US3923517A - Method for rapidly forming photographic images - Google Patents

Method for rapidly forming photographic images Download PDF

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Publication number
US3923517A
US3923517A US442556A US44255674A US3923517A US 3923517 A US3923517 A US 3923517A US 442556 A US442556 A US 442556A US 44255674 A US44255674 A US 44255674A US 3923517 A US3923517 A US 3923517A
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Prior art keywords
gelatin
chloride
layer
isocyanate
photographic
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US442556A
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English (en)
Inventor
Nobuo Yamamoto
Ikutaro Horie
Kiyotaka Hori
Shigeru Nagatomo
Hidefumi Sera
Kenji Yokoo
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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
    • G03C1/7614—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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
    • 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
    • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/151—Matting or other surface reflectivity altering material

Definitions

  • ABSTRACT A method for rapidly forming photographic images which comprises processing a photographic light sensitive material comprising at least one silver halide emulsion layer, and a gelatin derivative-containing upper most layer at a temperature of at least 30C.
  • photographic light-sensitive materials contain a hydrophilic natural high molecular weight substance and/or a hydrophilic synthetic high molecular weight substance, as well as gelatin, in a silver halide emulsion layer. a photographic auxiliary layer such as an intermediate layer, a protective layer or an antihalation layer, or in a subbing layer interposed between these layers and a support.
  • Photographic materials containing these hydrophilic high molecular substances are usually processed, after exposure, in various aqueous solutions which differ from each other in pH, salt concentration and solution temperature in the steps of development, stopping, fixing and washing (and bleaching in the case of color light-sensitive materials), in order to form photographic images.
  • a pre-hardening bath containing a hardener immediately before developing the material
  • a method of conducting development and hardening at the same time using a developer containing a hardener, and like methods are known.
  • Additional method for controlling reticulation include a method of coating carboxymethylated casein or ethyl cellulose sulfate sodium salt in advance on the uppermost layer of the emulsion side as a replacement for a gelatin protective layer usually employed in a photographic light-sensitive material.
  • This method is believed to be advantageous in that the addition of a large amount of hardener to photographic layer is not required.
  • carboxymethylated casein has the disadvantage that removal therefom of impurities which adversely affect the photographic properties is difficult.
  • An additional production disadvantage is that it is difficult to form a uniform coating layer of this material on an emulsion layer due to the poor coating propety of an aqueous solution of carboxymethylated casein.
  • an object of the present invention to provide a method for rapidly forming images with good quality by processing a silver halide photographic lightsensitive material at an elevated temperature.
  • Another object of the present invention is to provide an excellent photographic light-sensitive material in which softening or reticulation of the photographic layer does not take place during or after rapid processing at an elevated temperature.
  • a further object of the present invention is to provide a method for producing a photographic light-sensitive material having practical productivity, photographic properties and physical properties, and for conducting photographic processing thereof at a high temperature without deteriorating these characteristics, thus rapidly obtaining images with high quality.
  • the present invention provides the advantage that photographic images having excellent quality photographic and physical properties can rapidly be obtained. That is, the present invention provides the ability to reduce the change in the photographic and physical properties of the light-sensitive material before processing and to conduct rapid photographic processing without a deterioration in the photographic properties, such as fogging, reduction in sensitivity, etc., and with out physical deterioration such as reticulation due to processing at an elevated temperature or over a wide pH range.
  • a further advantage of the present invention is that, since the gelatin derivative incorporated in the uppermost layer provided on a photographic light-sensitive material has excellent solubility, excellent compatibility with other high molecular weight substances, excellent coating properties and the like, no difficulties in the production of photographic light-sensitive materials are encountered.
  • the gelatin derivative used in the present invention is a chemically modified gelatin which is produced as a result of processing gelatin with a monofunctional agent capable of reacting with an amino group, an imino group, a carboxyl group and/or a hydroxy group, contained in the polar or hydrophilic residue in the various amino acid fractions forming the gelatin molecules.
  • the residue of the functional group containing agent suitably is present in an amount of from about 0.02 to about 1.5m mol/g, preferably from 0.05 to 1.0m mol/g in the gelatin derivative (on a dry basis).
  • gelatin which is used in the present specification as referring to the starting material of the gelatin derivative of the present invention, is also used to described the proteinic substance derived from collagen. Also. this term includes any other products which are substantially equivalent thereto, such as synthetic gelatins.
  • gelatin there are known the socalled alkali-processed gelatin" derived from collagen through treatment with lime or the like, the so-called acid-processed gelatin with the processing being with hydrochloric acid or the like, the so-called enzyme-processed gelatin with the processing being with a hydrolase or the like. and low molecular weight gelatin obtained by further hydrolyzing the abovedescribed gelatins using various methods. Any of these gelatins can be used for the production of the gelatin derivative necessary for practicing the present inven tion.
  • any compound that possesses one functional group per molecule capable of reacting with an amino group, an imino group, a carboxyl group and/or a hydroxy group contained in the gelatin molecule can be used for preparing gelatin derivatives which are substantially equivalent in usefulness in the practice of the present invention.
  • Representative functional groups are illustrated by the following: -NCO, -NCS, --NHCOSO M or NHCS-SO ,M (where M is an alkali metal such as sodium, potassium, etc.
  • R, and R each is a hydrogen atom or a lower alkyl group e.g., having up to 4 carbon atoms such as a methyl group or ethyl group; and X is a halogen atom such as Cl, Br, etc.
  • isocyanates such as phenyl isocyanate, p-tolyl isocyanate, 4-bromophenyl isocyanate, 4-chlorophenyl isocyanate, 2-nitrophenyl isocyanate, 4-ethoxycarbonylphenyl isocyanate, l-naphthyl isocyanate, phenyl isocyanatebisulfite adduct, p-biphenyl isocyanatebisulfite adduct, etc. or a precursor thereof;
  • isothiocyanates such as phenyl isothiocyanatc, p'tolyl isothiocyanate, phenyl isothiocyanate-bisulfide adduct, etc. or a precursor thereof;
  • aziridines such as N-pentanoyl-2-ethyl-l-aziridine, l-phenylcarbamoylaziridine, 2-methyll -phenylcarbamoylaziridine, l-dimethylaminosulfonylaziridinc, lbenzoylazridine, 4nitrobenzyol-l-aziridine, l-(2- chlorophenyl )carbamoyll -aziridine, phenyl)carbamoylaziridine l-( n-butylsulfonyl )aziridine, l-( phenylsulfonyI-Z-methylaziridine, 2-( laziridinyl )-4, 6-bisethylaminol ,3,5-triazine, l-phenyl- 3-(2-chloroethyl)urea, etc. or a precursor thereof;
  • activated vinyl compounds eg, Containing groups such as a carbonyl group, a sulfonyl group, etc.
  • activated vinyl compounds such as N-vinylsulfonyl-p-toluidine.
  • sulfonyl halides such as, the arylsulfonyl halides, e.g., benzenesulfonyl chloride, 4-methoxybenzenesulfonyl chloride, 4-phenoxybenzenesulfonyl chloride. 4- chlorobenzenesulfonyl chloride, 4-bromobenzenesulfonyl chloride, 4-methylbenzenesulfonyl chloride. 3- nitrobenzenesulfonyl chloride, 3-carboxybenzenesulfonyl chloride.
  • Z-naphthalenesulfonyl chloride 4- aminobenzenesulfonyl fluoride, 3,4-diaminobenzenesulfonyl fluoride, 3-carboxybenzenesulfonyl fluoride. etc. and the lower alkylsulfonyl halides such as methanesulfonyl chloride and ethansulfonyl chloride, etc.;
  • carboxylic acid halides such as the arylcarboxylic acid halides. e.g., 4-nitrobenzoyl chloride, 4-carboxybenzoyl bromide, etc.; and the aliphatic carboxylic acid halides, e.g., butyric acid chloride, caproic acid chloride and caprylic acid chloride. etc,;
  • carboxylic acid anhydrides including aromatic and aliphatic carboxylic acid anhydrides such as succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, isatoic acid anhydride, monomethylsuccinic acid anhydride, glutaric acid anhydride. benzoic acid anhydride, trimellitic acid anhydride, 3,6-dichlorophthalic acid anhydride, diglycollic acid anhydride, nitrophthalic acid anhydride, etc.;
  • oxirane ring-containing compounds such as 3- phenyloxy-l ,2-epoxypropa ne. 3-( 3-methylphenyloxy l,2,-epoxypropane, 3-( 2,4-dibromophenyloxy)-1,2- epoxypropane, 3-(4-acetylaminophenyloxy )-l 2-epoxypropane, 3-( 2-biphenyloxy)-l ,2-epoxypropane, 3- (2,4-dinitrol-naphthoxy l ,2-epoxypropanc, lchloro-2-hydroxy-3-phenyloxypropane, epichlorohyl 3-methyl- (where Y is a lower alkyloxy group; an aryloxy group such as phenox an NH lovtci alkyl group; and
  • lower alkyl lowcr alkyl or an NH-aryl group such as such as bromoacetic acid, chloroacetic acid, 2- chloro-4,6-dimethoxy-l ,3,5-triazine and 2-chloro-4,6- diethylaminol ,3,S-triazine, etc.;
  • activated esters of carboxylic acids including aromatic acid and aliphatic acids such as o-nitrophcnyl benzoate, p-nitrophenyl acetate, p-nitrophenyl-lhydroxynaphthoate, etc.; and
  • maleimides such as N-ethylmaleimide, N-phenylmaleimide, N-(p-carboxyphenyl)-maleimide. N-(p-sulfophenyl )maleimide, N-( carboxymethyl )-maleimide, etc.
  • reagents can be used to chemically modify gelatin employing the method to be described hereinafter, and the resulting gelatin derivatives, as the material used in the uppermost layer of the photographic lightsensitive material of the present invention, influence greatly the ability of the photographic light-sensitive of the present invention to the aforesaid aptitude for rapid processing at an elevated temperature.
  • isocyanates such as phenyl isocyanate, p-tolyl isocyanate, etc.
  • aziridines such as phenylcarbamoylaziridine, 2-methyll -phenylcarbamoylaziridine, l-dimethylaminosulfonylaziridinc, lbenzoylaziridine, etc.
  • sulfonyl halides such as benzenesulfonyl chloride, 4-methoxybenzenesulfonyl chloride.
  • 4-chlorobenzenesulfonyl chloride, 4-hromobenzenesulfonyl chloride, 4-methylbenzenesulfonyl chloride, etc. are particularly preferred reagents, either because they are economically advantageous due to their availability, or because they have a marked effect in preventing reticulation in processing at higher temperatures, for example, 48C or 52C.
  • the gelatin derivatives necessary for practicing the present invention can be prepared using a conventional technique by reacting gelatin with the above-described monofunctional reagent (compound having one functional group per molecule capable of reacting with the reactive group in the gelatin molecule) in a solvent for gelatin such as water, an organic solvent (e.g., dimethylsulfoxide, dimethylformamide, acetic acid, etc.) or a mixture of an organic solvent and water, in the presence of, if necessary, a base or an acid as a pH-adjusting agent.
  • a solvent for gelatin such as water, an organic solvent (e.g., dimethylsulfoxide, dimethylformamide, acetic acid, etc.) or a mixture of an organic solvent and water, in the presence of, if necessary, a base or an acid as a pH-adjusting agent.
  • the above-described process for preparing the gelatin derivatives used in the present invention is the same as or similar to known processes and described in, e.g., US. Pat. No
  • the present invention is clearly distinguished from the above-described known patents. According to the descriptions in the above described patents, all of the objects and the effects thereof relate to processes for the production of gelatin derivatives or to processes for the production of precipitated silver halide emulsions. Therefore, the present invention which relates to the method of incorporating gelatin derivatives prepared by treating gelatin with the foregoing monofunctional reagents, in the uppermost layer of a photographic light-sensitive material for the purpose of producing photographic light-sensitive materials having good characteristics for rapid processing at an elevated temperature, is completely different from the above recited prior art.
  • the gelatin derivative is not necessarily incorporated in the photographic emulsion layer of a photographic light-sensitive material to be processed at a high temperature. All that is required is that the gelatin derivative be incorporated in the protective layer on an emulsion layer or to provide a layer comprising the gelatin derivative alone as the protective layer on the emulsion layer. in this case, two or more gelatin derivatives can be used in combination. Also, a photographic light-sensitive material used in the invention having good characteristics for rapid processing at an elevated temperature can be obtained by insubstances such as non-modified gelatin, albumin, ca-
  • cellulose derivatives such as carboxy cellulose alkyl (e.g., methyl) esters, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, etc.
  • synthetic polymers such as polyvinyl alcohol, partially esterified polyvinyl alcohol, polyacrylamide or derivatives thereof, polyvinylpyrrolidone, polyacrylic acid or polyacrylate, or various copolymer thereof, and various copolymers of maleic anhydride and another vinyl compound; etc., are preferable.
  • the ratio of the gelatin derivative to these hydrophilic binders is not particularly limited and can vary; but, in order to markedly promote the effect obtained by the practice of the present invention, the gelatin derivative content is preferably not than based on the weight of total binders forming the uppermost layer.
  • any developer capable of reducing silver halide to silver can be used.
  • Suitable polyhydroxy benezenes include, e.g., hydroquinone, Z-methylhydroquinone, 2-phenylhydroquinone, Z-chlorohydroquinone, pyrogallol, catechol, etc.
  • Suitable 4-aminophenol include, e.g., 4-N-methyl-aminophenol hemisulfate (conventionally called Metol"), 4-N-benzyl-aminophenol chloride, 4-N,N-diethylaminophenol chloride, 4- aminophenol sulfate. etc.
  • Suitable 3-pyrazol1dones include, e.g., l-phenyl 3-pyrazolidone, 4,4-dimethyl-lphenyl-3-pyrazolidone, 4-methy1- l -phenyl-3-pyrazolidone, etc.
  • developers containing as the developing agent an aromatic primary amines such as p-phenylenediamine for example, inorganic acid salts of 4-amino-N,N-diethylaniline; 2- amino-5-diethylaminotoluene; 2-amino-5-(N-ethyl-N- laurylamino )toluene; 4-[N-ethyl-N-( fl-hydroxyethyl amino aniline; 3 -methyl-4-amino-N-ethyl-N-( B- hydroxyethyl)aniline; 4-amino-3-methyl-N,N-diethylaniline; 4-amino- 3-methyl-N-ethyl-N-( 2- methanesulfonylaminoethyl)aniline as disclosed in US.
  • an aromatic primary amines such as p-phenylenediamine
  • a hardener in order to further promote the effects of the present invention, a hardener, a matting agent, a lubricant or the like can be used in suitable amounts in combination with the gelatin derivative incorporated in the uppermost layer. It is well known, as a means necessary for promoting the effect of the protective layer, to add the above-described gelatin additives to the protective layer of conventional photographic light-sensitive materials. 1n the present invention it is preferable to use them for the same purpose also. That is, a hardener is effective to suitably harden the uppermost layer to maintain the physical strength of the surface layer.
  • hardeners are: aldehyde series compounds such as formaldehyde, glutaraldehyde and halocarboxyaldehydes (e.g. mucochloric acid); ketones such as diacetyl and cyclopentanedione; active halogen-containing compounds such as bis(2- chloethyl urea), 2-hydroxy-4,6-dichloro-1 ,3,5-triazine and those compounds as disclosed in US. Pat. Nos. 3,288,775 and 2,732,303 and British Pat. Nos.
  • active olefin-containing compounds such as divinylsulfone, 5-acetyl-1,3-diacryloylhexahydro- 1 ,3,5-triazine and those compounds as disclosed in US. Pat. Nos. 3,635,718; 3,232,763; 3,490,911 and 3,642,486 and British Pat. No. 994,869; N-methylol compounds such as N-hydroxymethylphthalimide and those compounds as disclosed in US. Pat. Nos.
  • dioxane derivatives such as dihydroxydioxane and dichlorodioxane and inorganic hardeners such as chrom alum and zirconium sulfate, precursors of the abovedescribed materials such as addition compounds of an alkali metal bisulfite and an aldehyde, methylol derivaties of hydrazine, and primary aliphatic nitro alcohols and those compounds as disclosed in U.S. Pat. Nos. 3,288,775; 3,017,280 and 2,983,611 and British Pat. No. 1,167,207.
  • a matting agent is useful for preventing inconvenient adhesion difficulties between the uppermost layer and the surface of other substances.
  • the matting agent there are preferably used silver halide grains of a suitable grain size; inorganic compounds such as silica, strontium barium sulfate, etc.; water-dispersable vinyl polymers such as polymethyl methacrylate, etc.
  • a lubricant is useful for preventing adhesion difficulties similar to the matting agent and, in addition, is effective for improving friction properties which relates to the camera adaptation of movie films upon photographing or projection.
  • waxes such as liquid paraffin, higher fatty acid esters, etc.; polyfluorinated hydrocarbons or derivatives thereof; silicones such as polyalkylpolysiloxane, polyarylpolysiloxane, polyalkylpolysiloxane or the alkylene oxide adduct derivaties thereof; and the like are preferably used.
  • These materials are each used for their known purposes and are used suitably in an amount effective to achieve the purpose of their use.
  • An effective amount of the materials can each range from 0.01 to 90% wt., preferably from 0.05 to 50 wt% on a solids basis of the uppermost layer.
  • a coating acid can be used for coating the uppermost layer for the same reasons such is used in coating other hydrophilic colloidal layers constituting a photographic light-sensitive material.
  • Any of the known surface active agents can be employed and specifically, anionic surface active agents containing acidic groups such as a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfate group, a phosphate group, etc., ampholytic surface active agents of carboxylic acid type, sulfonic acid type, sulfate type or phosphate type; nonionic surface active agents of the polyalkyleneoxide series or the polyglycerin series; and natural surface active agents such as saponin, are preferably used. Suitable such materials and the amounts thereof generally suitable for use are disclosed for example, in U.S. Pat. Nos. 2,600,831,
  • a positive light-sensitive material for movie use which conventionally has been photographically processed at a temperature as low as 24C for a comparactively long period of time, can be processed at an elevated temperature of, for example, 52C in a short time to thereby form images of high quality.
  • a temperature preferably not higher than about 60C can be employed. While it is necessary in the method of the present invention to develop the photographic light-sensitive material at a temperature of at least 30C., processings other than development can be practiced at a temperature of some what lower than 30C.
  • the present invention is markedly effective where it is intended to improve the processing steps of reversal color light-sensitive materials by shortening the processing time. Such steps involve black-andwhite development and color development and, therefore, take a long time in comparison with other lightsensitive materials. That is, the present invention enables reversal color light-sensitive materials to be processed without reticulation resulting when the temperature of the processing steps is changed completely or partially from a low temperature of 24C or 29C to a high temperature of, for example, 38C or 46C and, therefore, enables images to be formed with excellent quality in a short time.
  • the present invention enables first development, color development, bleach-fixation and like processing to be conducted immediately after photographing, without the necessity for a pre-hardening bath treatment which has conventionally been inevitable with reversal color photo graphic light-sensitive materials.
  • the present invention provides the advantage that the processing time can be shortened and the processing steps can be reduced in the number of baths required without delaying the developing speed (or reduction in sensitivity) which has been encountered in the case of an exceptional hardening of the photographic layers so as to prevent reticulation.
  • gelatin derivative used in the invention can be used as the subbing layer between the support and the photographic emulsion layer, or as the binder for an intermediate layer. a filter layer, a stripping layer or a backing layer. as well as the element for the uppermost layer or for the protective layer.
  • the photographic layers having the gelatin derivative-containing uppermost layer thereon can include a photographic emulsion layer wherein various silver salts such as silver chloride, silver bromide, silver iodide, and mixed silver halides (e.g., silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc.) are used.
  • various silver salts such as silver chloride, silver bromide, silver iodide, and mixed silver halides (e.g., silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc.) are used.
  • Illustrative of such emulsions are various silver halide photographic emulsions such as orthochromatic emulsions, panchromatic emulsions, emulsions for infrared rays, emulsions for recording invisible light such as X-rays, color photographic emulsions (e.g., emulsions containing a color former, emulsions containing a dye developing agent, emulsions containing a bleachable dye, etc.).
  • orthochromatic emulsions such as orthochromatic emulsions, panchromatic emulsions, emulsions for infrared rays, emulsions for recording invisible light such as X-rays, color photographic emulsions (e.g., emulsions containing a color former, emulsions containing a dye developing agent, emulsions containing a bleachable dye, etc.).
  • gelatin As the dispersing medium (or binder) for these photographic emulsions, gelatin, colloidal albumin, various gelatin derivatives (e.g., phthaloylated gelatin, malonoylated gelatin, etc.), cellulose derivatives (e.g., cellulose sulfate, hydroxyethyl cellulose, etc.), synthetic high polymers such as polyvinyl compounds (e.g., polyvinyl a1- cohol, polyvinyl pyrrolidone, polyacrylamide, polystyrenesulfonic acid, etc.), gelatin-synthetic high polymer mixtures, and the like can be used.
  • various gelatin derivatives e.g., phthaloylated gelatin, malonoylated gelatin, etc.
  • cellulose derivatives e.g., cellulose sulfate, hydroxyethyl cellulose, etc.
  • synthetic high polymers such as polyvinyl compounds (e.g., polyvin
  • various photographic supports such as a cellulose ester film, a polyvinyl acetate film, a polyethylene terephthalate film, a polystyrene film, relating films, paper, polyethylene-coated paper, synthetic paper, and the like are preferably used.
  • the silver halide photographic emulsion used in the present invention can be chemically sensitized in a conventional manner.
  • suitable chemical sensitizers are active gelatin, gold compounds such as chloroanrate and gold chloride as disclosed in US. Pat. Nos. 2,399,083, 2,540,085, 2,597,856 and 2,597,915; salts of noble metals such as platinum, paladium, iridium, rhodium and ruthenium as disclosed in US. Pat. Nos. 2,448,060; 2,540,086; 2,566,245; 2,566,263 and 2,598,079; sulfur compounds which are capable of reacting with silver halide to produce silver sulfide as disclosed in US. Pat. Nos.
  • the silver halide photographic emulsion used can be spectrally sensitized or supersensitized with at least one of the polymethinedyes such as the cyanine dyes including the merocryanine dyes and the like, optionally in combination with a styryl dyestuft" or a substantially colorless aromatic compound.
  • the polymethinedyes such as the cyanine dyes including the merocryanine dyes and the like, optionally in combination with a styryl dyestuft" or a substantially colorless aromatic compound.
  • blue-sensitizing dyes are those as disclosed in US. Pat. Nos. 2,493,748; 2,519,001; 2,977,229; 3,480,434; 3,672,897 and 3,703,377.
  • green-sensitizing dyes are those as disclosed in US. Pat. Nos.
  • stabilizing agents or antifogging agents are heterocyclic compounds such as 4-hydroxy fi-methyll ,3,3a, 7-tetrazaindene, S-methylbenzothiazole and l-phenyl-S-mercaptotetrazole, mercury-containing compounds, mercapto compounds and metal salts as disclosed in CEK Mees The Theory of The Photographic Process Third Ed.
  • the photographic emulsion and/or the auxiliary layer used in the present invention can contain a hardener, such as an aldehyde, a formaldehyde precursor containing methylol group or alkylarninomethyl group, a 1,4-dioxane, an aziridine, an isoxazole, a carbodiimide, an active halogen containing compound or, an active vinyl compound; a gelatin plasticizer such as an aliphatic alcohol or a glycol; various surface active agents as a coating aid or as an antistatic agent as well known in the art; a ultraviolet absorbant; a fluorescent brightening agent; and antihalation dyes or filter dyes.
  • a hardener such as an aldehyde, a formaldehyde precursor containing methylol group or alkylarninomethyl group, a 1,4-dioxane, an aziridine, an isoxazole, a carbodiimide, an active halogen containing
  • Phenyl Isocyanate-Processed Gelatin (abbreviated as Gd-l 118 Grams of lime-processed gelatin prepared from cow bone was dissolved in 650 ml of distilled water at 50C and the resulting solution was cooled to 40C. A solution prepared by dissolving 6 g of phenyl isocyanate in 20 ml of acetone was added thereto over a 20 minute period while adding thereto a 10% sodium hydroxide aqueous solution under sufficient stirring in order to mainain the pH of the solution at 9.5. After the addition of the isocyanate solution, stirring was continued for an additional 20 minutes while maintaining the temperature and the pH of the solution at the same levels. Thereafter, the pH of the solution was adjusted to 7 using dilute sulfuric acid (5 wt%) followed by lyophilization. Thus, g of the gelatin derivative (Gd-l as a solid was obtained.
  • Gd-l 118 Grams of lime-processed gelatin prepared from cow bone was dissolved in 650
  • the solution was desalted by passing it through a mixed bed of a commercially available cation exchange resin (IR-I20 produced by 01'- gano Co. Ltd.) and a commercially available anion exchange resin (IR-45 produced by Organo Co. Ltd).
  • a commercially available cation exchange resin IR-I20 produced by 01'- gano Co. Ltd.
  • IR-45 commercially available anion exchange resin
  • the pH of the solution, after desalting was adjusted to 6-7 using a dilute caustic aqueous solution. Upon condensing the solution and drying in warm air, 420 g of the gelatin derivative (Gd-4) was obtained.
  • PRODUCTION EXAMPLE 5 4-Methylbenzenesulfonyl Chloride-Processed Gelatin (Gd-5).
  • the same procedures as described in Production Example 4 were conducted except for changing the amount of 4-methylbenzenesulfonyl chloride from 25.5 g to 34 g and changing the desalting method (the same noodle washing as described in Production Example 3 being conducted instead of ion exchange resin-processing of Production Example 4).
  • the gelatin derivative (Gd-5) was obtained.
  • AH Stabilizing Agent Name layer: containing black colloidal silver, gelatin,
  • Green-Sensitive Layer (hereinafter abbreviated as Mamng Assn Name Tab 6 GL): a gelatino-silver bromoiodide emulsion layer (containing 7 mol% of silver iodide) containing g lfaghgjggas Grams Color former No. 3 and Color Former No. 4, Sen- No, 3 Silicon Dioxide Grains sitizing Dye No. l, Stabilizing Agent No. 1, Hard- No. 4 Polymethyl Methacrylate Grains 40 ener N 2 d C i Aid N 1;
  • No.2 Cetyl Palrnitate BL Liquid Paraffin Blue-Sensitive Layer
  • No.3 Cetyl Palrnitate BL a gelatino-silver bromoiodide emulsion layer No. 3 Silicone Oil (containing 7 mol% of silver iodide) containing Color former No. 2, Stabilizing Agent No. l, and Hardener No. 2.
  • Light-sensitive Material No, 2 (coupler-in-emulsion color reversal film) comprising:
  • TAC Subbing Layer: containing gelatin, salicyclic acid, ac-
  • Light-Sensitive Material No. 1 (color negative film) comprising: etone, methanol, methlene chloride and water;
  • AH Layer containing black colloidal silver, gelatin
  • Subbing Layer containing gelatin, salicylic acid, acetone, methanol, methylene chloride and water;
  • RL a gelatino-silver bromoiodide emulsion layer (containing 0.5 mol% of silver iodide) containing Color former No. 9, Spectral Sensitizing Agent No. 2, Stabilizing Agent No. I, Hardener No. 3 and Coating Aid No. l;
  • Gelatin Intermediate Layer containing Hardener No. 3 and Coating Aid No. 1;
  • GL a gelatino-silver bromoiodide emulsion layer (containing 0.8 mol% of silver iodide) containing Color Former No. 4, Spectral Sensitizing Agent No. l, Stabilizing Agent No. I, Hardener No. 3, and Coating Aid No. l;
  • YF Layer containing Hardener No. 3, Coating Aid No. l and colloidal silver;
  • BL a gelatino-silver bromoiodide emulsion layer (containing l mol% of silver iodide) containing Color Former No. l, Stabilizer No. l, Hardener No, 3, and Coating Aid No. 1.
  • Light-Sensitive Material No. 3 (color positive film) comprising:
  • Subbing Layer containing gelatin, salicylic acid, acetone, methanol, methylene chloride and water;
  • BL a gelatino-silver bromoiodide emulsion layer (containing 1.2 mol% of silver iodide) containing Color Former No. l, Stabilizer No. l and Stabilizer No. 2, Hardener No. 3, Coating Aid No. I and Coating Aid No. 5;
  • Gelatin Intermediate Layer containing Hardener No. 3, Coating Aid No. 1 and Coating Aid No. 5;
  • RL a gelatino-silver chlorobromide emulsion layer (containing 45 mol% of silver bromide) containing Color former No. 6, Spectral Sensitizing Agent No. 2, Stabilizer No. l, Stabilizer No. 2, Hardener No. 3, Coating Aid No. l and Coating Aid No. S;
  • Gelatin Intermediate Layer containing Hardener No. 3, Coating Aid No. l and Coating Aid No. 5;
  • GL a gelatino-silver chlorobromide emulsion layer (containing 45 mol% of silver bromide) containing Color former No. 4, Spectral Sensitizing Agent No. l, Stabilizing Agent No. l, Stabilizing Agent No. 2, Hardener No. 3, Coating Aid No. l and Coating Aid No. 5.
  • Light-Sensitive Material No. 4 (color paper) comprising:
  • Subbing Layer containing gelatin, ethanol and water;
  • BL a gelatino-silver chlorobromoiodide emulsion layer (containing l mol% of silver iodide) containing Color Former No. l, Stabilizer No. 1, Hardener No. 3, Hardener No. 4 and Coating Aid No. l;
  • Gelatin Intermediate Layer containing Hardener No. 3, Hardener No. 4, and Coating Aid No. 1;
  • RL a gelatino-silver chlorobromide emulsion layer (containing 50 mol% of silver bromide) containing Color Former No. 7 Spectral sensitizing Agent No.
  • Light-Sensitive Material No.5 (coupler-free reversal color film) comprising:
  • Base polyethylene te rephthalate
  • Subbing Layer containing gelatin, salicyclic acid, ni-
  • RL a gelatino-silver bromoiodide emulsion layer (containing l mol% of silver iodide) containing Spectral Sensitizing Agent No. 2, Stabilizing Agent No. l Stabilizing Agent N0. 3, Hardener No. 6 and Coating Aid No. 1;
  • GL a gelatino-silver bromoiodide emulsion layer (containing 4 mol% of silver iodide) containing Spectral Sensitizing Agent No. l, Stabilizing Agent No. l Stabilizing Agent No. 3, Hardener No. 6 and Coating Aid No. l;
  • YF Layer containing Hardener No. 6, Coating Aid No. l and colloidal silver
  • BL a gelatino-silver bromoiodide emulsion layer (containing 4 mol% of silver iodide) containing Stabilizing Agent No. l, Stabilizing Agent No. 3,
  • Hardener No. 6 and Coating Aid No. l The processing temperatures, processing periods of time and compositions of the processing solutions used in the samples are given below.
  • compositions of the processing solutions were the same as described in The British Journal of Photography, I968, Oct. 27th number, pp.83 8-840 as follows: The compounds were dissolved in the order indicated, at a maximum temperature of 35C.

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4010035A (en) * 1974-05-29 1977-03-01 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide color photographic material and a process for developing thereof
US4021245A (en) * 1974-04-30 1977-05-03 Fuji Photo Film Co., Ltd. Photographic light-sensitive material
US4142894A (en) * 1976-07-08 1979-03-06 Fuji Photo Film Co., Ltd. Method for forming images
US4166050A (en) * 1975-12-01 1979-08-28 Fuji Photo Film Co., Ltd. Method of increasing the viscosity of photographic coating solutions
US4179296A (en) * 1975-12-29 1979-12-18 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4212672A (en) * 1977-07-12 1980-07-15 Fuji Photo Film Co., Ltd. Lithographic silver halide photosensitive material
US4266010A (en) * 1974-07-01 1981-05-05 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US4367284A (en) * 1980-05-26 1983-01-04 Minnesota Mining And Manufacturing Company Photographic elements with improved surface characteristics
DE3233218A1 (de) * 1981-09-07 1983-03-17 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Silberhalogenidhaltiges, fotografisches lichtempfindliches material und verfahren zur abschwaechung desselben
US4476218A (en) * 1981-06-16 1984-10-09 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
DE3730319A1 (de) * 1987-09-10 1989-03-30 Agfa Gevaert Ag Fotografisches aufzeichnungsmaterial
US5518877A (en) * 1994-02-07 1996-05-21 Agfa-Gevaert Ag Photographic silver halide material
WO2023064370A1 (en) * 2021-10-13 2023-04-20 Board Of Trustees Of Michigan State University Soluble epoxide hydrolase inhibitors and use thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4394089A (en) * 1981-09-23 1983-07-19 Logetronics, Inc. Color photoprinting with a scanning memory mask
JPS59121327A (ja) * 1982-08-17 1984-07-13 Fuji Photo Film Co Ltd 製版用ハロゲン化銀写真感光材料及びその減力処理方法
DE3608998A1 (de) * 1986-03-18 1987-10-01 Agfa Gevaert Ag Fotografisches aufzeichnungsmaterial

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312553A (en) * 1963-10-30 1967-04-04 Gen Aniline & Film Corp Photographic materials
US3536486A (en) * 1969-02-03 1970-10-27 Eastman Kodak Co High temperature processing of exposed photographic elements
US3591379A (en) * 1968-04-09 1971-07-06 Eastman Kodak Co Photographic overcoat compositions and photographic elements

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312553A (en) * 1963-10-30 1967-04-04 Gen Aniline & Film Corp Photographic materials
US3591379A (en) * 1968-04-09 1971-07-06 Eastman Kodak Co Photographic overcoat compositions and photographic elements
US3536486A (en) * 1969-02-03 1970-10-27 Eastman Kodak Co High temperature processing of exposed photographic elements

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021245A (en) * 1974-04-30 1977-05-03 Fuji Photo Film Co., Ltd. Photographic light-sensitive material
US4010035A (en) * 1974-05-29 1977-03-01 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide color photographic material and a process for developing thereof
US4266010A (en) * 1974-07-01 1981-05-05 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material
US4166050A (en) * 1975-12-01 1979-08-28 Fuji Photo Film Co., Ltd. Method of increasing the viscosity of photographic coating solutions
US4179296A (en) * 1975-12-29 1979-12-18 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4142894A (en) * 1976-07-08 1979-03-06 Fuji Photo Film Co., Ltd. Method for forming images
US4212672A (en) * 1977-07-12 1980-07-15 Fuji Photo Film Co., Ltd. Lithographic silver halide photosensitive material
US4367284A (en) * 1980-05-26 1983-01-04 Minnesota Mining And Manufacturing Company Photographic elements with improved surface characteristics
US4476218A (en) * 1981-06-16 1984-10-09 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
DE3233218A1 (de) * 1981-09-07 1983-03-17 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Silberhalogenidhaltiges, fotografisches lichtempfindliches material und verfahren zur abschwaechung desselben
DE3730319A1 (de) * 1987-09-10 1989-03-30 Agfa Gevaert Ag Fotografisches aufzeichnungsmaterial
GB2212288A (en) * 1987-09-10 1989-07-19 Agfa Gevaert Ag A silver halide photographic recording material
GB2212288B (en) * 1987-09-10 1991-01-02 Agfa Gevaert Ag A photographic recording material
US5518877A (en) * 1994-02-07 1996-05-21 Agfa-Gevaert Ag Photographic silver halide material
WO2023064370A1 (en) * 2021-10-13 2023-04-20 Board Of Trustees Of Michigan State University Soluble epoxide hydrolase inhibitors and use thereof

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GB1426967A (en) 1976-03-03
JPS578455B2 (enrdf_load_html_response) 1982-02-16
JPS49107538A (enrdf_load_html_response) 1974-10-12
DE2407347A1 (de) 1974-09-05

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