EP0409665A1 - Matériel photographique à halogénure d'argent avec revêtement antistatique - Google Patents

Matériel photographique à halogénure d'argent avec revêtement antistatique Download PDF

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Publication number
EP0409665A1
EP0409665A1 EP90308018A EP90308018A EP0409665A1 EP 0409665 A1 EP0409665 A1 EP 0409665A1 EP 90308018 A EP90308018 A EP 90308018A EP 90308018 A EP90308018 A EP 90308018A EP 0409665 A1 EP0409665 A1 EP 0409665A1
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EP
European Patent Office
Prior art keywords
group
silver halide
photographic material
halide photographic
material according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP90308018A
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German (de)
English (en)
Inventor
Takeshi Habu
Yasuhiko Takamuki
Taketoshi Yamada
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Konica Minolta Inc
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Konica Minolta Inc
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Publication date
Priority claimed from JP1189663A external-priority patent/JP2796845B2/ja
Priority claimed from JP1197484A external-priority patent/JP2829635B2/ja
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0409665A1 publication Critical patent/EP0409665A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/061—Hydrazine compounds
    • 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
    • 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/067—Additives for high contrast images, other than hydrazine compounds
    • 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
    • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • G03C1/89—Macromolecular substances therefor
    • 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
    • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • G03C1/89—Macromolecular substances therefor
    • G03C1/895—Polyalkylene oxides
    • 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
    • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives

Definitions

  • This invention relates to a silver halide photographic material having an antistatic coating on a plastic film support. More particularly, this invention relates to a silver halide photographic material having improved antistatic quality.
  • Plastic film supports generally have a great tendency to experience static buildup, which in many cases have put various limitations on the use of these supports.
  • plastic film supports such as polyethylene terephthalate films are commonly used but they often experience static buildup, particularly at low temperatures in the winter season. Provisions against this static buildup problem bear particular importance to recent practices in the photographic industry including high-speed coating of high-­sensitivity photographic emulsions and exposure of high-­sensitivity photographic materials in automatic printers.
  • antistatic agents are customarily used in photographic materials and recently employed antistatic agents include fluorine-containing surfactants, cationic surfactants, amphoteric surfactants, surfactants or high-molecular weight compounds containing polyethylene oxide groups, and polymers having sulfonic acid or phosphoric acid groups in the molecule.
  • an object of the present invention to provide a silver halide photographic material having a highly transparent and haze-free antistatic coating.
  • Another object of the present invention is to provide a highly stable silver halide photographic material that exhibits high antistatic capability and which yet will not undergo desensitization with time even if a tetrazolium or hydrazine compound is used.
  • a silver halide photographic material having at least a light-sensitive emulsion layer and an antistatic coating containing (1) a water soluble conductive polymer, (2) hydrophobic polymer particles and (3) a curing agent on a plastic film support, which hydrophobic polymer particles contain an acrylamide group or contain styrene and an alkyl acrylate and/or an alkyl methacrylate that have 1 - 12 carbon atoms, and form a stable dispersion with the aid of a nonionic surfactant having 3 or more alkylene oxide chains.
  • the light-sensitive emulsion layer in this photographic material desirably contains a tetrazolium or hydrazine compound.
  • the water-soluble conductive polymer used in the present invention is capable of forming a transparent layer even if it is used alone but the resulting layer can readily crack if the drying conditions vary even by the slightest degree. In accordance with the present invention, this problem is effectively prevented by incorporating hydrophobic polymer particles.
  • the water-soluble conductive polymer for use in the present invention may be a polymer having at least one conductive group selected from the group consisting of a sulfonic acid group, a sulfate ester group, a quaternary ammonium salt group, a tertiary ammonium salt group, a carboxyl group and a polyethylene oxide group.
  • a sulfonic acid group, a sulfate ester group and a quaternary ammonium salt group are preferred.
  • These conductive groups must be present in an amount of at least 5 wt% per molecule of the polymer.
  • the water-soluble conductive polymer may also contain a carboxyl group, a hydroxyl group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group or a vinylsulfone group.
  • a carboxyl group, a hydroxyl group, an amino group, an epoxy group, an aziridine group and an aldehyde group are preferred.
  • These groups are preferably contained in an amount of at least 5 wt% per molecule of the polymer.
  • the water-soluble conductive polymer generally has a molecular weight in the range of 3,000 - 100,000, with the range of 3,500 - 50,000 being preferred.
  • the water-soluble conductive polymer that can be used in the present invention may be exemplified by, but not limited to, the following compounds.
  • x, y, z and w each represents the mol% of the relevant monomer component, and M represents the average molecular weight (the term "average molecular weight” as used herein means the number average molecular weight).
  • the polymers enumerated above can be synthesized by polymerizing monomers that are either commercially available or obtainable in the usual manner. These compounds are added in amounts that generally range from 0.01 to 10 g/m2, preferably form 0.1 to 5 g/m2.
  • the hydrophobic polymer particles to be incorporated in the water-soluble conductive polymer layer used in the present invention are contained in the form of a "latex" that is substantially insoluble in water.
  • the hydrophobic polymer contains an acrylamide group or contains styrene and an alkyl acrylate and/or an alkyl methacrylate that have 1 - 12 carbon atoms.
  • Hydrophobic polymers containing an acrylamide group are obtained by polymerizing monomers selected from among any desired combinations of acrylamide and methacrylamide derivatives.
  • an acrylamide derivative and/or a methacrylamide derivative is contained in an amount of at least 0.1 mol%, with the content of at least 1 mol% being particularly preferred.
  • Hydrophobic polymers that are composed of styrene and an alkyl acrylate and/or an alkyl methacrylate having 1 - 12 carbon atoms are obtained by polymerizing monomers selected from among any desired combinations of styrene, styrene derivatives, alkyl acrylates and alkyl methacrylates.
  • a styrene derivative, an alkyl acrylate or an alkyl methacrylate is contained in an amount of at least 10 mol%, with the content of at least 30 mol% being particularly preferred.
  • Latices of these hydrophobic polymers can be formed by either one of the following two methods: i) emulsion polymerization and ii) dissolving a solid polymer in a low-­boiling solvent, forming a fine dispersion of the polymer particles, and then distilling off the solvent.
  • Emulsion polymerization is preferred since it is capable of producing a latex of fine polymer particle of a uniform size.
  • Nonionic surfactants are preferably used in emulsion polymerization and, in the present invention, nonionic surfactants having 3 or more alkylene oxide chains to be described below are used. These nonionic surfactants are used in amounts of no more than 10 wt% of the monomers. The excessive use of surfactants will make the conductive layer cloudy and hence should be avoided.
  • Molecular weights of at least 3,000 will suffice for the hydrophobic polymer and the transparency of the conductive layer will be little affected by the difference in the molecular weight of the hydrophobic polymer if it is no less than 3,000.
  • the hydrophobic polymer particles are preferably used in an amount of 0.1 to 10 g/m2, more preferably from 0.3 to 5 g/m2.
  • hydrophobic polymer that can be used in the present invention are listed below.
  • the antistatic coating is formed on a transparent support.
  • All photographic transparent supports may be used but preferred examples are polyethylene terephthalate and cellulose triacetate films that are adapted to transmit at least 90% of visible light.
  • These transparent supports can be prepared by methods that are well known to one skilled in the art. If desired, they may be blued by adding dyes in small amounts that will not substantially impair light transmission.
  • the supports to be used in the present invention may coated with a subbing layer containing a latex polymer after corona discharge treatment.
  • Corona discharge treatment is preferably performed to provide an energy of 1 mW - 1 kW/m2 per minute.
  • supports coated with a latex-containing subbing layer may be subjected to another corona discharge treatment before an antistatic coating is applied.
  • a polyfunctional aziridine is preferably used as a curing agent to cure the antistatic coating provided in accordance with the present invention.
  • Particularly preferred are bifunctional or trifunctional aziridines that have molecular weights of no more than 600.
  • the curing agent is preferably used in an amount of 0.01 to 10 g/m2, with the range of 0.05 to 5 g/m2 being particularly preferred.
  • the antistatic coating may be positioned closer to the support than a light-sensitive layer, or it may be provided on the back side of the support which is opposite the light-sensitive layer.
  • a nonionic surfactant is used as a dispersant in the present invention and a polyalkylene oxide compound is a preferred nonionic surfactant.
  • the polyalkylene oxide compound to be used in the present invention is a compound that contains at least 3, preferably no more than 500, polyalkylene oxide chains in the molecule.
  • Such compounds can be synthesized either by condensation reaction between polyalkylene oxides and compounds having active hydrogen atoms such as aliphatic alcohols, phenols, aliphatic acids, aliphatic mercaptans or organic amines, or by condensing polyols such as polypropylene glycol or polyoxytetramethylene polymers with aliphatic mercaptans, organic amines, ethylene oxide or propylene oxide.
  • Each of the polyalkylene oxide chains in the molecule of the polyalkylene oxide compound may be divided into two or more segments to form a block copolymer.
  • the polyalkylene oxide has a total degree of polymerization in the range of 3 - 100.
  • the nonionic surfactant is preferably used in an amount ranging from 0.0001 to 0.1 g/m2, with the range of 0.0005 to 0.05 g/m2 being more preferred.
  • the hydrazine compound to be used in the present invention is preferably represented by the following general formula (H): where R1 is a monovalent organic residue; R2 is a hydrogen atom or a monovalent organic residue; Q1 and Q2 are each a hydrogen atom, an optionally substituted alkylsulfonyl group, or an optionally substituted arylsulfonyl group; X1 is an oxygen atom or a sulfur atom.
  • Monovalent organic groups represented by R1 and R2 include aromatic residues, heterocyclic residues and aliphatic residues.
  • Illustrative aromatic residues include a phenyl group and a naphthyl group, which may have such substituents as alkyl, alkoxy, acylhydrazinol dialkylamino, alkoxycarbonyl, cyano, carboxy, nitro, alkylthio, hydroxy, sulfonyl, carbamoyl, halogen, acylamino, sulfonamido, urea and thiourea.
  • Substituted phenyl groups include 4-methyl­phenyl, 4-ethylphenyl, 4-oxyethylphenyl, 4-dodecylphenyl, 4-carboxyphenyl, 4-diethylaminophenyl, 4-octylaminophenyl, 4-benzylaminophenyl, 4-acetamido-2-methylphenyl, 4-(3-­ethylthioureido_phenyl, 4-[2-(2,4-di-tert-butyl­phenoxy)butylamido]phenyl and 4-[2-(2,4-di-tert-butyl­phenoxy) butylamido]phenyl.
  • heterocyclic residues are 5- or 6-­membered single or fused rings having at least one of oxygen, nitrogen, sulfur and selenium atoms. These rings may have substituents.
  • Specific examples of heterocyclic residues include: pyrroline, pyridine, quinoline, indole, oxazole, benzoxazole, naphthoxazole, imidazole, benzimidazole, thiazoline, thiazole, benzothiazole, naphthothiazole, selenazole, benzoselenazole and naphthoselenazole rings.
  • hetero rings may be substituted by alkyl groups having 1 - 4 carbon atoms such as methyl and ethyl, alkoxy groups having 1 - 4 carbon atoms such as methoxy and ethoxy, aryl groups having 6 - 18 carbon atoms such as phenyl, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups, cyano group, amino group, etc.
  • Illustrative aliphatic residues include straight-­chained or branched alkyl groups, cycloalkyl groups, substituted alkyl or cycloalkyl groups, alkenyl groups and alkynyl groups.
  • Exemplary straight-chained or branched alkyl groups are alkyl groups having 1 - 18, preferably 1 - 8, carbon atoms, such as methyl, ethyl, isobutyl and 1-­octyl.
  • Exemplary cycloalkyl groups include cyclopropyl, cyclohexyl, adamantyl, etc. having 3-10 carbon atoms.
  • Substituents on alkyl and cycloalkyl groups include an alkoxy group (e.g. methoxy, ethoxy, propoxy or butoxy), an alkoxycarbonyl group, a carbamoyl group, a hydroxy group, an alkylthio group, an amido group, an acyloxy group, a cyano group, a sulfonyl group, a halogen atom (e.g. Cl, Br, F or I), an aryl group (e.g. phenyl, halogen-substituted phenyl or alkyl-substituted phenyl), etc.
  • an alkoxy group e.g. methoxy, ethoxy, propoxy or butoxy
  • an alkoxycarbonyl group e.g. methoxy, ethoxy, propoxy or butoxy
  • a carbamoyl group e.g. methoxy, ethoxy, propoxy or but
  • substituted alkyl or cycloalkyl group examples include 3-methoxypropyl, ethoxycarbonylmethyl, 4-chloro­cyclohexyl, benzyl, p-methylbenzyl and p-chlorobenzyl.
  • An exemplary alkenyl group is an allyl group, and an exemplary alkynyl group is a propargyl group.
  • the hydrazine compound represented by the general formula (H) is incorporated in a silver halide emulsion layer and/or a non-light-sensitive layer on the same side as silver halide emulsion layers on a support.
  • the hydrazine compound is incorporated in a silver halide emulsion layer and/or an underlying layer.
  • the hydrazine compound is preferably added in an amount of 10 ⁇ 5 to 10 ⁇ 1 mole per mole of Ag, more preferably from 10 ⁇ 4 to 10 ⁇ 2 mole per mole of Ag.
  • This tetrazolium compound to be used in the present invention is described below.
  • This tetrazolium compound may be represented by the following general formula (T): where R1, R2 and R3 are each independently a substituted or unsubstituted phenyl group; X ⁇ is an anion; and n is 2.
  • Preferred substituents are either a hydrogen atom or those which have a negative or positive value of Hamett's sigma ( ⁇ P) which represents an electron withdrawing ability. Substituents having a negative value of ⁇ P are particularly preferred.
  • Hamett's sigma value in relation to phenyl substitution is found in many documents including the article of C. Hansch et al. in Journal of Medical Chemistry, 20 , 304, 1977.
  • tetrazolium compounds to be used in the present invention can be easily synthesized by known methods, for example, the one described in Chemical Reviews, 55 , 335-­483.
  • the totrazolium compound to be used in the present invention is preferably incorporated in an amount of from about 1 mg to 10 g, more preferably from about 10 mg to about 2 g, per mole of the silver halide in the silver halide photographic material of the present invention.
  • the silver halide in the silver halide emulsion to be used in the photographic material of the present invention may be selected from among those which are commonly used in silver halide emulsions as illustrated by silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc.
  • Silver halide grains may be prepared by an acid method, a neutral method or an ammoniacal method.
  • the silver halide grains to be used in the present invention may have a uniform silver halide composition throughout the interior of grains, or they may be core/shell grains having different silver halide compositions in the bulk and the surface layer of grains.
  • the silver halide grains may be of a type in which a latent image is formed predominantly on the surface or of a type in which a latent image is formed predominantly in the bulk.
  • the silver halide emulsions to be used in the present invention may be stabilized with various compounds such as those described in prior patents including U.S. Patent Nos. 2,444,607, 2,716,062, 3,512,982, West German Patent Publication Nos. 1,189,380, 2,058, 626, 2,118,411, Japanese Patent Publication No. 4133/1968, U.S. Patent No. 3,342,596, Japanese Patent Publication No. 4417/1972, West German Patent Publication No. 2,149,789, Japanese Patent Publication Nos. 2825/1964 and 13566/1974.
  • Preferred examples of the compounds that can be used for stabilizing purposes include: 5,6-trimethylene-7-hydroxy-5-tria­zolo(1,5-a)pyrimidine, 5,6-tetramethylene-7-hydroxy-5-tria­zole(1,5-a)pyrimidine, 5-methyl-7-hydroxy-S-triazolo(1,5-­a)-pyrimidine, 5-methyl-7-hydroxy-S-triazolo(1,5-a)pyrim­idine, 7-hydroxy-S-triazolo(1,5-a)pyrimidine, 5-methyl-6-­boromo-7-hydroxy-S-triazolo(1,5-a)pyrimidine, gallic acid esters (e.g.
  • mercaptans e.g. 1-phenyl-5-­mercaptotetrazole, 2-mercaptobenzothiazole
  • benzotriazoles e.g. 5-bromobenzotriazole, 5-methylbenzotriazole
  • benzimidazoles e.g. 6-nitrobenzimidazole
  • the silver halide photographic material of the present invention and/or developers may have amino compounds incorporated therein.
  • developing agents such as phenidone and hydroquinone, or restrainers such as benzotriazole may be incorporated in emulsion layers.
  • developing agents and restrainers may be incorporated in backing layers in order to enhance the ability of various processing solutions.
  • Gelatin is used with particular advantage as a hydrophilic colloid in the present invention.
  • Gelatin to be used in the present invention may be pretreated with either an alkali or an acid. If ossein gelatin is to be used, it is preferably freed of the calcium or iron content.
  • the preferred calcium content is from 1 to 999 ppm, with the range of 1 - 500 ppm being more preferred.
  • the preferred iron content is from 0.01 to 50 ppm, with the range of 0.1 - 10 ppm being more preferred. Adjustments of the calcium or iron content can be accomplished by passing an aqueous gelatin solution through an ion-exchanging device.
  • Illustrative developing agents that can be used to develop the silver halide photographic material of the present invention include chlorohydroquinone, bromohydroquinone, methylhydroquinone, 2,3-dibromohydro quinone, 2,5-diethylhydroquinone, catechol, its derivatives such as 4-chlorocatechool, 4-phenylcatechol, 3-methyoxy­catechol, pyrogallol, its derivatives such as 4-­acetylpyrogallol, ascorbic acid and its derivatives such as sodium ascorbate.
  • heterocyclic developing agents include 3-­pyrazolidones such as 1-phenyl-3-pyrazolidone, 1-phenyl-­4,4-dimethl-3-pyrazolidone and 1-phenyl-4-methyl-4-­hydroxymethyl-3-pyrazolidone, 1-phenyl-4-amino-5-­pyrazolone, and 5-aminouracil.
  • the developing agents that can be used effectively in the present invention are described in T.H. James, ed., The Theory of the Photographic Process, 4th ed., pp. 291-334 and Journal of the American Chemical Society, 73 , 3,100 (1951). These developing agents may be used either singly or as admixtures and they are preferably used as admixtures. Developers that are used to develop the photographic material of the present invention may contain preservatives selected from among sulfites such as sodium sulfite and potassium sulfite and the inclusion of such preservatives will not be deleterious to the objects of the present invention. Hydroxylamines and hydrazide compounds may also be used as preservatives and, in this case, they are preferably used in amounts of 5 - 500 g, more preferably from 20 to 200 g, per liter of the developer.
  • Glycols may be contained as organic solvents in the developer and exemplary glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol and 1,5-pentanediol, with diethylene glycol being preferably used. These glycols are preferably used in amounts of 5 - 500 g, more preferably from 20 to 200 g, per liter of the developer. These organic solvents may be used either singly or as admixtures.
  • the silver halide photographic material of the present invention has very good keeping quality if it is processed with a developer that contains one or more of the development restrainers described above.
  • the developer of the composition described above preferably has a pH of 9 - 13, with the range of 10 - 12 being more preferred from the viewpoint of preservability and photographic characteristics.
  • the proportion of potassium ions is preferably higher than that of sodium ions in order to enhance the activity of the developer.
  • the silver halide photographic material of the present invention can be processed under various conditions.
  • the processing temperature for example, the development temperature is preferably not higher than 50°C, more preferably within the range of about 25 - about 40°C.
  • the development time is typically set to be no longer than 2 min, and particularly good results are often achieved by completing the development within 10 - 50 sec.
  • Other processing steps such as washing, stopping, stabilizing and fixing may also be performed under usual conditions. If desired, prehardening, neutralizing and any other necessary steps may be included. Of course, these steps may be omitted depending on the case.
  • Development may be carried out either manually (e.g. tray development or rack development) or mechanically (e.g. roller development or hanger development).
  • the applied antistatic coatings were dried at 90°C for 2 min and subsequently heat-treated at 140°C for 90 sec.
  • Gelatin was applied onto these antistatic coatings to provide a deposit of 2.0 g/m2.
  • the so prepared samples were subjected to a haze test.
  • Formaldehyde and 2,4-­dichloro-6-hydroxy-S-triazine sodium were used as hardeners of gelatin.
  • the results of the haze test are shown in Table 1.
  • Table 1 shows that the samples prepared in accordance with the present invention had satisfactory haze resistance.
  • Silver chlorobromide (5 mol% AgBr) grains that contained a rhodium salt in an amount of 10 ⁇ 5 mole per mole of silver and which had an average grain size of 0.11 ⁇ m with a monodispersibility of 15 were prepared by a controlled double-jet method in an acidic atmosphere (pH 3.0). The grains were grown in a system containing 30 mg of benzyladenine in 1,000 ml of a 1% aqueous gelatin solution. After mixing silver and the halide, 6-methyl-4-­hydroxy-1,3,3a-7-tetraazaindene was added in an amount of 600 mg per mole of silver halide, and the mixture was subsequently washed and desalted.
  • 6-methyl-4-hydroxy-1,3,3a,7-­tetraazaindene was added in an amount of 60 mg per mole of silver halide and thereafter sodium thiosulfate was added in an amount of 15 mg per mole of silver halide, followed by sulfur sensitization at 60°C. After the sulfur sensitization, 6-methyl-4-hydroxy-1,3,3a,7-tetraazaindene was added as a stabilizer in an amount of 600 mg per mole of silver halide.
  • Coating solution for the protective film for the emulsion layer was prepared to provide the deposits described below and was applied together with the emulsion to be superposed on the latter.
  • the other side of the support which was opposite the emulsion layer was subjected to corona discharge treatment at a power of 30 W/m2 per min and coated with a poly(styrene-butyl acrylate-glycidyl methacrylate) latex polymer in the presence of a hardener (hexamethylene aziridine), and further overlaid with an antistatic coating as in Example 1.
  • a coating solution for backing layer was prepared to the formula indicated below in such a way the additives contained would have the deposits also shown below. The so prepared solution was coated to form a backing layer.
  • a coating solution for the protective film for backing layer was prepared to the formula shown below in such a way that the additives used would provide the deposits also shown below.
  • the so prepared coating solution was applied together with the backing layer in superposion on the latter.
  • Dioctyl sulfosuccinate ester 200 mg/m2 Matting agent (polymethyl methacrylate; average particle size, 4.0 ⁇ m) 50 mg/m2 Alkali-processed gelatin (isoelectric point 4.9) 1.0 g/m2 Fluorinated sodium dodecylbenzene-sulfonate 50 mg/m2 Bis(vinylsulfonylmethyl)ether 20 mg/m2
  • Each of the samples thus prepared was divided into two parts; one part was stored at 23°C ⁇ 55% r.h. for 3 days, and the other part was humidified at 23°C ⁇ 55% for 3h. packed in superposion on the another in a moisture-proof bag and stored under accelerated aging conditions (at 55°C for 3 days) to prepare aged specimens. Both types of specimens were exposed through an optical step wedge and processed with a developer and a fixing solution that had the formulations shown below. Thereafter, the sensitivity and specific surface resistance of each specimen were measured. The sensitivity was determined as the amount of exposure necessary to provide an optical density of 1.0 and expressed in terms of relative values.
  • Silver chlorobromide (2 mol% AgBr) grains that contained a rhodium salt in an amount of 10 ⁇ 5 mole per mole of silver and which had an average grain size of 0.20 ⁇ m at a monodispersibility of 20 were prepared as in example 2. These grains were desalted and subjected to sulfur sensitization as in Example 2.
  • Additives prepared to provide the deposits described below were added to the emulsion thus prepared, and the resulting coating solution was applied to subbed polyethylene terephthalate films of the same type as used in Example 1.
  • the coating solution described above was applied after preliminary pH adjustment to 6.5 with sodium hydroxide.
  • a coating solution for protective film for the emulsion layer was prepared using the additives described below in such a way that they would provide the deposits also shown below, and the thus prepared coating solution was applied together with the emulsion coating solution in superposition on the latter.
  • This coating solution was applied after preliminary pH adjustment to 5.4 with citric acid.
  • an antistatic coating and a backing layer were provided as in Example 2 on the other side of the support which was opposite the emulsion layer, except that formaldehyde was used as a hardener in the backing layer.
  • the present invention successfully provides a highly stable silver halide photographic material that has a haze-­free and highly transparent antistatic coating and which will undergo less increase in specific surface resistance over time as well as less desensitization even if a supercontrasty agent such as a tetrazolium or hydrazine compound is used.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP90308018A 1989-07-21 1990-07-20 Matériel photographique à halogénure d'argent avec revêtement antistatique Withdrawn EP0409665A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP1189663A JP2796845B2 (ja) 1989-07-21 1989-07-21 帯電防止処理をしたハロゲン化銀写真感光材料
JP189663/89 1989-07-21
JP197484/89 1989-07-27
JP1197484A JP2829635B2 (ja) 1989-07-27 1989-07-27 帯電防止処理をしたハロゲン化銀写真感光材料

Publications (1)

Publication Number Publication Date
EP0409665A1 true EP0409665A1 (fr) 1991-01-23

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EP90308018A Withdrawn EP0409665A1 (fr) 1989-07-21 1990-07-20 Matériel photographique à halogénure d'argent avec revêtement antistatique

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EP (1) EP0409665A1 (fr)
KR (1) KR910003430A (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2246870A (en) * 1990-07-31 1992-02-12 Ilford Ltd Photographic materials with anti-static coatings
EP0497265A1 (fr) * 1991-01-29 1992-08-05 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
US5238706A (en) * 1992-06-26 1993-08-24 Minnesota Mining And Manufacturing Company Antistatic film bases and their process of manufacturing
EP0566374A3 (fr) * 1992-04-15 1994-10-26 Konishiroku Photo Ind Matériau photographique sensible à la lumière à base d'halogénure d'argent et procédé pour l'obtention d'une image.

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1548799A (en) * 1976-08-31 1979-07-18 Fuji Photo Film Co Ltd Light-sensitive silver halide photographic material
US4192683A (en) * 1975-12-17 1980-03-11 Konishiroku Photo Industry Co., Ltd. Photographic light-sensitive material
US4225665A (en) * 1978-12-20 1980-09-30 E. I. Du Pont De Nemours And Company Photographic element in which the antistatic layer is interlinked in the base

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4192683A (en) * 1975-12-17 1980-03-11 Konishiroku Photo Industry Co., Ltd. Photographic light-sensitive material
GB1548799A (en) * 1976-08-31 1979-07-18 Fuji Photo Film Co Ltd Light-sensitive silver halide photographic material
US4225665A (en) * 1978-12-20 1980-09-30 E. I. Du Pont De Nemours And Company Photographic element in which the antistatic layer is interlinked in the base

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2246870A (en) * 1990-07-31 1992-02-12 Ilford Ltd Photographic materials with anti-static coatings
EP0497265A1 (fr) * 1991-01-29 1992-08-05 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
US5244773A (en) * 1991-01-29 1993-09-14 Konica Corporation Silver halide photographic light sensitive material
EP0566374A3 (fr) * 1992-04-15 1994-10-26 Konishiroku Photo Ind Matériau photographique sensible à la lumière à base d'halogénure d'argent et procédé pour l'obtention d'une image.
US5238706A (en) * 1992-06-26 1993-08-24 Minnesota Mining And Manufacturing Company Antistatic film bases and their process of manufacturing

Also Published As

Publication number Publication date
KR910003430A (ko) 1991-02-27

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