemical sensitization. Alternatively, spectral sensitization can be performed
concurrently with chemical sensitization, can entirely precede chemical sensitization,
and can even commence prior to the completion of silver halide precipitation. When
the spectral sensitization is performed before the chemical sensitization, it is believed
that the preferential absorption of spectral sensitizing dyes on the crystallographic
faces of the tabular grains allows chemical sensitization to occur selectively at
unlike crystallographic surfaces of the tabular grains. Preferably , the spectral
sensitizers produce J aggregates, if adsorbed on the surface of the silver halide
grains, and a sharp absorption band (J-band) with a bathochromic shift with respect
to the absorption maximum of the free dye in aqueous solution.
[0050] It is known in the art of radiographic photographic elements that the intensity of
the sharp absorption band (J-band) shown by the spectral sensitizing dye absorbed
on the surface of the light-sensitive silver halide grains will vary with the quantity
of the specific dye chosen as well as the size and chemical composition of the grains.
The maximum intensity of J-band has been obtained with silver halide grains having
the above described sizes and the chemical compositions absorbed with J-band spectral
sensitizing dyes in a concentration of from 25 to 100 percent or more of monolayer
coverage of the total available surface area of the silver halide grains. Optimum
dye concentration levels are chosen in the range of 0.5 to 20 millimoles per mole
of silver halide, preferably, in the range of 2 to 10 millimoles.
[0051] Spectral sensitizing dyes producing J aggregates are well known in the art, as illustrated
by F. M. Hamer,
Cyanine Dyes and Related Compounds, John Wiley and Sons, 1964, Chapter XVII and by T. H. James,
The Theory of the Photographic Process, 4th Edition, MacMillan, 1977, Chapter 8.
[0052] In a preferred form, J-band exhibiting dyes are cyanine dyes. Such dyes consist of
two basic heterocyclic nuclei joined by a linkage of methine groups. The heterocyclic
nuclei preferably include fused benzene rings to enhance J aggregation. The heterocyclic
nuclei are preferably quinolinium, benzoxazolium, benzothiazolium, benzoselenazolium,
benzimidazolium, naphthoxazolium, naphthothiazolium and naphthoselenazolium quaternary
salts.
[0053] The cyanine dyes, which are joined by a methine linkage, include two basic heterocyclic
nuclei, such as pyrrolidine, oxazoline, thiazoline, pyrrole, oxazole, thiazole, selenazole,
tetrazole and pyridine and nuclei obtained by fusing an alicyclic hydrocarbon ring
or an aromatic hydrocarbon ring to each of the above nuclei, such as indolenine, benzindolenine,
indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole,
benzimidazole and quinoline. These nuclei can have substituents groups.
[0054] The merocyanine dyes, which are joined by a methine linkage, include a basic heterocyclic
nucleus of the type described above and an acid nucleus, such as a 5- or 6-membered
heterocyclic nucleus derived from barbituric acid, 2-thiobarbituric acid, rhodanine,
hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-isoxazolin-5-one,
indan-1,3-dione, cyclohexane-1-3-dione, and isoquinolin-4-one.
[0055] The preferred dyes are cyanine dyes, such as those represented by the following formula:
wherein n, m and d each independently represents 0 or 1, L represents a methine linkage,
e.g., =CH-, ≡C(C
2H
5), etc., R
1 and R
2 each represents a substituted or unsubstituted alkyl group, preferably, a lower alkyl
group of from 1 to 4 carbon atoms, e.g., methyl, ethyl, propyl, butyl, cyclohexyl
and dodecyl, a hydroxyalkyl group, e.g., β-hydroxyethyl and Ω-hydroxybutyl, an alkoxyalkyl
group, e.g., β-methoxyethyl and Ω-butoxyethyl, a carboxyalkyl group, e.g., β-carboxyethyl
and Ω-carboxybutyl, a sulfoalkyl group, e.g., β-sulfoethyl and Ω-sulfobutyl, a sulfatoalkyl
group, e.g., β-sulfatoethyl and Ω-sulfatobutyl, an acyloxyalkyl group, e.g., β-acetoxyethyl,
γ-acetoxypropyl and Ω-butyryloxybutyl, an alkoxycarbonylalkyl group, e.g., β-methoxycarbonylethyl
and Ω-ethoxycarbonylbutyl, benzyl, phenethyl, or an aryl group of up to 30 carbon
atoms, e.g., phenyl, tolyl, xylyl, chlorophenyl and naphthyl, X represents an acid
anion, e.g., chloride, bromide, iodide, thiocyanate, sulfate, perchlorate, p-toluenesulfonate
and methylsulfate; the methine linkage forming an intramolecular salt when p is 0;
Z
1 and Z
2, the same or different, each represents the non-metallic atoms necessary to complete
the same simple or condensed 5- or 6-membered heterocyclic nucleus, such as a benzothiazole
nucleus (e.g., benzothiazole, 3-, 5-, 6- or 7-chloro-benzothiazole, 4-, 5- or 6-methylbenzothiazole,
5- or 6-bromobenzothiazole, 4- or 5-phenyl-benzothiazole, 4-, 5- or 6-methoxybenzothiazole,
5,6-dimethyl-benzothiazole and 5- or 6-hydroxybenzothiazole), a naphthothiazole nucleus
(e.g., α-naphthothiazole, β-naphthothiazole, 5-methoxy-β-naphthothiazole, 5-ethoxy-α-naphthothiazole
and 8-methoxy-α-naphthothiazole), a benzoselenazole nucleus (e.g., benzoselenazole,
5-chloro-benzoselenazole and tetrahydrobenzoselenazole), a naphthoselenazole nucleus
(e.g., α-naphtho-selenazole and β-naphthoselenazole), a benzoxazole nucleus (e.g.,
benzoxazole, 5- or 6-hydroxy-benzoxazole, 5-chloro-benzoxazole, 5-or 6-methoxy-benzoxazole,
5-phenyl-benzoxazole and 5,6-dimethyl-benzoxazole), a naphthoxazole nucleus (e.g.,
α-naphthoxazole and β-naphthoxazole), a 2-quinoline nucleus (e.g., 2-quinoline, 6-,
7, or 8-methyl-2-quinoline, 4-, 6- or 8-chloro-2-quinoline, 5-, 6- or 7-ethoxy-2-quinoline
and 6- or 7-hydroxy-2-quinoline), a 4-quinoline nucleus (e.g., 4-quinoline, 7- or
8-methyl-4-quinoline and 6-methoxy-4-quinoline), a benzimidazole nucleus (e.g., benzimidazole,
5-chloro-benzimidazole and 5,6-dichloro-benzimidazole), a thiazole nucleus (e.g.,
4- or 5-methyl-thiazole, 5-phenyl-thiazole and 4,5-di-methyl-thiazole), an oxazole
nucleus (e.g., 4- or 5-methyl-oxazole, 4-phenyl-oxazole, 4-ethyl-oxazole and 4,5-dimethyl-oxazole),
and a selenazole nucleus (e.g., 4-methyl-selenazole and 4-phenyl-selenazole. More
preferred dyes within the above class are those having an internal salt group and/or
derived from benzoxazole and benzimidazole nuclei as indicated before. Typical methine
spectral sensitizing dyes include those listed below.
[0056] The methine spectral sensitizing dyes are generally known in the art. Particular
reference can be made to U.S. Pat. Nos. 2,503,776; 2,912,329; 3,148,187; 3,397,060;
3,573,916; and 3,822,136 and FR Pat. No. 1,118,778. Also their use in photographic
emulsions is very well known wherein they are used in optimum concentrations corresponding
to desired values of sensitivity to fog ratios. Optimum or near optimum concentrations
of spectral sensitizing dyes generally go from 10 to 500 mg per mole of silver, preferably,
from 50 to 200, and more preferably, from 50 to 100.
[0057] Spectral sensitizing dyes can be used in combinations which result in supersensitization,
i.e., spectral sensitization which is greater in a spectral region than that from
any concentration of one dye alone or which would result from an additive effect of
the dyes. Supersensitization can be obtained with selected combinations of spectral
sensitizing dyes and other addenda, such as stabilizers and antifoggants, development
accelerators and inhibitors, optical brighteners, surfactants and antistatic agents,
as described by Gilman,
Photographic Science and Engineering, 18, pp. 418-430, 1974 and in U.S. Pat. Nos. 2,933,390; 3,635,721; 3,743,510; 3,615,613;
3,615,641; 3,617,295; and 3,635,721.
[0058] The resulting silver halide emulsion is then coated on a proper support to prepare
a silver halide photographic material. According to the method of the present invention,
an aryl compound having at least two substituents each of which is represented by
an hydroxyl group or a sulfonic group is added to the silver halide emulsion in an
amount of less than 0.03 moles per mole of silver before the coating of the silver
halide emulsion.
[0060] The amount of the above described aryl compound is preferably in the range of from
0.0001 to less than 0.03 moles per mole of silver, more preferably from 0.001 to less
than 0.03 moles per mole of silver, and most preferably from 0.005 to less than 0.03
moles per mole of silver.
[0061] Other additives can be added to the silver halide. emulsion before or during coating,
such as, for example, stabilizers or antifoggants such as azaindenes, triazoles, tetrazoles,
imidazolium salts, polyhydroxy compounds and others; developing promoters such as
benzyl alcohol, polyoxyethylene type compounds, etc.; image stabilizers such as compounds
of the chromane, cumaran, bisphenol type,. etc.; and lubricants such as wax, higher
fatty acids glycerides, higher alcohol esters of higher fatty acids, etc. may be added.
Also, coating aids, modifiers of the permeability in the processing liquids, defoaming
agents, antistatic agents and matting agents may be used. Other useful additives are
disclosed in
Research Disclosure, Item 17643, December 1978;
Research Disclosure, Item 18431, August 1979;
Research Disclosure, Item 308119, Section IV, December 1989; and
Research Disclosure Item 36544, September 1994.
[0062] Suitable support materials include glass, paper, polyethylene-coated paper, metals,
polymeric film such as cellulose nitrate, cellulose acetate, polystyrene, polyethylene
terephthalate, polyethylene, polypropylene and the like.
[0063] Preferred light-sensitive silver halide photographic elements are radiographic light-sensitive
elements used in X-ray imaging comprising a silver halide emulsion layer(s) coated
on both surfaces of a support, preferably, a polyethylene terephthalate support. Preferably,
the silver halide emulsions are coated on the support at a silver coverage in the
range of 1.5 to 3 g/m
2 per side. Usually, the radiographic light-sensitive elements are associated with
intensifying screens so as to be exposed to radiation emitted by the screens. The
screens are made of relatively thick phosphor layers which transform the X-rays into
more imaging-effective radiation such as light (e.g., visible light). The screens
absorb a larger portion of X-rays than the light-sensitive elements do and are used
to reduce the X-ray dose necessary to obtain a useful image. Intensifying screens
absorbing more than 25% of the total X-radiation are preferably used. Depending on
their chemical composition, the phosphors can emit radiation in the ultraviolet, blue,
green or red region of the visible spectrum and the silver halide emulsions are sensitized
to the wavelength region of the radiation emitted by the screens. Sensitization is
performed by using spectral sensitizing dyes absorbed on the surface of the silver
halide grains as described above.
[0064] Other layers and additives, such as subbing layers, surfactants, filter dyes, intermediate
layers, protective layers, anti-halation layers, barrier layers, dye underlayers,
development inhibiting compounds, speed-increasing agents, stabilizers, plasticizers,
chemical sensitizers, UV absorbers and the like can be present in the radiographic
element. Dye underlayers are particularly useful to reduce the cross-over of the double
coated silver halide radiographic element. Reference to well-known dye underlayer
can be found in U.S. Pat. Nos. 4,900,652; 4,855,221; 4,857,446; and 4,803,150. Preferably,
a dye underlayer is coated on at least one side of the support, more preferably, on
both sides of the support, before the coating of at least two silver halide emulsion.
[0065] The silver halide radiographic elements are preferably fore-hardened. Typical examples
of organic or inorganic hardeners include chrome salts (e.g., chrome alum, chromium
acetate), aldehydes (e.g., formaldehyde and glutaraldehyde), isocyanate compounds
(hexamethylene diisocyanate), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine),
epoxy compounds (e.g., tetramethylene glycol diglycidylether), N-methylol derivatives
(e.g., dimethylolurea, methyloldimethyl hydantoin), aziridines, mucohalogeno acids
(e.g., mucochloric acid), active vinyl derivatives (e.g., vinylsulfonyl and hydroxy-substituted
vinylsulfonyl derivatives) and the like. Other references to well known hardeners
can be found in
Research Disclosure, December 1989, Vol. 308, Item 308119, Section X; and
Research Disclosure, September 1994, Vol. 365, Item 36544, Section II(b).
[0066] A detailed description of photographic elements and of various layers and additives
may be found in
Research Disclosure 17643 December 1978;
Research Disclosure 18431 August 1979;
Research Disclosure 18716 November 1979;
Research Disclosure 22534 January 1983;
Research Disclosure 308119 December 1989; and
Research Disclosure 36544, September, 1994.
[0067] The silver halide photographic element can be exposed and processed by any conventional
processing technique. Any known developing agent can be added into the developer,
such as, for example, dihydroxybenzenes (e.g., hydroquinone), pyrazolidones (1-phenyl-3-pyrazolidone
or 4,4-dimethyl-1-phenyl-3-pyrazolidone), and aminophenols (e.g., N-methyl-p-aminophenol),
alone or in combinations thereof. Preferably, the silver halide photographic elements
are developed in a developer comprising dihydroxybenzenes as the main developing agent,
and pyrazolidones and p-aminophenols as auxiliary developing agents.
[0068] Other well known additives can be present in the developer, such as, for example,
antifoggants (e.g., benzotriazoles, indazoles, tetrazoles), silver halide solvents
(e.g., thiosulfates, thiocyanates), sequestering agents (e.g., aminopolycarboxylic
acids, aminopolyphosphonic acids), sulfite antioxidants, buffers, restrainers, hardeners,
contrast promoting agents, surfactants, and the like. Inorganic alkaline agents, such
as KOH, NaOH, and LiOH are added to the developer composition to obtain the desired
pH which is usually higher than 10.
[0069] The silver halide photographic element can be processed with a fixer of a typical
composition for the application required. Suitable fixing agents include thiosulfates,
thiocyanates, sulfites, ammonium salts, and the like. The fixer composition can comprise
other well known additives, such as, for example, acid compounds (e.g., metabisulfates),
buffers (e.g., carbonic acid, acetic acid), hardeners (e.g., aluminum salts), tone
improving agents, and the like.
[0070] The exposed radiographic elements can be processed by any of the conventional processing
techniques. Such processing techniques are illustrated for example in
Research Disclosure, Item 17643 (cited above); and
Research Disclosure 36544, September 1994. Roller transport processing is particularly preferred, as
illustrated in U.S. Pat. Nos. 3,025,779; 3,515,556; 3,545,971; and 3,647,459 and UK
Patent 1,269,268. Hardening development can also be used, as illustrated in U.S. Patent
3,232,761.
[0071] With regard to the processes for the silver halide emulsion preparation and the use
of particular ingredients in the emulsion and in the light-sensitive element, reference
is made to
Research Disclosure, September 1996, Item 38957, and particularly to the following chapters:
I. Emulsion grains and their preparation.
II. Vehicles, vehicle extenders, vehicle-like addenda and vehicle related addenda.
III. Emulsion washing.
IV. Chemical sensitization
V. Spectral sensitization and desensitization
VI. UV dyes/optical brighteners/luminescent dyes
VII. Antifoggants and stabilizers
VIII. Absorbing and scattering materials.
IX. Coating physical property modifying addenda.
X. Dye image formers and modifiers.
XI. Layers and layer arrangements
XV. Supports
[0072] The present invention will be now described in greater detail with reference to the
following not limiting examples. All the amounts referred to in the following examples
are relative to one mole of silver in the resulting silver halide emulsion, unless
differently specified.
Example 1
Sample 1 (control )
[0073] A silver bromoiodide emulsion with an average grain equivalent diameter of 1.25 micron,
an average grain thickness of 0.18 micron, a COV of 37 % and 0.9 percent iodide in
mole respect to the total halide ions was prepared by double jet method.
[0074] The emulsion was chemically and spectrally sensitized using sulfur, gold, mercury
and palladium sensitizers plus a triethyl ammonium salt of 5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)
oxacarbocyanine as spectral sensitization dye. The digest was performed about 120
to 130 minutes at 60° and stabilized successively with 200 mg of potassium iodide
and 1366 mg of 5-methyl-7-hydroxy-2-3-4-triazoindolizine (4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene)
before chilling.
[0075] The sensitized silver halide emulsion was melted at 45°C and subjected to coating
finals in laboratory. As coating auxiliaries were added 1293 mg of calcium nitrate,
80 mg of azodicarboxylic dimorpholide, 18338 mg of polyethylacrylate (in dispersion
at 20% in water plus 367 mg of lauryl sulfate), 66738 mg of dextran (manufactured
by Pharmacosmos) as gel extender, 267 mg of Colanyl blue™ (manufactered by Hoechst
Chemical Co.) as chromatic corrector. The pH was corrected to 6.3 before adding 3774
mg of SSMA copolymer (Copolymer of Styrene sulfonic acid and maleic anhydride, manufactured
by Aquaness Corp., Texas, USA).
[0076] The resulting silver halide emulsion was immediately coated on the two faces of blue
7 mil polyester base code with a conventional antistatic top-coat containing hardening
agents. The coating speed was 8.3 meters per minute and the covering weight was around
2.25 g of silver per m
2 per side.
[0077] The fresh film samples were kept 3 days at 38°C before being subjected to X-ray exposure
using of 75 Kv and 300 mA for 0.06 second with two Trimax™ Medium screens (manufactured
by Imation Corp., MN, USA).
[0078] The exposed films were processed through a 90 seconds dry to dry medical X-ray automatic
processor type XP 515 (manufactured by Imation Corp., MN, USA) with standard chemistry
(XAD 3 developer and XAF 3 fixer, both manufactured by Imation Corp., MN, USA).
[0079] The sensitometric results are :
Dmin = 0.20
Speed = 100
Ratio = 5 (speed/Dmin x 100)
[0080] The speed value was measured 0.1 Log E above Dmin and the sensitivity of the control
was normalized to 100.
Example 8
Sample 31 (control)
[0081] The procedure of sample 1 was repeated. The sensitometric results are reported in
the following Table 8.
Samples 32 through 43
[0082] The procedure of sample 31 was repeated except that, during addition of coating finals,
0.022 moles of the compounds of the following Table 8 were added per one mole of silver
. The sensitometric results are reported in the following Table 8.
The data of Table 8 clearly show the good results of the comounds of the present
invention in comparison with those outside of the present invention.
The formula of compounds 5 through 15 employed in the above samples can be found in
the following Table 9.