EP0459456B1 - Photographisches Silberhalogenidmaterial - Google Patents

Photographisches Silberhalogenidmaterial Download PDF

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Publication number
EP0459456B1
EP0459456B1 EP19910108816 EP91108816A EP0459456B1 EP 0459456 B1 EP0459456 B1 EP 0459456B1 EP 19910108816 EP19910108816 EP 19910108816 EP 91108816 A EP91108816 A EP 91108816A EP 0459456 B1 EP0459456 B1 EP 0459456B1
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EP
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Prior art keywords
silver halide
photographic
group
layer
photographic material
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EP19910108816
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English (en)
French (fr)
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EP0459456A1 (de
Inventor
Takashi c/o Fuji Photo Film Co. Ltd. Usami
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs therefor
    • G03C1/832—Methine or polymethine dyes

Definitions

  • 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.
  • a colored layer is usually formed at the side farther from the support than the photographic emulsion layer.
  • a colored layer is known as a filter layer.
  • a filter layer may be added between the photographic emulsion layers.
  • 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.
  • the antihalation layer is sometimes interposed between these photographic emulsion layers.
  • 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").
  • colored layers are formed of hydrophilic colloids.
  • a dye is usually incorporated in the hydrophilic colloid layers.
  • the dye being used for the purpose must satisfy the following requirements.
  • 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.
  • JP-A as used herein means an "unexamined published Japanese patent application”
  • 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.
  • 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.
  • a satisfying sharpness could not yet be achieved in a reversal development process nor in a negative development process.
  • 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.
  • the dyes are used in form of a solution in an organic solvent.
  • 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.
  • 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.
  • 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 3 R 4 , -OR 2 , -NHCOR 3 , or -NR 3 R 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.
  • R 1 represents a hydrogen atom, an aryl group, a cyano group, a halogen atom, -COOR 2 , -COR 3 , -CONR 3 R 4 ,
  • 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.
  • 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.
  • 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
  • cyano group e.g., cyano group
  • R 1 may be bonded directly or through a divalent linkage group such as -O-, -S-, -NRCO-, -CONR-, -(CH 2 ) p OCO-, -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].
  • a divalent linkage group such as -O-, -S-, -NRCO-, -CONR-, -(CH 2 ) p OCO-, -NHCONH-, -NHOCO-, etc.
  • R 1 represents -OR 2 , with R 2 being an alkyl group having from 1 to 5 carbon atoms.
  • L 1 , L 2 , L 4 , and L 5 are CH.
  • 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”).
  • 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.
  • the compound of general formula (I) when 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.
  • the compound of general formula (I) can be used in a silver halide emulsion layer or other hydrophilic colloid layer.
  • 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].
  • a solvent e.g., water and an alcohol
  • 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.
  • 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.
  • the mean particle size of the fine crystal particles of the compound of general formula (I) in the dispersion is not larger than 10 ⁇ m, preferably not larger than 2 ⁇ m, and more preferably not larger than 0.5 ⁇ m. Fine crystal particles having a mean particle size of not larger than 0.1 ⁇ m is particularly preferred.
  • 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.
  • silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, or silver chloride is preferably used.
  • 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.
  • 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.
  • 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).
  • the silver halide grains forming latent images mainly on the surface are preferably used.
  • 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 ⁇ m, and preferably not more than 0.3 ⁇ m, a diameter of preferably at least 0.6 ⁇ m, 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.
  • a mixture of tabular grain silver halide emulsion(s) and monodisperse silver halide emulsion(s) may be used.
  • 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.
  • 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.
  • 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.
  • gelatin is advantageously used, but other hydrophilic colloid can be used.
  • 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.
  • 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.
  • 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.
  • a hardening agent examples include chromium salts, aldehydes (e.g., formaldehyde, glyoxal, and glutaraldehyde), and N-methylol series compounds (e.g., dimethylolurea).
  • active halogen compounds e.g., 2,4-dichloro-6-hydroxy-1,3,5-triazine and the sodium salts thereof
  • 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.
  • N-carbamoylpyridinium salts such as (1-morpholinocarbonyl-3-gyridinio)methane sulfonate, etc.
  • haloamidinium salts such as 1-(1-chloro-1-pyridinomethylene)pyrrolidinium-2-naphthalene sulfonate, etc., are excellent in hardening rate.
  • 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.
  • 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
  • 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.
  • sensitizing dyes may be used singly or in combination. A combination of sensitizing dyes is frequently used for the purpose of supersensitization.
  • 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).
  • 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.
  • 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.
  • 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
  • azoles e
  • 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.).
  • 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.).
  • 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.
  • water-soluble dye examples 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a light-insensitive layer may be interposed between two or more emulsion layer each having the same color sensitivity.
  • an emulsion layer having a different color sensitivity may be inserted.
  • 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.
  • the red-sensitive emulsion layer contains a cyan-forming coupler
  • the green-sensitive emulsion layer contains a magenta-forming coupler
  • the blue-sensitive emulsion layer contains a yellow-forming coupler.
  • other combinations can be employed.
  • the photographic light-sensitive material may be used for a pseudo color photograph or a semiconductor laser exposure.
  • 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.
  • 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 ⁇ -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.
  • the surface of the support is generally subjected to a subbing treatment for improving adhesion with a photographic emulsion layer, etc.
  • a subbing treatment for improving adhesion with a photographic emulsion layer, etc.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a polymer acid layer protected by a neutralization timing layer it is useful for widening the allowable range of the processing temperature to use a polymer acid layer protected by a neutralization timing layer.
  • 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.
  • 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.
  • natural light unsun light
  • an incandescent lamp a halogen atom-containing lamp
  • a mercury lamp a fluorescent lamp
  • a flash light source such as an electronic flash or a metal burning flash bulb
  • 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.
  • a fluorescent plane emitting light from a fluorescent substance excited by electron rays e.g., CRT
  • 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.
  • the spectral distribution of a light source which is used for exposure can be controlled by a color filter.
  • 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.
  • 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- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -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.
  • 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.
  • 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.
  • 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.
  • a preservative such as hydroxyamines, dialkylhydroxylamines, hydrazines, triethanolamines, triethylened
  • 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.
  • photographic light-sensitive materials not only a color developer but also any photographic developing process may be used.
  • 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).
  • 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.
  • a sulfite ion buffer such as carbonyl bisulfite together with hydroquinone.
  • 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
  • examples of the p-aminophenol series developing agent are p-aminophenol and N-methyl-p-aminophenol.
  • 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.
  • a formaldehyde sodium bisulfite condensation product which hardly provides any free sulfite ions in the developer, may be used.
  • potassium hydroxide sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, potassium tertiary phosphate, diethanolamine, triethanolamine, etc.
  • the pH of the developer is usually at least 9 and is preferably at least 9.7.
  • the developer may contain an organic compound as an antifoggant or a development inhibitor.
  • organic compound such 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
  • the developer for use in the present invention may contain a polyalkylene oxide as a development inhibitor as described above.
  • 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.
  • the developer for use in this invention preferably contain nitrilotriacetic acid, ethylenediamine tetraacetic acid, triethylenetetramine, acetic acid, diethylenetetraminepentaacetic acid, etc., as a water softener.
  • 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.
  • 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.
  • boric acid described in JP-A-62-186259
  • saccharose described in JP-A-60-93433 oximes
  • phenols e.g., 5-sulfosalicylic acid
  • tertiary phosphates e.g., the sodium salt and the potassium salt
  • 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.
  • 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.
  • a development accelerator is necessary for carrying out a rapid development process. 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.
  • Amino compounds useful in the present invention as the amino compound include both inorganic amines such as hydroxylamine and organic amines.
  • organic amine aliphatic amines, aromatic amines, cyclic amines, aliphatic-aromatic mixed amines, or heterocyclic amines can be used.
  • primary, secondary, and tertiary amines and quaternary ammonium compounds are all effective.
  • 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.
  • 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.
  • aminopolycarboxylic acids e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ni
  • ethylenediaminetetraacetic acid iron(III) salts are preferred from the view points of quick processing and less environmental pollution.
  • an ethylenediaminetetraacetic acid iron(III) salt is particularly useful for an independent bleach solution and a blix solution.
  • the bleach solution the blix solution and the pre-bath thereof, if necessary, a bleach accelerator can be used.
  • bleach accelerator examples include 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.
  • 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.
  • Fixing agents include thiosulfates, thiocyanates, thioether series compounds, thioureas, and a large amount of an iodide, but thiosulfates are generally used.
  • sulfites, bisulfites, or carbonyl bisulfite addition products are preferable.
  • various compounds may be used for the purposes of preventing precipitation and saving water.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 e.g., brightening agents, hardening agents, etc.
  • ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc., to the stabilization solution.
  • 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).
  • formalin may be removed from the stabilization solution.
  • 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.
  • the silver halide color photographic material of the present invention may contain a color developing agent for simplifying and quickening processing.
  • a color developing agent for simplifying and quickening processing.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the photographic light-sensitive material of the present invention is a color photographic paper
  • a blixing process is generally employed.
  • blixing may also be employed.
  • 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.
  • 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.
  • 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.
  • TX-200R Triton X-200R
  • ZrO zirconium oxide
  • the diameters of the dye particles thus pulverized had a wide distribution from 0.05 ⁇ m to 1.15 ⁇ m in diameter.
  • a transparent polyethylene terephthalate (PET) film support having a thickness of 100 ⁇ m was used.
  • PET polyethylene terephthalate
  • 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.
  • 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.
  • 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
  • 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.
  • solution IV was added thereto after 7 minutes since the initiation of the addition of solution II over a period of 5 minutes.
  • 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.
  • the layer structure of the light-sensitive material and the composition of each layer were as follows.
  • the emulsion layer, the surface protective layer, the back electrically conductive layer, and gelatin layer other than the antihalation layer were coated as shown below to provide a photographic light-sensitive material.
  • the samples were subjected to reversal development processing and negative development processing as described below.
  • 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 - -
  • 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 - -
  • MTF was measured with an aperture of 400 ⁇ 2 ⁇ m 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.

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  • Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (8)

  1. Photographisches Silberhalogenidmaterial, das auf einem Träger eine hydrophile Kolloidschicht aufweist, die mindestens einen 2-Pyrazolin-5-on-oxonol-Farbstoff der allgemeinen Formel (I) in Form einer Dispersion feiner fester Teilchen davon enthält:
    Figure imgb0016
     worin R1 ein Wasserstoffatom, eine Aryl-Gruppe, eine Cyano-Gruppe, ein Halogenatom, -COOR2, COR3, CONR3R4, OR2, NHCOR3 oder NR3R4 (worin R2 eine Alkyl-Gruppe oder eine Aryl-Gruppe und R3 und R4 jeweils ein Wasserstoffatom, eine Alkyl-Gruppe oder eine Aryl-Gruppe repräsentieren) repräsentiert; wenn R1 eine Aryl-Gruppe ist, so kann diese unsubstituiert oder mit einer Alkyl-Gruppe, einer Alkoxy-Gruppe, einem Halogenatom, einer Amino-Gruppe, einer Cyano-Gruppe oder einer Phenoxy-Gruppe substituiert sein; R1 kann direkt oder durch eine divalente Verbindungsgruppe wie -O-, -S-, -NRCO-, -CONR-, -(CH2)pOCO-, -NHCONH- und -NHOCO- gebunden sein, worin R eine Alkyl-Gruppe mit 1 bis 6 Kohlenstoffatomen und p eine ganze Zahl von 0 bis 5 repräsentiert; und L1, L2, L3, L4 und L5 repräsentieren jeweils eine Methin-Gruppe, die unsubstituiert oder mit einer Methyl-, Ethyl- oder Phenyl-Gruppe substituiert sein kann; und der Farbstoff wird nach Dispergierung in einem flüssigen Medium verwendet.
  2. Photographisches Silberhalogenidmaterial gemäß Anspruch 1, worin R1 -OR2 repräsentiert, und R2 ist eine Alkyl-Gruppe mit 1 bis 5 Kohlenstoffatomen.
  3. Photographisches Silberhalogenidmaterial gemäß Anspruch 1, worin die Verbindung der Formel (I) in einer Menge von 1 bis 1000 mg/m2 vorhanden ist.
  4. Photographisches Silberhalogenidmaterial gemäß Anspruch 3, worin die Verbindung der Formel (I) in einer Menge von 1 bis 800 mg/m2 vorhanden ist.
  5. Photographisches Silberhalogenidmaterial gemäß Anspruch 1, worin die Teilchengröße der feinen festen Teilchen in der Dispersion nicht größer ist als 10 µm.
  6. Photographisches Silberhalogenidmaterial gemäß Anspruch 1, worin die Teilchengröße der feinen festen Teilchen in der Dispersion nicht größer ist als 2 µm.
  7. Photographisches Silberhalogenidmaterial gemäß Anspruch 1, worin die Teilchengröße der feinen festen Teilchen in der Dispersion nicht größer ist als 0,5 µm.
  8. Photographisches Silberhalogenidmaterial gemäß Anspruch 1, worin die Teilchengröße der feinen festen Teilchen in der Dispersion nicht größer ist als 0,1 m.
EP19910108816 1990-06-01 1991-05-29 Photographisches Silberhalogenidmaterial Expired - Lifetime EP0459456B1 (de)

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JP2745363B2 (ja) * 1992-09-25 1998-04-28 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
EP0643328B1 (de) * 1993-09-09 2001-05-09 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial und Farbbildherstellungsverfahren

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GB1114323A (en) * 1965-02-12 1968-05-22 Fuji Photo Film Co Ltd Silver halide light-sensitive materials
BE684714A (de) * 1965-07-28 1967-01-03
GB1338799A (en) * 1971-07-26 1973-11-28 Wolfen Filmfab Veb Oxonol dyestuffs and photographic material comprising silver halide emulsions
CA1130130A (en) * 1979-03-02 1982-08-24 Raymond G. Lemahieu Photographic silver halide materials comprising a 2-pyrazolin-5-one pentamethine oxonol dye
US4294917A (en) * 1979-05-22 1981-10-13 Ciba-Geigy Ag Photographic silver halide material containing a dye filter or a dye anti-halation layer
JPS59111641A (ja) * 1982-11-29 1984-06-27 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
JPS6426850A (en) * 1987-04-04 1989-01-30 Konishiroku Photo Ind Silver halide photographic sensitive material having superior rapid processability and superior sharpness of obtained dye image
JP2533367B2 (ja) * 1988-06-20 1996-09-11 富士写真フイルム株式会社 反射型カラ―感光材料とそのカラ―画像形成法

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