WO1998026330A1 - Emulsion photographique a l'halogenure d'argent a lisse renforce, et procede correspondant de formation d'image - Google Patents

Emulsion photographique a l'halogenure d'argent a lisse renforce, et procede correspondant de formation d'image Download PDF

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Publication number
WO1998026330A1
WO1998026330A1 PCT/JP1997/004591 JP9704591W WO9826330A1 WO 1998026330 A1 WO1998026330 A1 WO 1998026330A1 JP 9704591 W JP9704591 W JP 9704591W WO 9826330 A1 WO9826330 A1 WO 9826330A1
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WIPO (PCT)
Prior art keywords
silver halide
group
sensitive material
coupler
image forming
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PCT/JP1997/004591
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English (en)
Japanese (ja)
Inventor
Toshio Hirosawa
Kouji Katsube
Junichi Komiyama
Yoshiro Hayafuchi
Toshiko Nakamura
Tsuyoshi Fujita
Noboru Sonda
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Oriental Photo Industrial Co., Ltd.
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Application filed by Oriental Photo Industrial Co., Ltd. filed Critical Oriental Photo Industrial Co., Ltd.
Publication of WO1998026330A1 publication Critical patent/WO1998026330A1/fr

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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers
    • 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
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03517—Chloride content
    • 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
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • G03C2001/7635—Protective layer
    • 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
    • G03C2200/00—Details
    • G03C2200/16—Black-and-white material

Definitions

  • the present invention relates to a silver halide photographic light-sensitive material and an image forming method, and more particularly to a silver halide photographic light-sensitive material which can be processed with a benzyl alcohol-free color developer which has improved slipperiness on the surface thereof.
  • the present invention relates to a silver halide photographic light-sensitive material using a dye image and an image forming method.
  • a black-and-white photographic image is formed by processing a black-and-white photographic light-sensitive material with a black-and-white developer and forming a black-and-white image with a black image or a sepia-tone black and white image by toning.
  • it is also known to obtain a black-and-white image by adjusting the filter of a multilayer photographic material using a yellow coupler for the regular photosensitive layer, a magenta coupler for the orthophotosensitive layer, and a cyan coupler for the puncture-sensitive layer. .
  • Such a black-and-white image forming material is usually cut into sheets and stacked and packaged, or rolled and packaged.
  • the black-and-white image forming material packaged in this manner suffers from a drawback that the gloss of the surface is reduced due to adhesion, and it is difficult to pull out the rolled material when trying to pull it out.
  • the surface suffers from scratches due to abrasion and abrasion capri. Disclosure of the invention
  • a first object of the present invention is to provide a silver halide photograph having improved slipperiness and abrasion capri which can form a black-and-white image by a dye image by processing with a color developer substantially containing no benzyl alcohol.
  • the purpose is to provide photosensitive materials.
  • a second object of the present invention is to provide an image forming method capable of forming a black-and-white image by a dye image by processing with a color developer substantially containing no benzyl alcohol, having improved slipperiness and abrasion capri. It is to provide.
  • the present invention relates to a silver octogenide photographic material having at least one silver halide emulsion layer and a top protective layer on a support,
  • a silver halide content of the silver halide grains is 95 mol% or more
  • the silver halide emulsion layer contains a yellow coupler, a magenta coupler and a cyan blur
  • the top protective layer Is a silver halide photographic light-sensitive material containing at least one selected from a fluorine-based surfactant, silicon oil and liquid paraffin, and this silver halide photographic light-sensitive material that has been imagewise exposed is substantially treated with benzyl alcohol.
  • the silver halide photographic light-sensitive material of the present invention has improved slipperiness, has less abrasion capri, and can be processed into a color developer substantially free of benzyl alcohol to obtain a black-and-white image by a dye image.
  • fluorinated surfactant used in the present invention examples include, for example, fluoroalkyl (2 to 10 carbon atoms) carboxylic acid, N-perfluorooctanesulfonyl disodium glutamate, 3- [fluoroalkyl (carbon 6 to 11 1) oxy] — 1 —alkyl (3 to 4 carbon atoms) sodium sulfonate, 3— [ ⁇ —fluoroalkanoyl (6 to 8 carbon atoms) — ⁇ —ethylamino ] — 1 — Sodium propanesulfonate, ⁇ — [3 — (Perfluorooctanesulfonamide) propyl] mono, ⁇ — dimethyl ⁇ — power Rupoxymethylene ammonium betaine, fluoroalkyl (C 1 1 -20) carboxylic acid, perfluoroalkyl carboxylic acid (C7-C13), perfluorooctanesulfonic acid diethanol
  • Preferred compounds as the fluorine-based surfactant are compounds represented by the following general formula (I).
  • R> is a perfluorinated alkyl group having 3 to 9 carbon atoms
  • R 2 is an alkylene group having 1 to 6 carbon atoms
  • R 3 is a hydrogen atom or a carbon atom having 1 to 9 carbon atoms
  • X represents three alkyl groups, and X represents a hydrogen atom or a metal atom.
  • Specific examples include potassium N-perfluorooctylsulfonyl-N-n-propylglycine, potassium N-perfluorooctylsulfonyl N-ethylglycine, and the like.
  • the amount of the fluorosurfactant to be used is preferably from 0.1 mg to 1.0 g, particularly preferably from 1 mg to 100 mg per 1 m 2 .
  • the silicone oil used in the present invention is a compound represented by the following general formula (II).
  • R 4 represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms
  • R 5 represents an alkyl group having 1 to 3 carbon atoms
  • R 6 represents Represents an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms.
  • m represents an integer of 0 to 2000.
  • the amount of silicone for oil is lm 2 per 5 mg ⁇ 2. 0 g, in particular 1 0 mg ⁇ 1 0 0 mg range preferred.
  • Liquid paraffin used in the present invention can be obtained by purchasing a commercial product.
  • the amount of the liquid paraffin to be used is preferably in the range of 5 mg to 2.0 g per m 2 , particularly preferably in the range of 10 mg to 100 mg.
  • top protective layer In order to incorporate the fluorosurfactant, silicone oil and liquid paraffin of the present invention into the top protective layer, it is necessary to dissolve or disperse in water or an organic solvent such as methanol, isopropyl alcohol, acetone, or a mixed solvent thereof. Add to the top protective layer coating solution and apply dip coat, air knife coat, slide hopper, etc. or apply two or more layers at the same time to protect the top. It can be contained in a layer.
  • an organic solvent such as methanol, isopropyl alcohol, acetone, or a mixed solvent thereof.
  • the halogen composition of the silver halide emulsion used in the present invention is such that 95 mol% or more of the silver halide grains are silver chloride and are composed of silver chlorobromide containing substantially no silver iodide. preferable.
  • the particle diameter and, in the case of cubic particles, the ridge length divided by the particle size and expressed as an average based on the projected area) are not particularly limited, but are preferably 3 m or less.
  • the particle size distribution may be narrow or wide.
  • the silver halide grains may have a regular crystal form such as a cube or an octahedron, or may have an irregular crystal form such as a sphere or a plate, or these crystal forms. May be used. It may consist of a mixture of particles of various crystal forms.
  • an emulsion may be used in which tabular silver halide grains having a diameter of 5 times or more the thickness of the grains occupy 50% or more of the total projected area.
  • the particles may be such that the latent image is mainly formed on the surface, or may be the particles that are mainly formed inside the particle.
  • the silver halide grains may have a layered structure having layers with different halogen compositions on the inside and the outside, and may be joined to silver halide grains with different halogen compositions by epitaxy. Good.
  • the silver halide grains of the silver halide emulsion have a localized layer having a silver bromide content of 30 to 60 mol% locally grown on the surface of the halogen particles, particularly on the corners of the grains.
  • This localized phase is preferably composed of 0.5 to 5% of silver based on the total silver constituting the silver halide grains.
  • the method for producing these epitaxy silver halide grains is described in the specification of U.S. Pat. No. 2,733,430.
  • the silver halide emulsion used in the present invention is described in P. Glafkides, Chimieet Physique P hotographique (Paul Monte 1 company, 1967), GF Duffin. P hotographic Emulsion C hemistry (published by T He Focal Press, 1966), V.L.
  • the method of reacting a soluble silver salt with a soluble halide salt includes a forward flow method, a reverse flow method, a simultaneous mixing method, and a combination thereof. Either may be used.
  • a method in which pAg in a solution in which silver halide is formed is kept constant, or a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.
  • Two or more silver halide emulsions formed separately may be used as a mixture.
  • Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts, or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. during the formation of silver halide grains or during the physical ripening process. You may.
  • Silver halide emulsions are usually chemically sensitized.
  • sulfur sensitization using a compound containing sulfur that can react with active gelatin or silver for example, thiosulfate, thioureas, mercapto compounds, rhodanines, etc.
  • a reducing substance for example, stannous tin
  • noble metal sensitization using noble metal compounds for example, complex salts of metals such as gold, platinum, iridium, and palladium. Sensation Can be used alone or in combination.
  • the silver halide emulsion of the present invention comprises at least one sensitizing dye represented by the general formula (m), at least one sensitizing dye represented by the general formula (IV), and It is preferable that at least one of the sensitizing dyes represented by (VI) or (VI) is spectrally sensitized.
  • R 7 and R 8 are an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group) , An n-hexyl group, an isohexyl group, etc.), a substituted alkyl group having 1 to 4 carbon atoms [for example, a hydroxylalkyl group (for example, a 2-hydroxyshethyl group, a 3-hydroxypropyl group, 2-hydroxypropyl group, etc., sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, etc.), carboxyalkyl group (for example, 2-carboxyethyl) Group, 3-carboxypropyl group,
  • R 1 and R 8 are a substituted alkyl group.
  • 2 1 and sigma 2 is In example substituents (e.g., halogen atom, alkyl group, alkoxy group, Ariru group, Shiano group.
  • a benzene nucleus or a naphthalene nucleus which may have an alkoxycarbonyl group, a trifluoromethyl group, an alkylsulfonyl group, an alkylsulfamoyl group, an acylamino group, an alkylsulfamoyl group, an acetyloxy group, etc.
  • Represents a group of nonmetallic atoms required for X> represents a commonly used anion group (eg, chlorine ion, bromine ion, iodine ion, perchlorate ion, p-toluenesulfonate ion, ethylsulfate ion, etc.), P, represents 1 or 2 When P i is 1, an inner salt is formed.
  • alkyl group having 1 carbon atoms which may 6 have a sulfo group as a substituent e.g., methyl group, Echiru group, n- flop port building Group, isopropyl group, ⁇ -butyl group, isobutyl group, n-hexyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, etc.
  • A is a hydrogen atom, and has 1 to 3 carbon atoms.
  • An alkyl group (eg, methyl group; ethyl group, n-propyl group, isopropyl group, etc.), an aryl group (eg, phenyl group, etc.), Y, and Y 2 represent an ⁇ atom, an oxygen atom, a selenium atom, a ⁇ — , R! !
  • Represents an alkyl group having 1 to 3 carbon atoms eg, a methyl group, an ethyl group, n-propyl group, an isopropyl group, etc.).
  • Z 3 and Z 4 represent a substituent (for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, A non-metallic atom group necessary for forming a benzene ring or a naphthylene ring which may have a benzyl group, an alkoxycarbonyl group or a cyano group.
  • chi 2 represents ⁇ two one group (e.g., chloride, bromide, iodide ion, perchlorate ion, .rho. toluenesulfonate ion, Echiru sulfate ion).
  • [Rho 2 is 1 or 2
  • [rho 2 forms an intramolecular salt when 1.
  • R 12 , R 13 , R 14 and R 15 represent an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, —Butyl, isobutyl, n-hexyl, iso- A substituted alkyl group having 1 to 4 carbon atoms [eg, a hydroxyalkyl group (eg, a 2-hydroxyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, etc.)], a sulfoalkyl group Groups (eg, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, etc.), carboxyalkyl groups (eg, 2-carboxyethyl group, 3-carboxypropyl group, 3-carboxybutyl group, etc.), carboxyalkyl groups (
  • R 12 and R 13 is a substituted alkyl group.
  • R 14 and R 5 is a substituted alkyl group.
  • a 2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc.), and an aryl group (eg, a phenyl group, etc.).
  • Z 5 , ⁇ , ⁇ 7 and ⁇ 8 represent a substituent (for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a cyano group, an alkoxycarbonyl group, a trifluoromethyl group, an alkylsulfonyl group, an alkylsulfamoyl group) , An acylamino group, an alkyl group, a rubamoyl group, an acetyloxy group, etc.), which represents a group of non-metallic atoms necessary for forming a benzene nucleus or a naphthalene nucleus, and 9 represents a substituent (for example, an alkyl group) Represents a group of non-metallic atoms necessary to form a 6-membered ring nucleus which may have.
  • a substituent for example, a halogen atom, an alkyl group, an alkoxy group, an
  • ⁇ 3 and ⁇ ⁇ ⁇ represent commonly used anion groups (for example, chloride ion, bromide ion, iodine ion, perchlorate, ⁇ -toluenesulfonic acid ion, ethyl sulfate ion, etc.).
  • sensitizing dyes per mol of silver halide 1 0 'in the silver halide emulsion; used at a concentration of ⁇ 1 0 3 mol.
  • a method of dispersing the sensitizing dye directly in a silver octalogen emulsion may be used, and a suitable solvent such as methyl alcohol or ethyl alcohol may be used. Alcohol, acetone, ⁇ , ⁇ -dimethylformamide, ethyl acetate, or a mixed solvent of these, or dissolved in a solvent containing a surfactant, and then added to the silver halide emulsion Method can be applied.
  • sensitizing dyes can be added to a silver halide emulsion at the time of forming silver halide grains or after completion of physical ripening. Preferably, it is added to the silver halide emulsion after completion of physical ripening, before chemical ripening, during chemical ripening, or after chemical ripening. These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used particularly for supersensitization.
  • the emulsion may contain a dye which has no sensitizing effect or a substance which does not substantially absorb visible light and which exhibits supersensitization.
  • aminostyryl compounds substituted with a nitrogen-containing heterocyclic group for example, described in U.S. Pat. Nos. 2,933,390 and 3,635,721)
  • An aromatic organic acid formaldehyde condensate for example, a compound described in US Pat. No. 3,743,510
  • a cadmium salt for example, an azaindene compound and the like. Is also good.
  • Yellow couplers that can be used in the present invention include Oil Pro Tact-type acylacetamide-based couplers can be mentioned. Specific examples thereof are described in U.S. Pat. Nos. 2,407,210, 2,875,057, and 3,265,506. Has been described. In the present invention, it is preferable to use a two-equivalent yellow coupler, as described in U.S. Patent Nos. 3,408,194, 3,447,928, and Oxygen atom departure type yellow couplers described in each specification such as 933, 501 and 4,401,752, JP-B-58-10739 U.S. Pat. Nos. 4,022,620 and 4,326,024, Research Disclosure, 18, 053 (Apr. 1987) British Patent Nos.
  • the pivaloylacetanilide couplers are characterized by the fastness of the coloring dye, while the benzoylacetanilide couplers are characterized by good color development.
  • the magenta couplers usable in the present invention include oil-protected indazolone-based or cyanoacetyl-based couplers, and preferably 5-pyrazolone-based and pyrazoloazol-based couplers such as pyrazotriazole-based couplers. Can be mentioned.
  • the 5-pyrazolone-based couplers, in which the 3-position is substituted with an arylamino group or an acylamino group, are preferred from the viewpoint of the hue and the coloring speed of the coloring dye. Specific examples thereof are described in US Pat. No. 2,311, No. 08, No. 2, 334, 703, No. 2, 600, 788, No. Nos. 2, 908, 573, No. 3, 062; No. 653, No.
  • a 2-equivalent 5-pyrazolone-based coupler is particularly preferred.
  • the leaving group a nitrogen atom leaving group described in U.S. Pat. No. 4,310,619, U.S. Pat.
  • An arylthio group described in the specification of Japanese Patent No. 8997 can be mentioned.
  • a 5-pyrazolone-based coupler having a ballast group described in European Patent No. 73,636 is a preferred coupler having high color-forming reactivity.
  • Examples of the pyrazoloazole couplers include pyrazolo [1,5-b] [1,2,4] triazoles described in European Patent No.
  • Examples of the cyan coupler that can be used in the present invention include oil-protected naphthol-based couplers and phenol-based couplers, which are described in US Pat. No. 2,474,293. No. 4,052,212, No. 4,143,396, No. 4,228,233 No. 4 and Nos. 4, 296, 200 Oxygen atom-elimination-type highly active 2 equivalent naphthol couplers described in the detailed description can be mentioned.
  • Examples of phenolic couplers include U.S. Pat. Nos. 2,369,929, 2,423,730, 2,772,162, and Couplers described in each specification, such as No. 81, 171 and Nos. 2, 895, 826, can be mentioned.
  • Cyan couplers which are robust to temperature and humidity are preferred, and phenolic cyan couplers described in U.S. Pat. No. 3,772,022, U.S. Pat. No. 2,772,1.
  • the coupler used in the present invention can be introduced into a silver halide emulsion by various dispersion methods.
  • a solid dispersion method an alkali dispersion method, preferably a latex dispersion method, more preferably an oil-in-water dispersion method can be used.
  • the oil-in-water dispersion method after dissolving in a single solution of a high-boiling organic solvent having a boiling point of 175 ° C or more and a low-boiling auxiliary solvent alone or in a mixture of both, water is added in the presence of a surfactant.
  • it is finely dispersed in an aqueous medium such as an aqueous gelatin solution.
  • the high-boiling organic solvent is described in U.S. Pat. No. 2,322,027.
  • the dispersion may be accompanied by a phase inversion, and if necessary, the auxiliary solvent can be removed or reduced by distillation, noodle washing, ultrafiltration or the like before use for coating.
  • high-boiling organic solvents examples include fluoric acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), and esters of phosphoric acid or phosphonic acid (trifenyl phenol) Phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tree 2-ethylhexyl phosphate, trididecyl phosphate, tributoxyshethyl phosphate, triclopropyl propyl phosphate, G2 —Ethylhexyl phenyl phosphate, benzoic acid ester (2-ethylhexylbenzoate, dodecylpentolate, 2-ethyltyloxyl p-hydroxybenzolate, etc.), amide (
  • auxiliary solvent one having a boiling point of about 30 ° C. to about 60 ° C. can be used. Specific examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, and cycloalkyl. Hexanone, 2-ethoxyshethyl acetate, dimethylformamide and the like can be mentioned.
  • Gelatin is mainly used as a binder or protective colloid which can be used in the emulsion layer or other hydrophilic colloid layers of the photographic light-sensitive material of the present invention.
  • gelatin derivatives for example, gelatin derivatives, albumin , A protein such as casein, cellulose derivatives such as ethylcellulose and carboxymethylcellulose, a sugar derivative such as a starch derivative, a mono- or copolymer such as polyvinyl alcohol, polyacrylic acid, polyacrylamide, and polymethacrylic acid.
  • hydrophilic polymers can be used.
  • the emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention may prevent capri during the manufacturing process, storage or development, or Various compounds can be added for the purpose of stabilizing the performance.
  • this compound include azoles such as nitroindazoles, nitrobenzimidazoles, mercaptothiazols, mercaptobenzodimidazoles, mercaptothiadiazoles, aminotriazols, and benzols.
  • Mercapto triazines, thioketone compounds, azaindenes such as triazoles, mercaptotetrazoles (especially, 1-fluoro-5-mercaptotetrazole), such as triazaindenes, tetraazaindenes (especially, 4-hydroxy-1 , 3,3a, 7-tetrazaindenes), pentaazaindenes, benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc., have been known as antifoggants or stabilizers. Many compounds can be mentioned. Of these, particularly preferred are benzotriazoles and nitroindazoles. These compounds may be contained in a processing solution used for the development processing.
  • the emulsion layer and the other hydrophilic colloid layer of the photographic light-sensitive material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color capri inhibitor.
  • the emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention can contain an inorganic or organic hardener.
  • Hardening agents include, for example, chromium salt (chromium alum, etc.), N-methylol compound, dioxane derivative, active vinyl compound (eg, 1,2,5—triacryloylurexahydro-s—triazine, 1,3-vinylsulfonyl-2-propanol, etc., active halogen compounds (for example, 2,4-dichloro-16-hydroxy) Droxy S-triazine, etc.), and mucohalic acids (eg, mucochloric acid, mucophenoxycyclolic acid, etc.). These hardeners can be used alone or in combination.
  • the emulsion layer and the other hydrophilic colloid layer of the photographic light-sensitive material of the present invention may be composed of a coating aid, an antistatic agent, an improvement in slipperiness, an emulsification dispersion, an adhesion prevention and an improvement in photographic properties.
  • Surfactants can be included for various purposes such as (eg, development acceleration, high contrast, sensitization, etc.).
  • the surfactant include saponin, alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglycerides, alkylphenol polyglycerides, etc.), fatty acid esters of polyhydric alcohols , Nonionic surfactants such as alkyl esters of sugars, and acidic acids such as carboxy groups, sulfo groups, sulfate groups, and phosphate groups such as alkyl carboxylate salts, alkyl sulfate esters, and alkyl phosphate esters.
  • the emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention may contain a dispersion of a water-soluble or poorly-soluble synthetic polymer for the purpose of improving dimensional stability and the like.
  • a water-soluble or poorly-soluble synthetic polymer for the purpose of improving dimensional stability and the like.
  • a combination of monounsaturated dicarboxylic acid, styrene sulfonic acid and the like can be used in combination with a polymer as a monomer component.
  • hydrophilic colloid layers other than the silver halide emulsion layer in the present invention include a surface protective layer, a filter layer, an anti-halation layer and an antistatic layer.
  • a hydrophilic colloid layer such as a surface protective layer may contain a matting agent for the purpose of preventing adhesion and improving the surface condition.
  • a matting agent for the purpose of preventing adhesion and improving the surface condition.
  • As the matting agents US Pat. Nos. 2,701,245, 2,992,101, 4,142,894, Fine particles such as homopolymers of polymethyl methacrylate, copolymers of methyl methacrylate and methacrylic acid, starch, silica, magnesium oxide, etc. described in the specifications of 396 and 706 can be used. .
  • the photographic light-sensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer.
  • an ultraviolet absorber in the hydrophilic colloid layer.
  • U.S. Pat. Nos. 3,533,794 and 4,236 013, Japanese Patent Publication No. 51-65040, and U.S. Pat.
  • the photographic light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic color layer as a filter dye or for various purposes such as prevention of image formation.
  • a water-soluble dye in the hydrophilic color layer as a filter dye or for various purposes such as prevention of image formation.
  • Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and mechanin dyes are useful.
  • an anti-fading agent can be used in the emulsion layer and other hydrophilic colloid layers, and the anti-fading agent can be used alone or in combination of two or more.
  • the anti-fading agent include phenols or phenyl ether compounds described in JP-A-59-125732 and JP-A-60-97353.
  • Metal complexes and the like are examples of the anti-fading agent.
  • borols such as trimethylolpropane, pentanediol, butanediol and ethylene glycol and glycerin can be used as plasticizers.
  • a fluorescent whitening agent, a development accelerator, a pH adjuster, a thickener, an antistatic agent, and the like can be added to the emulsion layer and other hydrophilic colloid layers.
  • Examples of the support used in the photographic light-sensitive material of the present invention include films made of synthetic polymers such as cellulose acetate, cellulose acetate, nitrocellulose, polystyrene, polyethylene terephthalate, and polycarbonate. No writer paper or ⁇ -olefin polymer (for example, polyethylene , Polypropylene) or the like, or paper coated or laminated, synthetic paper, or the like.
  • the support may be colored using a dye or a pigment. When such a support is used for a reflective material, it is preferable to add a white pigment to the support or the laminate layer.
  • the white pigment examples include titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white, alumina white, and titanium phosphate.
  • titanium dioxide, barium sulfate, and zinc oxide are useful.
  • the surface of these supports is generally subbed to improve adhesion to the photographic emulsion.
  • the surface of the support may be subjected to a treatment such as corona discharge or ultraviolet irradiation before or after the undercoating treatment.
  • a hydrophilic color layer containing a high density of a white pigment is further provided between the support and the emulsion layer to improve whiteness and sharpness of a photographic image.
  • a synthetic resin film into which a white pigment is kneaded is used, in addition to the improvement of smoothness, glossiness, and sharpness, saturation and depiction of a dark area can be improved. Excellent photographic images are obtained.
  • polyethylene terephthalate and cellulose acetate are particularly useful as the synthetic resin film
  • barium sulfate and titanium oxide are particularly useful as the white pigment.
  • the silver halide photographic light-sensitive material of the present invention can form a black-and-white image by exposing from a black-and-white negative film or a light-sensitive negative film.
  • the color developing solution that can be used in the present invention is preferably an aqueous solution mainly containing an aromatic primary amine developing agent.
  • developing agents 4-amino-N, N-getylaniline, 3-methyl-4-amino — N, N —Jetylaniline, 4-Amino— N —Ethyru N—3—Hide Mouth Quichetilaniline, 3-Methyl—4-amino—N—Ethyru N—3 —Hydroxicetilin, 3-Methyl-4-amino —N—Ethyru N—3—Methanesulfonamidoethylaniline, 4-Amino-3—Methyl N—Ethyru N—3—Methoxyxylaniline, etc.
  • the color developing solution can contain pH buffering agents such as carbonates, borates and phosphates, and anti-capri agents such as bromides, iodides and organic pre-preventive agents.
  • a development accelerator such as a water softener, an alkali metal sulfite, a polyethylene glycol, a polyethylene glycol, a quaternary ammonium salt, or an amine, a competitive coupler, a sodium boron hydride, or the like.
  • An auxiliary developing agent such as virazolidone, a viscosity-imparting agent, a polycarboxylic acid chelating agent described in US Pat. No.
  • benzyl alcohol is not substantially contained in the developer means that even if benzyl alcohol is contained in the developer, it is 5 m 1/1 or less. More preferably, it does not contain benzyl alcohol.
  • the silver halide photographic light-sensitive material of the present invention is usually bleached after color development.
  • the bleaching process may be performed simultaneously with the fixing process, or may be performed separately.
  • the bleaching agent for example, compounds of polyvalent metals such as iron (II), cobalt (II), chromium (VI), and copper (II), peracids, quinones, and nitros compounds are used.
  • the iron (m) complex salt of ethylenediaminetetraacetate is useful in both an independent bleaching solution and a single bath bleach-fixing solution.
  • a water washing process may be performed.
  • Color development can be performed at any temperature between 18 ° C and 55 ° C.
  • the reaction is carried out at 30 ° C. or higher, particularly preferably at 35 ° C. or higher.
  • the time required for development is in the range of about 1 minute 30 seconds to about 20 seconds, with shorter times being preferred.
  • replenishment of the solution is preferable, and 100 ml or more, preferably 160 ml or 330 ml of the solution is replenished per square meter of the processing area.
  • Bleaching and fixing can be carried out at any temperature from 18 ° C to 50 ° C, preferably at least 30 ° C.
  • the processing time can be reduced to 1 minute or less, and the replenishing amount of the liquid can be reduced.
  • the time required for washing after color development or bleach-fixing is usually within 1 minute, and processing can be performed within 1 minute using a stabilizing bath.
  • the dye that has developed develops and fades due to mold during storage.
  • the cyan dye is particularly susceptible to deterioration by mold, and it is preferable to use a protective agent.
  • Specific examples of the fungicide include 2-thiazolyl penzimidazoles described in JP-A-57-157244.
  • the fungicide is incorporated into the silver halide photographic material. It may be added from the outside in the development processing step, and can be added in any step as long as it coexists with the processed photosensitive material.
  • Silver chlorobromide emulsion (monodispersed cube, average grain size 0.5 m, silver bromide content 0.9 mol%, potassium hexaclo iridium (IV) acid salt on the grain surface 1 x 1 per mole of silver 0 and 5 mole is contained.) was prepared, by adding Chio sulfate sodium ⁇ beam, optimally after chemical sensitization, which 1 per mole of silver sensitizing dye a to X 1 0 4 . mole, of sensitizing dye B 1 3 X 1 0- 4 mol, 4 X 1 0 sensitizing dye C - were added 5 mol. After standing for 20 minutes, 50 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer per mol of silver halide.
  • UV absorber A 0.15 g m UV absorber B 0.20 g m High boiling solvent 0.2 g m
  • Anti-irradiation dye A 0.3 g / m Anti-irradiation dye B 0.03 g / antioxidant 0.3 g / m Support Polyethylene-coated paper Fluorinated surfactants are available from Dainippon Ink and Chemicals, Inc.
  • the product name is F-120 (N-perfluorooctylsulfonyl-N-n-propylglycine) and the silicone oil is KF-410 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the liquid paraffin used was a special grade manufactured by Kanto Chemical Co., Ltd.
  • the fluorinated surfactants, silicone oils, fluidized paraffins used, and the amounts used (per lm 2 ) are shown in Table 1.
  • Other additives are as follows. High-boiling solvent n-dibutylphthalate UV absorber A 5Hn (t UV absorber B
  • Tivanol S FP is a fluorescent whitening agent manufactured by Ciba Geiger-Akchenmaschine. Bleaching fixer

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

Abstract

La présente invention concerne une émulsion photographique à l'halogénure d'argent qui peut donner des images en noir et blanc par développement avec un bain de développement couleurs exempt de benzyl alcool. Cette émulsion se caractérise notamment un meilleur lissé provoquant de meilleur qualité donnant naissance à moins de brouillard d'abrasion. L'invention concerne également le procédé correspondant de formation d'image. En l'occurrence, on utilise un produit photographique à l'halogénure d'argent constitué d'un support, recouvert d'au moins une couche d'émulsion photographique à l'halogénure d'argent et d'une couche supérieure de protection. La teneur molaire en chlorure d'argent des grains d'halogénure d'argent constituant la couche d'émulsion à l'halogénure d'argent est d'au moins 90 %. De plus, la couche d'émulsion à l'halogénure d'argent contient un coupleur jaune, un coupleur magenta et un coupleur cyan. La couche supérieure de protection contient l'un au moins des produits du groupe des agents tensio-actifs fluorés, huiles siliconées et paraffine liquide. Le procédé de formation de l'image consiste à exposer à l'image objective l'émulsion photographique et à développer le matériau résultant dans un bain de développement sensiblement exempt de benzyl alcool.
PCT/JP1997/004591 1996-12-13 1997-12-12 Emulsion photographique a l'halogenure d'argent a lisse renforce, et procede correspondant de formation d'image WO1998026330A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP8352852A JPH10171068A (ja) 1996-12-13 1996-12-13 滑り性の改良されたハロゲン化銀写真感光材料及び画像形成方法
JP8/352852 1996-12-13

Publications (1)

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WO1998026330A1 true WO1998026330A1 (fr) 1998-06-18

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PCT/JP1997/004591 WO1998026330A1 (fr) 1996-12-13 1997-12-12 Emulsion photographique a l'halogenure d'argent a lisse renforce, et procede correspondant de formation d'image

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Country Link
JP (1) JPH10171068A (fr)
WO (1) WO1998026330A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9259549B2 (en) 2002-01-17 2016-02-16 Resmed R&D Germany Gmbh Breathing mask arrangement and a forehead support device for same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5972439A (ja) * 1982-10-19 1984-04-24 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
JPH06118543A (ja) * 1992-10-08 1994-04-28 Konica Corp ハロゲン化銀写真感光材料及び画像形成方法及び直接鑑賞用写真プリント材料
JPH06505580A (ja) * 1991-12-19 1994-06-23 イーストマン コダック カンパニー 写真要素及び黒白像の形成方法
JPH0792603A (ja) * 1993-09-21 1995-04-07 Konica Corp ハロゲン化銀写真感光材料及び直接鑑賞用写真プリント材料とそのプリント画像形成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5972439A (ja) * 1982-10-19 1984-04-24 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
JPH06505580A (ja) * 1991-12-19 1994-06-23 イーストマン コダック カンパニー 写真要素及び黒白像の形成方法
JPH06118543A (ja) * 1992-10-08 1994-04-28 Konica Corp ハロゲン化銀写真感光材料及び画像形成方法及び直接鑑賞用写真プリント材料
JPH0792603A (ja) * 1993-09-21 1995-04-07 Konica Corp ハロゲン化銀写真感光材料及び直接鑑賞用写真プリント材料とそのプリント画像形成方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9259549B2 (en) 2002-01-17 2016-02-16 Resmed R&D Germany Gmbh Breathing mask arrangement and a forehead support device for same

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