FIELD OF THE INVENTION
[0001] The present invention relates to a silver halide photographic material having a dyed
hydrophilic colloid layer, and more particularly to a silver halide photographic material
having a hydrophilic colloid layer containing a dye which is photochemically inactive
and is easily decolored and/or dissolved out in a photographic processing step.
BACKGROUND OF THE INVENTION
[0002] In silver halide photographic materials, it has been frequently practiced to color
the photographic silver halide emulsion layers and other hydrophilic colloid layer(s)
for absorbing light of a specific wavelength.
[0003] When it is necessary to control the spectral composition of light entering a photographic
silver halide emulsion layer of a silver halide photographic material, a colored layer
is usually formed at the side farther from the support than the photographic emulsion
layer. Such a colored layer is known as a filter layer. When a photographic light-sensitive
material has plural photographic emulsion layers, a filter layer may be added between
the photographic emulsion layers.
[0004] A colored layer known as an antihalation layer is provided to prevent dimming of
images (halation) caused by light that is scattered during or after passing through
photographic emulsion layers, which scattered light is reflected at the interface
between the emulsion layer and the support and/or at the surface of the support opposite
to the emulsion layer side, and then reenters the photographic emulsion layer. When
plural photographic emulsion layers are present, the antihalation layer is sometimes
interposed between these photographic emulsion layers.
[0005] Furthermore, the photographic emulsion layer(s) can be colored to prevent a reduction
in image sharpness caused by light scattering at photographic emulsion layer(s) (this
phenomenon is generally known as "irradiation").
[0006] In many cases, colored layers are formed of hydrophilic colloids. For coloring these
hydrophilic colloid layers, a dye is usually incorporated in the hydrophilic colloid
layers. The dye being used for the purpose must satisfy the following requirements.
(1) The dye has an appropriate spectral absorption according to the desired application.
(2) The dye is photochemically inactive. Specifically, the dye does not exert adverse
chemical effects on the performance of the silver halide photographic emulsion layers,
for example, a reduction in sensitivity, fading of latent images formed and fog.
(3) The dye is decolorized during photographic processing or is dissolved out in the
processing solution or wash water during processing so as to not leave harmful residual
color in the photographic light-sensitive material after processing.
(4) The dye does not diffuse into other layers from the dyed layer.
(5) The dye is excellent in stability over time in solution or in the photographic
light sensitive material and does not cause discoloration or fading.
[0007] In particular, when the colored layer is a filter layer or an antihalation layer
provided at the same side as the photographic emulsion layer side of the support,
it is frequently required that the layer only is selectively colored and the coloring
does not substantially affect other layers. The reason is that if the coloring affects
other layers, it not only provides a harmful spectral effect to other layers, but
also the efficacy of the filter layer or the antihalation layer is reduced.
[0008] However, when the layer containing the dye is brought into contact with other hydrophilic
colloid layer in a wet state, a part of the dye frequently diffuses from the dye layer
to the other layer. For preventing this diffusion of the dye many methods have been
proposed.
[0009] For example, a method of providing a dissociated anionic dye and a hydrophilic polymer
having an opposite charge as a mordant in a layer to localize the dye in the specific
layer by the interaction of the mordant with the dye molecule is disclosed in U.S.
Patents 2,548,564, 4,124,386, and 3,625,694.
[0010] Also, a method of dyeing a specific layer using fine particles of a metal salt adsorbed
with a dye is disclosed in U.S. Patents 2,719,088, 2,496,841, and 2,496,843 and JP-A-60-45237
(the term "JP-A" as used herein means an "unexamined published Japanese patent application").
[0011] Also, a method of dyeing a specific layer using a water-insoluble solid dye is disclosed
in JP-A-55-120030, JP-A-56-12639, JP-A-55-155350, JP-A-55-155351, JP-A-63-27838, JP-A-63-197943,
JP-A-52-92716, European patents 15601, 276566, 274723, 276566, and 299435, and WO
88/04794.
[0012] EP-0015601 discloses photographic silver halide materials comprising 2-pyrazolin-5-one
pentamethine oxonol dyes as light absorbing species in the visible spectral region,
which are substituted by two C
1 to C
5 groups. These dyes are incorporated in a dispersed form in at least one light sensitive
silver halide emulsion layer or in an antihalation layer. However, with the compounds
disclosed in EP-0015601 included in a photographic material, a satisfying sharpness
could not yet be achieved in a reversal development process nor in a negative development
process.
[0013] GB-R-1338799 describes a photographic material comprising at least one silver halide
emulsion which contains an oxonol dyestuff in at least one layer. These oxonol dyestuffs
are used for dyes for improved antihalation of filter layers in photographic materials
and show the ability to easily de-colorize in photographic processing baths. As can
be derived from the examples, the dyes are used in form of a solution in an organic
solvent.
[0014] GB-A-1114323 concerns silver halide light sensitive materials having improved filter
layers, antihalation layers and/or layers containing anti-radiation dyes. The compounds
incorporated into the silver halide light sensitive material are oxonol dyes having
no acid radicals, which are coated on a photographic emulsion layer in form of a solution
of the dye in an organic solvent.
[0015] However, even when using these methods, there is a problem of diffusion of the dye
in a dye-fixing layer. When changing various factors to quicken processing, such as
improving the compositions of processing solutions or improving the composition of
photographic silver halide emulsions there is a problem in that the decolorizing function
of the dye is not always satisfactory due to the delayed decolorizing rate at photographic
processing.
SUMMARY OF THE INVENTION
[0016] An object of the present invention is to provide a silver halide photographic material
containing dispersed fine solid particles of a dye so as to dye a specific hydrophilic
colloid layer in the photographic light-sensitive material and be quickly decolorized
during development processing without diffusing into other layers especially during
the storage of the photographic light-sensitive material.
[0017] It has now been discovered that the above and other objects have been achieved by
a silver halide photographic material having on a support a hydrophilic colloid layer
containing at least one compound represented by general formula (I) in the form of
a dispersion of fine solid particles thereof;
wherein R
1 represents a hydrogen atom, an aryl group, a cyano group, a halogen atom, -COOR
2, -COR
3, -CONR
3R
4, -OR
2, -NHCOR
3, or -NR
3R
4 (wherein R
2 represents an alkyl group or an aryl group and R
3 and R
4 each represents a hydrogen atom, an alkyl group, or an aryl group), and L
1, L
2, L
3, L
4, and L
5 each represents a methine group.
[0018] It is preferable that the methine group represented by L
1, L
2, L
3, L
4, and L
5 is unsubstituted, but the methine group may have a substituent such as methyl, ethyl,
phenyl, etc.
[0019] The compound represented by the above-described general formula (I) is described
in detail below.
DETAILED DESCRIPTION OF THE INVENTION
[0020] The aryl group shown by R
1 may have a substituent such as an alkyl group (e.g., methyl and ethyl), an alkoxy
group (e.g., methoxy and ethoxy), a halogen atom (e.g., chlorine, bromine, and fluorine),
an amino group (e.g., dimethylamino and diethylamino), a cyano group, and a phenoxy
group. Further, R
1 may be bonded directly or through a divalent linkage group such as -O-, -S-, -NRCO-,
-CONR-, -(CH
2)
pOCO-, -NHCONH-, -NHOCO-, etc., [wherein R represents an alkyl group having from 1
to 6 carbon atoms (e.g., methyl, ethyl, and n-hexyl) and p represents an integer of
from 0 to 5].
[0021] Preferably, R
1 represents -OR
2, with R
2 being an alkyl group having from 1 to 5 carbon atoms.
[0022] Specific examples of the compound represented by general formula (I) are illustrated
below but the invention is not limited to them.
[0023] In the compounds shown above, L
1, L
2, L
4, and L
5 are CH.
[0024] The compounds of general formula (I) can be synthesized according to the methods
described in JP-A-52-92716, JP-A-63-316853, JP-A-64-40827, and JP-B-58-35544 (the
term "JP-B" as used herein means an "examined published Japanese patent application").
[0025] The compound of general formula (I) is used in an amount of from 1 to 1000 mg, and
preferably from 1 to 800 mg per square meter of a photographic light-sensitive material.
[0026] When the compound of general formula (I) is used as a filter dye or an antihalation
dye, any suitable amount can be used, but it is preferred that the compound of formula
(I) is used in an amount such that the optical density becomes from 0.05 to 3.5. The
dye may be added to the coating composition of the layer at any step before coating.
[0027] The compound of general formula (I) can be used in a silver halide emulsion layer
or other hydrophilic colloid layer.
[0028] The dispersion of fine particles of the compound of general formula (I) can be formed
by a method of precipitating the compound of general formula (I) in the form of a
dispersion thereof and/or a method of forming a dispersion using a known pulverizing
means such as ball milling (e.g., using a ball mill, a vibrating ball mill, and an
epicyclic ball mill), sand milling, colloid milling, jet milling, roller milling,
etc., in the presence of a dispersing agent [in this case, a solvent (e.g., water
and an alcohol) may be present in the system]. Alternatively, after dissolving the
compound of general formula (I) in a proper solvent, a fine crystal powder of the
compound may be precipitated by adding a poor solvent for the compound to the solution
and in this case, a surface active agent for dispersion may also be added. Furthermore,
the compound of general formula (I) can be first dissolved in a solvent by controlling
the pH thereof, and then finely crystallized by changing the pH thereof.
[0029] The mean particle size of the fine crystal particles of the compound of general formula
(I) in the dispersion is not larger than 10 µm, preferably not larger than 2 µm, and
more preferably not larger than 0.5 µm. Fine crystal particles having a mean particle
size of not larger than 0.1 µm is particularly preferred.
[0030] As the hydrophilic colloid for use in the present invention, gelatin is typical but
other hydrophilic colloids which are suitable for use with photographic light-sensitive
materials can be used.
[0031] For the silver halide emulsion for use in the present invention, silver bromide,
silver iodobromide, silver iodochlorobromide, silver chlorobromide, or silver chloride
is preferably used.
[0032] The silver halide grains for use in the present invention may have a regular crystal
form such as a cube and an octahedron, an irregular crystal form such as a sphere
and a tabular form, or a composite form of these crystal forms. Also, a mixture of
silver halide grains having various crystal forms can be used. In this invention,
however, the use of the silver halide grains having a regular crystal form is preferably
used.
[0033] The silver halide grains for use in the present invention may differ in phase between
the inside and the surface layer thereof or may be uniform in phase throughout the
whole grain. Also, the silver halide grains may form latent images mainly on the surface
(e.g., a negative-working silver halide emulsion) or may form latent images mainly
in the inside (e.g., an internal latent image type silver halide emulsion and a previously
fogged direct reversal type silver halide emulsion). In this invention, the silver
halide grains forming latent images mainly on the surface are preferably used.
[0034] The silver halide emulsion for use in the present invention is preferably a tabular
grain silver halide emulsion containing silver halide grains wherein the grains having
a thickness of not more than 0.5 µm, and preferably not more than 0.3 µm, a diameter
of preferably at least 0.6 µm, and a mean aspect ratio of at least 5 account for at
least 50% of the total projected area or a monodisperse silver halide emulsion having
a statistical coefficient of variation (the value S/d obtained by dividing a standard
deviation S by a diameter d in the distribution shown by the diameter in case where
the projected area is approximated to a circle) of 20% or lower. Also, a mixture of
tabular grain silver halide emulsion(s) and monodisperse silver halide emulsion(s)
may be used.
[0035] The silver halide emulsions for use in the present invention can be prepared using
the methods described in P. Glafkides,
Chimie et Physique Photographique, published by Paul Montel Co., 1967; G.F. Duffin,
Photographic Emulsion Chemistry, published by Forcal Press, 1966; and V.L. Zelkiman et al,
Making and Coating Photographic Emulsion, published by Focal Press, 1964.
[0036] At the formation of the silver halide grains, ammonia, potassium thiocyanate, ammonium
thiocyanate, thioether compounds (described in U.S. Patents 3,271,157, 3,574,628,
3,704,130, 4,297,439 and 4,276,374), thione compounds (described in JP-A-53-144319,
JP-A-53-82408, and JP-A-55-77737), or amine compounds (described in JP-A-54-100717)
can be used as a silver halide solvent for controlling the growth of the silver halide
grains.
[0037] At the step of forming or physically ripening silver halide grains, a cadmium salt,
a zinc salt, a thallium salt, an iridium salt or complex salt thereof, a rhodium salt
or complex salt thereof, or an iron salt or complex salt thereof may be present in
the emulsion.
[0038] As the binder or the protective colloid which is used for the silver halide emulsion
layers, interlayers, etc., of the photographic light-sensitive material of the present
invention, gelatin is advantageously used, but other hydrophilic colloid can be used.
For example, proteins such as gelatin derivatives, graft polymers of gelatin and other
polymers, albumin, casein, etc.; cellulose derivatives such as hydroxyethyl cellulose,
carboxymethyl cellulose, cellulose sulfuric acid esters, etc.; saccharose derivatives
such as sodium alginate, starch derivatives, etc.; or various synthetic hydrophilic
homopolymers or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal,
poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl
imidazole, polyvinyl pyrazole, etc., can be used.
[0039] As gelatin, ordinary lime-processed gelatin as well as acid-processed gelatin and
enzyme-processed gelatin as described in
Bull. Soc. Sci. Phot. Japan, No. 16, p. 30 (1966) can be used. Also, the hydrolyzed product of gelatin can be
used.
[0040] The photographic light-sensitive material of the present invention may contain an
optional inorganic or organic hardening agent in optional hydrophilic colloid layers
constituting the photographic light-sensitive layers, and back layer thereof. Examples
of such a hardening agent are chromium salts, aldehydes (e.g., formaldehyde, glyoxal,
and glutaraldehyde), and N-methylol series compounds (e.g., dimethylolurea).
[0041] Also, active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-1,3,5-triazine and the
sodium salts thereof) and active vinyl compounds [1,3-bisvinylsulfonyl-2-propanol,
1,2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl) ether, and a vinylic
polymer having a vinylsulfonyl group at the side chain) are preferably used as the
hardening agent since they quickly harden hydrophilic colloids such as gelatin to
give stable photographic characteristics. Furthermore, N-carbamoylpyridinium salts
such as (1-morpholinocarbonyl-3-gyridinio)methane sulfonate, etc., and haloamidinium
salts such as 1-(1-chloro-1-pyridinomethylene)pyrrolidinium-2-naphthalene sulfonate,
etc., are excellent in hardening rate.
[0042] The silver halide photographic emulsions for use in this invention may be spectrally
sensitized with methine dyes, etc. The dyes which are used for this purpose include
cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar
dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes
are dyes belonging to cyanine dyes, merocyanine dyes, and complex merocyanine dyes.
[0043] Any nucleus ordinarily utilized in cyanine dyes as a basic heterocyclic nucleus can
be present in these dyes. Such basic heterocyclic nuclei include pyrroline nuclei,
oxazoline nuclei, thiazoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei,
selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc.; nuclei
formed by fusing an aliphatic hydrocarbon ring to the aforesaid nuclei, and nuclei
formed by fusing an aromatic hydrocarbon ring to the aforesaid nuclei, such as indolenine
nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, naphthoxazole nuclei,
benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benzimidazole
nuclei, quinoline nuclei, etc. These nuclei may have substituent(s) on carbon atoms.
[0044] 5-membered or 6-membered heterocyclic nuclei such as pyrazolin-5-one nuclei, thiohydantoin
nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazolidine-2,4-dione nuclei, rhodanine
nuclei, thiobarbituric acid nuclei, etc., may be present in the merocyanine dyes or
complex merocyanine dyes as nuclei that have a ketomethylene structure.
[0045] These sensitizing dyes may be used singly or in combination. A combination of sensitizing
dyes is frequently used for the purpose of supersensitization.
[0046] The silver halide emulsion for use in this invention may contain a dye having no
spectral sensitizing activity by itself or a substance which does not substantially
absorb visible light and shows supersensitizing activity, together with the sensitizing
dye(s). For example, the emulsions may contain aminostilbene compounds substituted
by a nitrogen-containing heterocyclic nucleus group (e.g., the compounds. described
in U.S. Patents 2,933,390 and 3,635,721), aromatic organic acid-formamide condensation
products (e.g., the compounds described in U.S. Patent 3,743,510), cadmium salts,
and azaindene compounds. The combinations described in U.S. Patents 3,615,613, 3,615,641,
3,617,295, and 3,635,721 are particularly useful.
[0047] The silver halide photographic emulsion used in the present invention can further
contain various compounds for inhibiting the formation of fog during the production,
storage, and photographic processing of the photographic light-sensitive material
or for stabilizing the photographic properties. For example, there are many compounds
known as antifoggants or stabilizers, such as azoles [e.g., benzothiazolium salts,
nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles,
benzotriazoles, nitrobenzotriazoles and merpcatotetrazoles (in particular, 1-phenyl-5-mercaptotetrazole)];
mercaptopyrimidines; mercaptotriazines; thioketo compounds (e.g., oxazolinethione);
azaindenes [e.g., triazaindenes, tetraazaindenes (in particular, 4-hydroxy-substituted
(1,3,3a,7)tetraazaindenes), and pentaazaindenes]; benzenethiosulfonic acid; benzenesulfinic
acid; and benzenesulfonic acid amide.
[0048] The photographic light-sensitive material of the present invention may contain one
or more kinds of surface active agents for use as coating aids, static prevention,
to improve slidability, to improve emulsified dispersions, to prevent sticking, and
to improve photographic characteristics (e.g., accelerating development, increasing
contrast, increasing sensitivity, etc.).
[0049] The photographic light-sensitive material of the present invention may contain a
water-soluble dye in the hydrophilic colloid layer as a filter dye, or as a dye to
prevent irradiation, or as a dye to inhibit halation, or for various other purposes.
[0050] Preferred examples of such a water-soluble dye include oxonol dyes, hemioxonol dyes,
styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes. Furthermore, cyanine
dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful
as a water-soluble dye. An oil-soluble dye can be incorporated into the hydrophilic
colloid layer by emulsifying with an oil drop-in-water dispersion method.
[0051] The present invention can be present in a multilayer multicolor photographic material
having at least two photographic emulsion layers each having a spectral sensitivity
on a support.
[0052] A multilayer natural color photographic material usually has at least one red-sensitive
emulsion layer, at least one green-sensitive emulsion layer, and at least one blue-sensitive
emulsion layer on a support. The arrangement of these emulsion layers can be desirably
selected as required.
[0053] A preferred order of the emulsion layers is a red-sensitive emulsion layer, a green-sensitive
emulsion layer, a blue-sensitive emulsion layer/support, or a blue-sensitive emulsion
layer, a green-sensitive emulsion layer, a red-sensitive emulsion layer/support, or
a blue-sensitive emulsion layer, a red-sensitive emulsion layer, a green-sensitive
emulsion layer/ support.
[0054] Also, an optional same color-sensitive emulsion layer may be composed of two or more
emulsion layers each having a different light sensitivity for improving the range
of light sensitivity or a same color-sensitive emulsion layer may be composed of three
emulsion layers to improve graininess. Also, a light-insensitive layer may be interposed
between two or more emulsion layer each having the same color sensitivity. Furthermore,
between emulsion layers having the same color sensitivity, an emulsion layer having
a different color sensitivity may be inserted. Also, a reflective layer containing
fine silver halide grains may be provided under a high-sensitive emulsion layer, in
particular, a high-sensitive blue-sensitive layer to improve the sensitivity.
[0055] In general the red-sensitive emulsion layer contains a cyan-forming coupler, the
green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive
emulsion layer contains a yellow-forming coupler. If desired, other combinations can
be employed. For example, by combining the color-sensitive emulsion layers with an
infrared-sensitive layer, the photographic light-sensitive material may be used for
a pseudo color photograph or a semiconductor laser exposure.
[0056] For producing the photographic light-sensitive material of the present invention,
the photosensitive emulsion layers and other layers are coated on a flexible support,
which is usually used for photographic light-sensitive materials, such as plastic
films, papers, cloths, etc., or a solid support such as glass plates, ceramics, metal
sheets, etc.
[0057] Examples of the useful flexible support are films of semi-synthetic or synthetic
polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate,
polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.,
and papers coated or laminated with a baryta layer or an α-olefin polymer (e.g., polyethylene,
polypropylene, and an ethylene/butylene copolymer). The support may be colored with
a dye or a pigment. The support may be colored black to shield the light.
[0058] The surface of the support is generally subjected to a subbing treatment for improving
adhesion with a photographic emulsion layer, etc. Before or after the subbing treatment,
the surface of the support may be subjected to a glow discharging treatment, a corona
discharging treatment, a ultraviolet irradiation treatment, a flame treatment, etc.
[0059] For coating the photographic emulsion layers and other hydrophilic colloid layers,
various known coating methods such as a dip coating method, a roller coating method,
a curtain coating method, an extrusion coating method, etc., can be utilized. If necessary,
multilayers may be coated simultaneously by the coating methods described in U.S.
Patents 2,681,294, 2,761,791, 3,526,528, and 3,508,947.
[0060] The present invention can be applied to various color and black-and-white photographic
light-sensitive materials, such as general or movie color negative films, color reversal
films for slides or television, color photographic papers, color positive films, color
reversal photographic papers, color diffusion transfer type photographic light-sensitive
materials, and heat developable type color photographic light-sensitive materials.
The present invention can also be applied to black-and-white light-sensitive materials
such as radiographic materials by utilizing a mixture of three color couplers described
in
Research Disclosure, No. 17123 (July, 1978) or by utilizing a black coloring coupler described in U.S.
Patent 4,126,461 and British Patent 2,102,136. Furthermore, the present invention
can also be applied for printing plate-making films such as lithographic films or
scanner films; direct or indirect medical X-ray films or industrial X-ray films; negative
black-and-white photographic films for camera use, black-and-white photographic papers,
COM or ordinary microfilms, silver salt diffusion transfer type light-sensitive materials,
and print-out type light-sensitive materials.
[0061] When the photographic material of the present invention is applied to a color diffusion
transfer photographic process, a peel apart type, an integrated type described in
JP-B-46-16356, JP-B-48-33697, JP-A-50-13040, and British Patent 1,330,524, or a peel
apart unnecessary type film unit structure as described in JP-A-57-119345 can be employed.
[0062] In any format described above, it is useful for widening the allowable range of the
processing temperature to use a polymer acid layer protected by a neutralization timing
layer. When the photographic material of this invention is used for a color diffusion
transfer photographic process, a polymer acid may be added to any layer of the photographic
light-sensitive material or may be incorporated into the processing container as a
developer component.
[0063] The photographic light-sensitive material of the present invention can be exposed
by various means. Any light source emitting a radiation corresponding to the light-sensitive
wavelengths of the photographic light-sensitive material can be used as an illuminating
light source or a recording light source. For example, natural light (sun light),
an incandescent lamp, a halogen atom-containing lamp, a mercury lamp, a fluorescent
lamp, and a flash light source such as an electronic flash or a metal burning flash
bulb can be generally used. A gas laser, a dye solution laser, or a semiconductor
laser, a light emitting diode (LED), and a plasma light source which emit light in
the wavelength region of from ultraviolet to infrared can be used as a recording light
source.
[0064] Further, a fluorescent plane emitting light from a fluorescent substance excited
by electron rays (e.g., CRT) or an exposure means composed of a combination of a micro
shutter array utilizing a liquid crystal (LCD) or lanthanum-doped lead titaniumzirconate
(PLZT) with a line-form or plate-form light source can be used. If necessary, the
spectral distribution of a light source which is used for exposure can be controlled
by a color filter.
[0065] A color developer which is used for developing the photographic light-sensitive material
of the present invention is preferably an alkaline aqueous solution containing an
aromatic primary amino developing agent as the main component.
[0066] As the color developing agent, aminophenol series compounds may be useful but p-phenylenediamine
series compounds are preferably used. Typical examples thereof are 3-methyl-4-amino-N,N-diethylaniline,
3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline,
3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and the sulfates, hydrochlorides,
or p-toluenesulfonates, etc., of the above-described compounds. These diamines are
preferably used as the salts, rather than as the salt-free compounds, since the salts
are generally more stable.
[0067] The color developer generally contains a pH buffer such as carbonates, borates, or
phosphates of an alkali metal or a development inhibitor or an antifoggant such as
bromides, iodides, benzimidazoles, benzothiazoles, and mercapto compounds. Also, if
necessary, the color developer may contain a preservative such as hydroxyamines, dialkylhydroxylamines,
hydrazines, triethanolamines, triethylenediamine, and sulfites; an organic solvent
such as triethanolamine, diethylene glycol, etc.; a development accelerator such as
benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, etc.; a dye-forming
coupler, a competing coupler; a nucleating agent such as sodium borohydride, etc.;
an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, etc.; a tackifier;
various chelating agents such as aminopolycarboxylic acid, aminopolyphosphoric acid,
anlkylphosphonic acid, and phosphonocarboxylic acid; and an antioxidant described
in West German Patent Application (OLS) 2,622,950.
[0068] In the development process of a reversal color photographic light-sensitive material,
after carrying out black-and-white development, color development is usually carried
out. For the black-and-white developer, known black-and-white developing agents such
as dihydroxybenzenes such as hydroquinone, etc.; 3-pyrazolidones such as 1-phenyl-3-pyrazolidone,
etc.; and aminophenols such as N-methyl-p-aminophenol, etc., can be used singly or
in combination.
[0069] For the photographic light-sensitive materials, not only a color developer but also
any photographic developing process may be used.
[0070] Developing agents which can be used for a developer include dihydroxybenzene series
developing agents, 1-phenyl-3-pyrazolidone series developing agents, and p-aminophenol
series developing agents, and they can be used singly or as a combination thereof
(e.g., a combination of a 1-phenyl-3-pyrazolidone and a dihydroxybenzene or a combination
of a p-aminophenol and a dihydroxybenzene).
[0071] Also, the photographic light-sensitive material of the present invention may be processed
with an infectious developer using a sulfite ion buffer such as carbonyl bisulfite
together with hydroquinone.
[0072] Examples of the above-described dihydroxybenzene series developing agent include
hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydrohydroquinone,
methylhydroquinone, 2,3-dichlorohydroquinone, and 2,5-dimethylhydroquinone; examples
of the 1-phenyl-3-pyrazolidone series developing agent are 1-phenyl-3-pyrazolidone,
4,4-dimethyl-1-phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone,
and 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone, and examples of the p-aminophenol
series developing agent are p-aminophenol and N-methyl-p-aminophenol.
[0073] The developer also can contain a compound providing free sulfite ions as a preservative,
for example, sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium
bisulfite. In the case of an infectious developer, a formaldehyde sodium bisulfite
condensation product, which hardly provides any free sulfite ions in the developer,
may be used.
[0074] As the alkali agent contained in the developer, potassium hydroxide, sodium hydroxide,
potassium carbonate, sodium carbonate, sodium acetate, potassium tertiary phosphate,
diethanolamine, triethanolamine, etc., can be used. The pH of the developer is usually
at least 9 and is preferably at least 9.7.
[0075] The developer may contain an organic compound as an antifoggant or a development
inhibitor. Examples thereof include azoles such as benzothiazolium salts, nitroindazoles,
nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles,
benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (in particular, l-phenyl-5-mercaptotetrazole),
etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione,
etc.; azaindenes such as triazaindenes, tetraazaindenes (in particular, 4-hydroxy-substituted
(1,3,3a,7)tetraazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic
acid, benzenesulfonic acid amide, and sodium 2-mercaptobenzimidzole-5-sulfonate.
[0076] The developer for use in the present invention may contain a polyalkylene oxide as
a development inhibitor as described above. For example, a polyethylene oxide having
a molecular weight of from 1000 to 10,000 can be used in an amount of 0.1 to 10 g/liter.
[0077] The developer for use in this invention preferably contain nitrilotriacetic acid,
ethylenediamine tetraacetic acid, triethylenetetramine, acetic acid, diethylenetetraminepentaacetic
acid, etc., as a water softener.
[0078] The developer for use in this invention can contain compounds described in JP-A-56-24347
as a silver stain inhibitor, compounds described in JP-A-62-212651 as an uneven development
inhibitor, and compounds described in JP-A-61-267759 as a dissolution aid.
[0079] Furthermore, the developer for use in this invention can contain boric acid described
in JP-A-62-186259, saccharose described in JP-A-60-93433, oximes (e.g., acetoxime),
phenols (e.g., 5-sulfosalicylic acid), tertiary phosphates (e.g., the sodium salt
and the potassium salt), etc., as a buffer.
[0080] As the development accelerator for use in the present invention, various known compounds
can be used, and these compound may be incorporated in the photographic light-sensitive
materials or the developer. Examples of the preferred development accelerator are
amine series compounds, imidazole series compounds, imidazoline series compounds,
phosphonium series compounds, sulfonium series compounds, hydrazine series compounds,
thioether series compounds, thione series compounds, certain kinds of mercapto compounds,
mesoion series compounds, and thiocyanates.
[0081] In particular, for carrying out a rapid development process, a development accelerator
is necessary. It is desirable that a development accelerator is added to the color
developer, but according to the kind of development accelerator or a position of a
light-sensitive layer to be subjected to development acceleration on a support, the
accelerator can be incorporated into the photographic light-sensitive material. Also,
the development accelerator may be incorporated into both the color developer and
the photographic light-sensitive material. Furthermore, as desired, a pre-bath for
the color development bath may be formed, and the development accelerator may be added
to the pre-bath.
[0082] Amino compounds useful in the present invention as the amino compound include both
inorganic amines such as hydroxylamine and organic amines. As the organic amine, aliphatic
amines, aromatic amines, cyclic amines, aliphatic-aromatic mixed amines, or heterocyclic
amines can be used. Also, primary, secondary, and tertiary amines and quaternary ammonium
compounds are all effective.
[0083] After color development, the photographic emulsion layers are usually bleached. Bleaching
may be carried out simultaneously with or separately from fixing. Furthermore, for
quickening photographic processing, after bleaching, a blixing treatment may be applied.
[0084] Bleaching agents include, for example, compounds of a polyvalent metal such as iron
(III), cobalt(III), chromium(IV), copper(II), etc., peracids, quinones, and nitron
compounds. Typical examples of a bleaching agent are ferricyanides, bichromates, organic
complex salts of iron(III) or cobalt(III), such as the complex salts of aminopolycarboxylic
acids (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
nitrilotriacetic acid, and 1,3-diamino-2-propanoltetraacetic acid) or organic acids
(e.g., citric acid, tartaric acid, and malic acid); persulfates, manganates, and nitrosophenol.
In these compounds, ethylenediaminetetraacetic acid iron(III) salts, diethylenetriaminepentaacetic
acid iron(III) salts, and persulfates are preferred from the view points of quick
processing and less environmental pollution. Furthermore, an ethylenediaminetetraacetic
acid iron(III) salt is particularly useful for an independent bleach solution and
a blix solution.
[0085] For the bleach solution, the blix solution and the pre-bath thereof, if necessary,
a bleach accelerator can be used.
[0086] Specific examples of the bleach accelerator are the compounds having a mercapto group
or a disulfide group described in U.S. Patent 3,893,858, West German Patents 1,290,812
and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-65732, JP-A-53-72623,
JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426,
and
Research Disclosure; thiazolidine derivatives described in JP-A-50-140129; thiourea derivatives described
in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and U.S. Patent 3,706,561; iodides
described in West German Patent 1,127,715 and JP-A-58-16235; polyethylene oxides described
in West German Patents 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836;
the compounds described in JP-A-49-42434, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727,
JP-A-55-26506, and JP-A-58-163940; and iodine and bromine ions.
[0087] In these compounds, compounds having a mercapto group or a disulfide group are preferred
because they provide a large acceleration effect and in particular, the compounds
described in U.S. Patent 3,893,858, West German Patent 1,290,812, and JP-A-53-95630
are preferred. Furthermore, compounds described in U.S. Patent 4,552,834 are also
preferred. These bleach accelerators may be added to a light-sensitive material. When
a color photographic material for photographing (in camera use) is blixed, these bleach
accelerators are particularly effective.
[0088] Fixing agents include thiosulfates, thiocyanates, thioether series compounds, thioureas,
and a large amount of an iodide, but thiosulfates are generally used.
[0089] As a preservative for the blixing solution or the fixing solution, sulfites, bisulfites,
or carbonyl bisulfite addition products are preferable.
[0090] After blixing or fixing, washing or stabilization is usually carried out. In the
washing and stabilizing steps, various compounds may be used for the purposes of preventing
precipitation and saving water. For example, for precipitation, a water softener such
as inorganic phosphoric acids, aminopolycarboxylic acids, organic aminopolyphosphonic
acids, organic phosphoric acids, etc.; germicides or antifungal agents for preventing
the growth of various kind of bacteria, algae, and molds; metal salts such as magnesium
salts, aluminum salts, and bismuth salts; surface active agents for preventing drying
load and uneven drying; and various hardening agents can be, if necessary, added thereto.
Moreover, the compounds described in L.E. West,
Phot. Sci. Eng., Vol. 6, 344-359(1965) may be added. The addition of a chelating agent or an anti-fungal
agent is particularly effective.
[0091] The washing step is generally carried out using 2 or more baths by a countercurrent
system for saving water. Furthermore, in place of the wash step, the multistage countercurrent
stabilization step described in JP-A-57-8543 may be employed. This step requires 2
to 9 countercurrent baths. To the stabilizing solution various kinds of compounds
are added for stabilizing images formed in addition to the above-described additives.
Examples of these compounds are various buffers for adjusting pH of the layers, for
example, pH of from 3 to 9. Examples of buffers include a combination of, for example,
borates, metaborates, borax, phosphates, carbonates, potassium hydroxides, sodium
hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic
aid, etc.; and aldehydes such as formalin. Furthermore, if necessary, chelating agents
(e.g., inorganic phosphoric acids, aminopolycarboxylic acids, organic phosphoric acids,
organic phosphonic acids, aminopolysulfonic acid, and phosphonocarboxylic acids),
germicides (e.g., benzoisothiazolinone, isothiazolone, 4-thiazolinebenzimidazole,
halogenated phenols, sulfanylamide, and benzotriazole), surface active agents, brightening
agents, hardening agents, etc., may be used, and two or more compounds having the
same or different purpose may be used together.
[0092] Also, as the pH controlling agent for layers after processing, it is preferable to
add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate,
ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc., to the stabilization
solution.
[0093] For the color photographic material for photographing, a wash-stabilizing step which
is usually carried out after fixing may be replaced with the above-described stabilizing
step and washing step (water-save processing). In this case, when a two equivalent
magenta coupler is used, formalin may be removed from the stabilization solution.
[0094] The washing time and the stabilizing time differ according to the kind of photographic
light-sensitive material and the processing conditions but is usually from 20 seconds
to 10 minutes, and preferably from 20 seconds to 5 minutes for each step.
[0095] The silver halide color photographic material of the present invention may contain
a color developing agent for simplifying and quickening processing. For incorporating
the color developing agent in the photographic light-sensitive material, it is preferable
to use various precursors for the color developing agents.
[0096] For example, there are indoaniline series compounds described in U.S. Patent 3,342,597,
the Schiff base type compounds described in U.S. Patent 3,342,599,
Research Disclosure, No. 14850, and
ibid., No. 15159, aldol compounds described in
Research Disclosure, No. 13924, metal salt complexes described in U.S. Patent 3,719,492, urethane series
compounds described in JP-A-53-135628, and various salts type precursors described
in JP-A-56-6235, JP-A-56-16133, JP-A-56-59232, JP-A-56-67842, JP-A-56-83734, JP-A-56-83735,
JP-A-56-83736, JP-A-56-89735, JP-A-56-81837, JP-A-56-54430, JP-A-56-106241, JP-A-107236,
JP-A-57-97531, and JP-A-57-83565.
[0097] The silver halide color photographic material of the present invention may, if necessary,
contains various kinds of 1-phenyl-3-pyrazolidones for accelerating the color development.
Typical compounds are described in JP-A-56-64339, JP-A-57-144547, JP-A-57-211147,
JP-A-58-50532, JP-A-58-50536, JP-A-58-50533, JP-A-58-50534, JP-A-58-50535, and JP-A-58-115438.
[0098] The various processing solutions for processing the photographic light-sensitive
materials of the present invention are used at a temperature of from 10°C to 50°C.
The standard processing temperature is from 33°C to 38°C. However, a higher temperature
can be employed for accelerating processing to shorten the processing time, or a lower
temperature can be employed for improving the image quality and improving the stability
of the processing solutions. Furthermore, for saving silver of the photographic light-sensitive
material, processing using cobalt intensification or hydrogen peroxide intensification
described in West German Patent 2,226,770 and U.S. Patent 3,674,499 may be employed
in this invention.
[0099] If necessary, each processing bath may be equipped with a heater, a temperature sensor,
a liquid level sensor, a circulating pump, a filter, a floating lid, a squeegee, etc.
[0100] Also, when using continuous processing, a constant finish is obtained by preventing
the deviation of the composition of processing solutions by using a replenisher for
each processing solution. The replenishing amount can be reduced to a half or lower
of a standard replenishing amount for reducing cost, etc.
[0101] When the photographic light-sensitive material of the present invention is a color
photographic paper, a blixing process is generally employed. In the case of a color
photographic material for photographing, if necessary, blixing may also be employed.
[0102] The silver halide photographic material of the present invention has the excellent
effect that the dye in the dye layer has an adequate spectral absorption, selectively
dyes the dye layer, and does not diffuse into other layers.
[0103] Also, the silver halide photographic material containing the dye of this invention
has the effect that the dye is easily decolorized or dissolved out by photographic
processing to give low Dmin without reducing the sensitivity. Further, the photographic
material shows less reduction of sensitivity after storage.
[0104] Additionally, the silver halide photographic material of the present invention gives
color images having improved sharpness. The photographs obtained from the silver halide
photographic material of this invention can be stably stored for a long period of
time without causing stains and without reducing the photographic performance.
[0105] Then, the invention is described in more detail based on the following example which
is illustrative and does not limit the invention in any way.
Example
Preparation of Dye-Fixing Layer
[0106] Each of the dyes described in Table 1 below was processed in a ball mill by the method
described in JP-A-63-197943.
[0107] Then, 434 ml of water and 791 ml of a 6.7% aqueous solution of a surface active agent,
Triton X-200R (TX-200R) (trade name, made by Rohm & Haas Co.) were placed in a 2 liter
ball mill and 20 g of the dye was added to the solution. Then, after adding thereto
400 ml of beads (diameter 2 mm) of zirconium oxide (ZrO), the mixture was pulverized
for 4 days. Thereafter, 160 g of 12.5% aqueous gelatin solution was added thereto.
[0108] When the dye dispersion thus obtained was observed, the diameters of the dye particles
thus pulverized had a wide distribution from 0.05 µm to 1.15 µm in diameter.
[0109] As a support, a transparent polyethylene terephthalate (PET) film support having
a thickness of 100 µm was used. For improving the adhesion for a hydrophilic colloid
layer, the surface of the support was previously subjected to a corona discharging
treatment, then a 1st subbing layer composed of a styrene-butadiene latex was formed
on the support, and a 2nd subbing layer of 0.08 g/m
2 of gelatin was further formed thereon.
[0110] On the support a gelatin dispersion of the above-described fine dye dispersion was
coated in the amount shown below. Thus, an antihalation layer was prepared.
Preparation of Emulsion Coating Composition
[0111] Emulsion #1 shown below is a surface latent image-type silver halide emulsion and
negative type characteristics are obtained by a commercially available processing
solution for microfilm. Furthermore, positive type characteristics are obtained by
applying reversal processing using a processing solution for reversal.
Preparation of Emulsion #1
[0112]
Solution I 75°C |
|
Inactive Gelatin |
24 g |
Distilled Water |
900 ml |
Potassium Bromide |
4 g |
Aqueous 10% Phosphoric Acid Soln. |
2 ml |
Sodium Benzenesulfinate |
5×10-1 mol |
1,2-Bis(2-hydroxyethylthio)ethane |
2.5×10-3 g |
Solution II 35°C |
|
Silver Nitrate |
170 g |
Distilled Water to make |
1000 ml |
Solution III 35°C |
|
Potassium Bromide |
230 g |
Distilled Water to make |
1000 ml |
Solution IV Room temperature |
|
Hexacyano Iron(III) Potassium |
3.0 g |
Distilled water to make |
100 ml |
[0113] To solution I while stirring well were simultaneously added solution II and solution
III over a period of 45 minutes and at the end of adding the total amount of the solutions,
a cubic grain monodisperse silver halide emulsion having a mean grain size of 0.28
µm was finally obtained.
[0114] In this case, the addition rate of solution III was controlled to the addition of
solution II such that the pAg value in the mixing container became always 7.50. In
addition, solution IV was added thereto after 7 minutes since the initiation of the
addition of solution II over a period of 5 minutes. After finishing the addition of
solution II, the emulsion obtained was washed with water by a flocculation method,
and after desalting, the emulsion was dispersed in an aqueous solution containing
100 g of inactive gelatin. To the emulsion were added 34 mg of sodium thiosulfate
and 34 mg of chloroauric acid tetra-hydrate per mole of silver to adjust the pH value
and the pAg value to 8.9 and 7.0 (40°C), respectively and then the emulsion was subjected
to a chemical sensitization treatment at 75°C for 60 minutes to provide a surface
latent image type silver halide emulsion.
[0115] The layer structure of the light-sensitive material and the composition of each layer
were as follows.
Back Electrically Conductive Layer
[0117]
SnO2/Sb (9/1 by weight ratio, mean particle size 0.25 µm) |
300 mg/m2 |
Inactive Gelatin |
170 mg/m2 |
1,2-Benzoisothiazolin-3-one |
7 mg/m2 |
Sodium Dodecylbenzenesulfonate |
10 mg/m2 |
Sodium Dihexyl-α-sulfosuccinate |
40 mg/m2 |
Sodium Polystyrenesulfonate |
9 mg/m2 |
[0118] Two comparison samples were prepared in the same manner as above, except that one
comparison sample did not contain any dye in the Antihalation Dye Layer, and the other
comparison sample contained a Comparison Dye A instead of Dye I-3.
[0119] The samples were subjected to reversal development processing and negative development
processing as described below.
Processing Process:
Reversal Development Process
[0120] The reversal development process was carried out under the following conditions using
a reversal deep tank automatic processor F-10R, trade name, made by Allen Products
Co., U.S.A., with a commercially available reversal processing solution, FR-531, 532,
533, 534, and 535 (trade names, made by FR Chemicals Co., U.S.A.)
|
Step |
Processing Soln. |
Temp. |
Time |
1. |
1st Development |
FR-531 (1 : 3) |
43°C |
15 sec. |
2. |
Wash |
Running water |
43°C |
15 sec. |
3. |
Bleach |
FR-532 (1 : 3) |
43°C |
15 sec. |
4. |
Cleaning |
FR-533 (1 : 3) |
43°C |
15 sec. |
5. |
Exposure |
- |
- |
- |
6. |
2nd Development |
FR-534 (1 : 3) |
43°C |
15 sec. |
7. |
Fix |
FR-535 (1 : 3) |
43°C |
15 sec. |
8. |
Wash |
Spray |
43°C |
15 sec. |
9. |
Drying |
Hot blast |
- |
- |
Negative Development Process
[0121] The negative development process was carried out under the following conditions using
a deep tank automatic processor, F-10, made by Allen Products Co., U.S.A. with a commercially
available processing solution for microfilm, FR-537 Developer (trade name, made by
FR Chemicals Co., U.S.A.).
|
Step |
Processing Soln. |
Temp. |
Time |
1. |
Development |
FR-537 (1 : 3) |
43°C |
15 sec. |
2. |
Wash |
Running water |
43°C |
15 sec. |
3. |
Fix |
FR-535 (1 : 3) |
43°C |
15 sec. |
4. |
Wash |
Spray |
43°C |
15 sec. |
5. |
Drying |
Hot blast |
- |
- |
Evaluation of Sharpness
[0122] The sharpness was evaluated by MTF. Each photographic light-sensitive material was
exposed by white light for 1/100 second using an MTF measurement wedge and processed
by the above-described automatic processor.
[0123] MTF was measured with an aperture of 400×2 µm
2 and the sharpness was evaluated at the portion of the optical density being 1.0 using
the MTF value of 20 cycles/mm in space frequency.
[0124] The results obtained are shown in Table 1 below.
Evaluation of Residual color
[0125] After processing each unexposed film using the above-described automatic processor,
a green transmission density and a blue transmission density were measured through
a Macbeth Status A filter.
[0126] The results are also shown in Table 1 below.
[0127] As is clear from the results shown in Table 1 above, it can be seen that according
to this invention, a photographic light-sensitive material providing images having
excellent sharpness and less residual color is obtained.