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EP0690338A1 - Matériau photographique à l'halogénure d'argent ayant des propriétés antistatiques - Google Patents

Matériau photographique à l'halogénure d'argent ayant des propriétés antistatiques Download PDF

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Publication number
EP0690338A1
EP0690338A1 EP95109067A EP95109067A EP0690338A1 EP 0690338 A1 EP0690338 A1 EP 0690338A1 EP 95109067 A EP95109067 A EP 95109067A EP 95109067 A EP95109067 A EP 95109067A EP 0690338 A1 EP0690338 A1 EP 0690338A1
Authority
EP
European Patent Office
Prior art keywords
silver halide
group
photographic material
halide photographic
carbon atoms
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Withdrawn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
EP95109067A
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German (de)
English (en)
Inventor
Dario Ballerini
Renzo Torterolo
Marco Bucci
William M. Lamanna
George Moore
William A. Huffman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Minnesota Mining and Manufacturing Co
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Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to EP95109067A priority Critical patent/EP0690338A1/fr
Publication of EP0690338A1 publication Critical patent/EP0690338A1/fr
Withdrawn legal-status Critical Current

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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
    • G03C1/85—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
    • G03C1/005—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
    • G03C1/38—Dispersants; Agents facilitating spreading
    • 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
    • G03C1/38—Dispersants; Agents facilitating spreading
    • G03C1/385—Dispersants; Agents facilitating spreading containing fluorine

Definitions

  • the present invention relates to a silver halide photographic material, more particularly to a silver halide photographic material having improved antistatic property and improved coating ability.
  • Silver halide photographic materials are generally composed of an electrically insulating support and photographic layers coated thereon. Such a structure promotes the formation and accumulation of static charges when subjecting the photographic materials to friction or separation, caused by contact with the surface of the same or different materials during steps for manufacturing of the photographic materials or when using them for photographic purposes. These accumulated static charges cause several drawbacks. The most serious drawback is discharge of accumulated charges prior to development processing, by which the light-sensitive silver halide emulsion layer is exposed to light to form dot, spots, or branched or feathery linear specks when development of the photographic film is carried out. This phenomenon is called "static marks". Such static marks cause a reduction of the commercial value of photographic films, which sometimes become useless.
  • Static marks are a particular problem because it becomes evident for the first time after development. Further, these static charges are also the origin of secondary problems such as adhesion of dust to the surface of films, uneven coating, and the like.
  • static charge is frequently accumulated when manufacturing and/or using silver halide photographic materials.
  • they are generated by friction of the photographic film contacting a roller or by separation of the emulsion surface from a support surface during a rolling or unrolling step.
  • they are generated on X-ray films in an automatic apparatus by contact with or separation from mechanical parts or fluorescent screens, or they are generated by contact with or separation from rollers and bars made of rubber, metal, or plastics in a bonding machine or an automatic developing machine or an automatic developing apparatus or in a camera in the case of color negative films or color reversal films.
  • they can be generated by contact with packing materials, and the like.
  • Silver halide photographic materials having high sensitivity and handling speed are subject to an increase of static mark appearance.
  • static marks are easily generated because of high sensitization of the photographic material and severe handling conditions such as high speed coating, high speed exposure, and high speed automatic processing.
  • antistatic agents conventionally used in other fields cannot be used universally for silver halide photographic materials, because they are subjected to various restrictions due to the nature of the photographic materials. More specifically, the antistatic agents which can be used in silver halide photographic materials must have excellent antistatic abilities while not having adverse influences upon photographic properties of the photographic materials, such as sensitivity, fog, granularity, and sharpness. Such antistatic agents also must not have adverse influences upon the film strength and upon antiadhesion properties. Furthermore, the antistatic agents must not accelerate exhaustion of processing solutions and not deteriorate adhesive strength between layers composing the silver halide photographic material.
  • charge control agents are ionic and non-ionic surfactants as well as ionic salts. Fluorinated surfactants are often mentioned as good antistatic agents in silver halide photographic materials.
  • Electrically conductive compounds are mainly focused on conductive polymers such as ionic polymers and electronically conductive polymers.
  • ionic and non-ionic surfactants as well as fluorinated surfactants is widely disclosed in many patents, such as, for example, US 2,600,831, 2,719,087, 2,982,651, 3,026,202, 3,428,456, 3,457,076, 3,454,625, 3,552,972, 3,655,387, 3,850,640, 3,850,642, 4,192,683, 4,267,265, 4,304,852, 4,330,618, 4,367,283, 4,474,873, 4,510,233, 4,518,354, 4,596,766, 4,649,102, 4,703,000, 4,847,186, 4,891,307, 4,891,308, 4,916,054, EP 245,090, 300,259, 319,951, 370,404, and the like.
  • US 4,272,615 discloses the use of a non-ionic perfluoroalkenylpolyoxyethylene surfactant
  • US 4,649,102 discloses the combination of a non-ionic surfactant and an anionic surfactant having a polyoxyethylene group therein
  • US 4,847,186 discloses the use of a fluorinated ionic or non-ionic compound
  • EP 245,090 discloses the combination of fluoroalkylpolyoxyethylene compounds with fluorine-containing polymers and a polyoxyethylene non-ionic surfactant together with a high-molecular high weight hardening agent
  • US 3,850,640 discloses the combination of a first layer comprising an anionic surfactant and a second layer comprising cationic and non-ionic surfactants
  • US 4,596,766 discloses the combination of a polyoxyethylene non-ionic surfactant and a fluorine-containing compound
  • US 4,367,283 discloses the combination of a polyoxyethylene non
  • polyethylene oxide compounds have antistatic effects, but they often have an adverse influence upon photographic properties, such as an increase in fog, desensitization, and deterioration of granularity, in particular in silver halide photographic materials in which both sides of the support are coated with silver halide emulsions, such as medical X-ray photographic materials.
  • the combination of polyoxyethylene compounds with organic salts can improve the surface resistivity, but also may increase of tackiness and film-to-film adhesion.
  • fluorinated surfactants for controlling the electricity generation caused by friction or contacting with different materials, such as, for example, rollers, increases the charging in negative polarity. Accordingly, although it is possible to adapt the electric characteristics of the silver halide photographic material for each roller, such as, for example, rubber rollers, DelrinTM rollers, and nylon rollers by suitably combining the fluorinated surfactants with surfactants, charging in positive polarity problems still occurs, because a general solution for all kind of rollers cannot be obtained.
  • the present invention relates to a silver halide photographic material comprising a support, at least one silver halide emulsion layer coated thereon, and a hydrophilic colloid layer coated on said at least one silver halide emulsion layer, wherein said hydrophilic colloid layer comprises a combination of (a) at least one surfactant selected from the group consisting of non-ionic perfluoroalkyl(ene)polyoxyethylene surfactants and polyoxyethylene-modified polysiloxane surfactants, and (b) at least one salt selected from the group of salts of perfluoroalkylsulfonyl imide or perfluoroalkylsulfonyl methide.
  • a surfactant selected from the group consisting of non-ionic perfluoroalkyl(ene)polyoxyethylene surfactants and polyoxyethylene-modified polysiloxane surfactants
  • at least one salt selected from the group of salts of perfluoroalkylsul
  • the silver halide photographic material according to the present invention comprises a combination of a non-ionic perfluoroalkyl(ene)polyoxy-ethylene surfactant and/or a polyoxyethylene-modified polysiloxane surfactant, and at least one salt of a perfluoroalkylsulfonyl imide or perfluoroalkylsulfonyl methide.
  • the combination is coated on the silver halide emulsion layer together with a hydrophilic binder as a top-coat protective layer.
  • non-ionic perfluoroalkyl(ene)polyoxyethylene surfactants means a non-ionic surfactant comprising a mixture of compounds consisting in an alkyl or alkylene group of from 4 to 16 carbon atoms wherein the hydrogens are totally replaced by fluorine atoms (at least 90% of the hydrogens are replaced by fluorine) joined to a polyoxyethylene group comprising from 6 to 30 oxyethylene groups.
  • the described chemical material includes the basic group and that group with conventional substitution.
  • moiety is used to describe a chemical compound or substituent only an unsubstituted chemical material is intended to be included.
  • the non-ionic perfluoroalkyl(ene)polyoxyethylene surfactants can be represented by the following formula: wherein Rf can be a perfluoroalkyl group, a perfluoroalkylene group, a perfluorocycloalkyl group, and a perfluorocycloalkylene group having from 4 to 16 carbon atoms, X can be -O-, -SO2NR''-, -CONR'', -CH2O-, or a single bond, R, R' and R'' are, independently, hydrogen or a lower alkyl of from 1 to 4 carbon atoms, and y is a number from 6 to 30.
  • a particularly preferred non-ionic perfluoroalkylpolyoxyethylene surfactant is the ZonylTM FSN, a trade name of DuPont Company.
  • Non-ionic perfluoroalkyl(ene)polyoxyethylene surfactants are used in amount of from 10 to 100 mg/m2, preferably from 20 to 60 mg/m2, more preferably of about 40 mg/m2 of top-coat protective layer.
  • Other useful non-ionic perfluoroalkyl(ene)poly-oxyethylene surfactants are listed below.
  • the polyoxyethylene-modified polysiloxane surfactant comprises a non-ionic polysiloxane polymer (preferably having a linear polymeric backbone) which has pendant polyoxyethylene polymeric units adhered to the polysiloxane backbone.
  • the polyoxyethylene chain is preferably linked to the polysiloxane through ether linkages, and the polyoxyethylene may also contain propylene units as random or block units throughout the polyoxyethylene chain.
  • the polyoxyethylene-modified polysiloxane surfactant can be better represented by the following formula: wherein R is a lower alkyl having from 1 to 4 carbon atoms, R' is a lower alkylene having from 1 to 4 carbon atoms, R'' is hydrogen or a lower alkyl of from 1 to 4 carbon atoms, m is an integer from 5 to 100, n is an integer from 2 to 50, p is an integer from 5 to 50, and q is an integer from 0 to 50.
  • R is a lower alkyl having from 1 to 4 carbon atoms
  • R' is a lower alkylene having from 1 to 4 carbon atoms
  • R'' is hydrogen or a lower alkyl of from 1 to 4 carbon atoms
  • m is an integer from 5 to 100
  • n is an integer from 2 to 50
  • p is an integer from 5 to 50
  • q is an integer from 0 to 50.
  • Compounds of this class are sold by Union Carbide Co.,
  • Examples of useful compounds for use in the combination of the present invention are SilwetTM L-7605, SilwetTM L-77, SilwetTM L-7001, and the like.
  • the polyoxyethylene-modified polysiloxane surfactants are used in amount of from 1 to 100 mg/m2, preferably from 5 to 50 mg/m2 of top-coat protective layer.
  • the salt of perfluoroalkylsulfonyl imide or perfluoroalkylsulfonyl methide useful in the combination of the present invention can be represented by the following formula: wherein Rf is a fluorinated alkyl group having 1 to 10 carbon atoms, X is nitrogen or carbon atom, M is an organic or inorganic cation, and v is the X valence, and wherein two Rf groups can join together to form a ring.
  • M can be any of alkali metal cations, alkaline-earth metal cations, an alkyl ammonium cation, or a quaternary ammonium cation.
  • M can be Li+, Na+, K+. In the most preferred embodiment M is Li+.
  • v is 3 when X is nitrogen atom, and v is 4 when X is a carbon atom.
  • the top-coat layer comprising the antistatic combination of the present invention can comprise other compounds conventionally known in the art, such as, for example, coating aids, hardeners, and the like. Particularly useful coating aids are ionic and non-ionic polyoxyethylene surfactants and alkylsulfate surfactants.
  • the antistatic layer of the present invention may contain other addenda which do not influence the antistatic properties of the layer, such as, for example, matting agents, plasticizers, lubricants, dyes, and haze reducing agents.
  • non-ionic polyoxyethylene surfactants useful as coating aids in the top-coat layer comprising the combination of the present invention can be represented by the following formula: wherein R2 represents an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 ring atoms (such as phenyl or naphthyl) or a combination thereof, R3 represents a hydrogen atom or a methyl group, D represents a group -O-, -S-, -COO-, -NR4-, -CO-NR4-, or -SO2-NR4-, wherein R4 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, q represents 0 or 1 and r represents an integer of 2 to 50.
  • non-ionic polyoxyalkylene surfactants examples include but are illustrated below.
  • the non-ionic polyoxyalkylene surfactants are employed in an amount of from 10 to 200 mg/m2, preferably from 20 to 150 mg/m2, more preferably from 30 to 120 mg/m2 of top-coat protective layer.
  • Anionic polyoxyethylene surfactants are surfactants of the type including a polyoxyethylene group linked to an anionic hydrophilic group and to a hydrocarbon residue directly or by means of a bridge consisting of a divalent organic residue, as expressed by the following formula: wherein R is an aliphatic, aromatic or a mixed hydrocarbon residue and preferably a linear or branched alkyl group having from 4 to 18 carbon atoms or an aryl group substituted with one or more alkyl groups altogether having from 4 to 18 carbon atoms,A is a divalent organic residue, preferably a carbonyl, a sulfonyl, an amino or an alkylene group preferably having from 1 to 3 carbon atoms, an oxygen atom or groups consisting of two or more of the above-mentioned groups, such as for example carbonylamino, sulfonylamino, aminocarbonyl, aminosulfonyl, or ester, X is an anionic group selected from the class
  • Me is an alkaline or alkaline-earth metal, such as Na, K, Li, Ca, Mg, and the like, and m is 0 or 1 and n is an integer of from 1 to 25.Anionic surface active agents of this type are described for example in Schwarz et al. "Surface Active Agents and Detergents", Vol. I and II, Interscience Publ., in the US Pat. Nos. 2,992,108, 3,068,101, 3,201,152 and 3,165,409, in the French Pat. Nos. 1,556,240 and 1,497,930 and in the British Pat. Nos.
  • anionic polyoxyethylene surfactants useful in the combination of the present invention are listed hereinbelow. C12H25 ⁇ O ⁇ (CH2CH2O)2-SO3 ⁇ Na+ C18H37 ⁇ SO2-NH ⁇ (CH2CH2O)4 ⁇ SO3 ⁇ Na+
  • the anionic polyoxyalkylene surfactants are employed in an amount of from from 10 to 200 mg/m2, preferably from 20 to 100 mg/m2, more preferably from 30 to 80 mg/m2 of top-coat protective layer.
  • Alkylsulfate surfactants normally used in photography, are surfactants of the type including an alkyl group linked to a sulfate group through an oxygen atom, as expressed by the following formula: wherein R is an aliphatic group and preferably a linear or branched alkyl group having from 4 to 18 carbon atoms, and Me is an alkali metal, such as Na, K, Li.
  • the alkylsulfate surfactants are employed in an amount of from 10 to 200 mg/m2, preferably from 10 to 100 mg/m2, more preferably from 10 to 50 mg/m2 of top-coat protective layer.
  • Photographic materials according to the invention generally comprise at least one light sensitive layer, such as a silver halide emulsion layer, coated on at least one side of a support.
  • Silver halide emulsions typically comprise silver halide grains which may have different crystal forms and sizes, such as, for example, cubic grains, octahedral grains, tabular grains, spherical grains and the like. Tabular grains are preferred.
  • the tabular silver halide grains contained in the silver halide emulsion layers of this invention have an average diameter:thickness ratio (often referred to in the art as aspect ratio) of at least 3:1, preferably 3:1 to 20:1, more preferably 3:1 to 14:1, and most preferably 3:1 to 8:1.
  • Average diameters of the tabular silver halide grains suitable for use in this invention range from about 0.3 to about 5 ⁇ m, preferably 0.5 to 3 ⁇ m, more preferably 0.8 to 1.5 ⁇ m.
  • the tabular silver halide grains suitable for use in this invention have a thickness of less than 0.4 ⁇ m, preferably less than 0.3 ⁇ m and more preferably less than 0.2 ⁇ m.
  • the tabular silver halide grain characteristics described above can be readily ascertained by procedures well known to those skilled in the art.
  • the term "diameter” is defined as the diameter of a circle having an area equal to the projected area of the grain.
  • the term “thickness” means the distance between two substantially parallel main planes constituting the tabular silver halide grains.
  • the diameter:thickness ratio of each grain can be calculated, and the diameter:thickness ratios of all tabular grains can be averaged to obtain their average diameter:thickness ratio.
  • the average diameter:thickness ratio is the average of individual tabular grain diameter:thickness ratios. In practice, it is simpler to obtain an average diameter and an average thickness of the tabular grains and to calculate the average diameter:thickness ratio as the ratio of these two averages. Whatever the used method may be, the average diameter:thickness ratios obtained do not greatly differ.
  • At least 15%, preferably at least 25%, and, more preferably, at least 50% of the silver halide grains are tabular grains having an average dia-meter:thickness ratio of not less than 3:1.
  • Each of the above proportions, "15%”, “25%” and “50%” means the proportion of the total projected area of the tabular grains having a diameter:thickness ratio of at least 3:1 and a thickness lower than 0.4 ⁇ m, as compared to the projected area of all of the silver halide grains in the layer.
  • Other conventional silver halide grain structures such as cubic, orthorhombic, tetrahedral, etc. may make up the remainder of the grains.
  • halogen compositions of the silver halide grains can be used.
  • Typical silver halides include silver chloride, silver bromide, silver iodide, silver chloroiodide, silver bromoiodide, silver chloro-bromoiodide and the like.
  • silver bromide and silver bromoiodide are preferred silver halide compositions for tabular silver halide grains with silver bromoiodide compositions containing from 0 to 10 mol% silver iodide, preferably from 0.2 to 5 mol% silver iodide, and more preferably from 0.5 to 1.5% mol silver iodide.
  • the halogen composition of individual grains may be homogeneous or heterogeneous.
  • Silver halide emulsions containing tabular silver halide grains can be prepared by various processes known for the preparation of photographic materials.
  • Silver halide emulsions can be prepared by the acid process, neutral process or ammonia process.
  • a soluble silver salt and a halogen salt can be reacted in accordance with the single jet process, double jet process, reverse mixing process or a combination process by adjusting the conditions in the grain formation, such as pH, pAg, temperature, form and scale of the reaction vessel, and the reaction method.
  • a silver halide solvent such as ammonia, thioethers, thioureas, etc.
  • ammonia such as ammonia, thioethers, thioureas, etc.
  • thioureas may be used, if desired, for controlling grain size, form of the grains, particle size distribution of the grains, and the grain-growth rate.
  • Preparation of silver halide emulsions containing tabular silver halide grains is described, for example, in de Cugnac and Chateau, "Evolution of the Morphology of Silver Bromide Crystals During Physical Ripening", Science and Industries Photographiques, Vol. 33, No.2 (1962), pp. 121-125, in Gutoff, "Nucleation and Growth Rates During the Precipitation of Silver Halide Photographic Emulsions", Photographic Science and Engineering, Vol. 14, No. 4 (1970), pp.
  • gelatin As a binder for silver halide emulsions and other hydrophilic colloid layers, gelatin is preferred, but other hydrophilic colloids can be used, alone or in combination, such as, for example, dextran, cellulose derivatives (e.g.,hydroxyethylcellulose, carboxymethyl cellulose), collagen derivatives, colloidal albumin or casein, polysaccharides, synthetic hydrophilic polymers (e.g., polyvinylpyrrolidone, polyacrylamide, polyvinylalcohol, polyvinylpyrazole) and the like.
  • Gelatin derivatives such as, for example, highly deionized gelatin, acetylated gelatin and phthalated gelatin can also be used.
  • Highly deionized gelatin is characterized by a higher deionization with respect to the commonly used photographic gelatins.
  • highly deionized gelatin is almost completely deionized which is defined as meaning that it presents less than 50 ppm (parts per million) of Ca++ ions and is practically free (less than 5 parts per million) of other ions such as chlorides, phosphates, sulfates and nitrates, compared with commonly used photographic gelatins having up to 5,000 ppm of Ca++ ions and the significant presence of other ions.
  • the amount of gelatin employed in the light-sensitive photographic material of the present invention is such as to provide a total silver to gelatin ratio lower than 1 (expressed as grams of Ag/grams of gelatin).
  • the silver to gelatin ratio of the silver halide emulsion layers is in the range of from 1 to 1.5.
  • Silver halide emulsion layers can be sensitized to a particular range of wavelengths with a sensitizing dye. Typical sensitizing dyes include cyanine, hemicyanine, merocyanine, oxonols, hemioxonols, styryls, merostyryls and streptocyanines.
  • the silver halide photographic material of the present invention can have one or more silver halide emulsion layers sensitized to the same or different regions of the electromagnetic spectrum.
  • the silver halide emulsion layers can be coated on one side or on both side of a support base.
  • materials suitable for the preparation of the support include glass, paper, polyethylene-coated paper, metals, polymeric film such as cellulose nitrate, cellulose acetate, polystyrene, polyethylene terephthalate, polyethylene, polypropylene and the like.
  • Specific photographic materials according to the invention are black-and-white light-sensitive photographic materials, in particular X-ray light-sensitive materials.
  • Preferred light-sensitive silver halide photographic materials according to this invention are radiographic light-sensitive materials employed in X-ray imaging comprising a silver halide emulsion layer(s) coated on one surface, preferably on both surfaces of a support, preferably a polyethylene terephthalate support.
  • the silver halide emulsions are coated on the support at a total silver coverage in the range of 3 to 6 grams per square meter.
  • the radiographic light-sensitive materials are associated with intensifying screens so as to be exposed to radiation emitted by said screens.
  • the screens are made of relatively thick phosphor layers which transform the X-rays into more imaging-effective radiation such as light (e.g., visible light).
  • the screens absorb a much larger portion of X-rays than the light-sensitive materials do and are used to reduce the X-ray dose necessary to obtain a useful image.
  • the phosphors can emit radiation in the ultraviolet, blue, green or red region of the visible spectrum and the silver halide emulsions are sensitized to the wavelength region of the radiation emitted by the screens. Sensitization is performed by using spectral sensitizing dyes absorbed on the surface of the silver halide grains as known in the art. More preferred light-sensitive silver halide photographic materials according to this invention are radiographic light-sensitive materials which employ intermediate diameter:thickness ratio tabular grain silver halide emulsions, as disclosed in US 4,425,426 and in EP Pat. Appl. 84,637.
  • black-and-white photographic materials such as lithographic light-sensitive materials, black-and-white photographic printing papers, black-and-white negative films, as well as light-sensitive photographic color materials such as color negative films, color reversal films, color papers, etc.
  • the light sensitive layers intended for use in color photographic material contain or have associated therewith dye-forming compounds or couplers.
  • a red-sensitive emulsion would generally have a cyan coupler associated therewith
  • a green-sensitive emulsion would generally have a magenta coupler associated therewith
  • a blue-sensitive emulsion would generally have a yellow coupler associated therewith.
  • the silver halide photographic materials of the present invention are fore-hardened.
  • organic or inorganic hardeners include chrome salts (e.g., chrome alum, chromium acetate), aldehydes (e.g., formaldehyde and glutaraldehyde), isocyanate compounds (hexamethylene diisocyanate), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine), epoxy compounds (e.g., tetramethylene glycol diglycidylether), N-methylol derivatives (e.g., dimethylolurea, methyloldimethyl hydantoin), aziridines, mucohalogeno acids (e.g., mucochloric acid), active vinyl derivatives (e.g., vinylsulfonyl arid hydroxy substituted vinylsulfonyl derivatives) and the like.
  • chrome salts e.g., chrome alum, chromium acetate
  • aldehydes e.g., formal
  • any known developing agent can be used into the developer, such as, for example, dihydroxybenzenes (e.g., hydroquinone), pyrazolidones (1-phenyl-3-pyrazo-lidone-4,4-dimethyl-1-phenyl-3-pyrazolid-one), and aminophenols (e.g., N-meth-yl-p-aminophenol), alone or in combinations thereof.
  • dihydroxybenzenes e.g., hydroquinone
  • pyrazolidones (1-phenyl-3-pyrazo-lidone-4,4-dimethyl-1-phenyl-3-pyrazolid-one
  • aminophenols e.g., N-meth-yl-p-aminophenol
  • the silver halide photographic materials are developed in a developer comprising dihydroxy-benzenes as the main developing agent, and pyrazolidones and p-aminophenols as auxiliary developing agents.
  • additives can be present in the developer, such as, for example, antifoggants (e.g., benzotriazoles, indazoles, tetrazoles), silver halide solvents (e.g., thiosulfates, thiocyanates), sequestering agents (e.g., aminopolycarboxylic acids, aminopolyphosphonic acids), sulfite antioxidants, buffers, restrainers, hardeners, contrast promoting agents, surfactants, and the like.
  • Inorganic alkaline agents such as KOH, NaOH, and LiOH are added to the developer composition to obtain the desired pH which is usually higher than 10.
  • the silver halide photographic material of the present invention can be processed with a fixer of typical composition.
  • the fixing agents include thiosulfates, thiocyanates, sulfites, ammonium salts, and the like.
  • the fixer composition can comprise other well known additives, such as, for example, acid compounds (e.g., metabisulfates), buffers (e.g., carbonic acid, acetic acid), hardeners (e.g., aluminum salts), tone improving agents, and the like.
  • acid compounds e.g., metabisulfates
  • buffers e.g., carbonic acid, acetic acid
  • hardeners e.g., aluminum salts
  • the processing temperature ranges from 20° to 60°C, preferably from 30° to 50°C and the processing time is lower than 90 seconds, preferably lower than 45 seconds.
  • the good antistatic and surface characteristics of the silver halide photographic material of the present invention allow the rapid processing of the material without having the undesirable appearance of static marks or scratches on the surface of the film. The invention will be described hereinafter by reference to the following example.
  • a tabular grain silver bromide emulsion (having an average dia-meter:thickness ratio of about 7.6:1, prepared in the presence of a deionized gelatin having a viscosity at 60°C in water at 6.67% w/w of 4.6 mPas, a conducibility at 40°C in water at 6.67% w/w of less than 150 ⁇ s/cm and less than 50 ppm of Ca++) was optically sensitized to green light with a cyanine dye and chemically sensitized with sodium p-toluenethiosulfonate, sodium p-toluenesulfinate and benzothiazoleiodoethylate.
  • non-deionized gelatin having a viscosity at 60°C in water at 6.67% w/w of 5.5 mPas, a conducibility at 40°C in water at 6.67% w/w of 1,100 ⁇ s/cm and 4,500 ppm of Ca++
  • Each portion was coated on each side of a blue polyester film support at a silver coverage of 2.15 g/m2 and a gelatin coverage of 1.5 g/m2 per side.
  • a non-deionized gelatin protective supercoat containing 1.01 g/m2 of gelatin per side and the compounds indicated in Table 1 was applied on each coating so obtaining seventeen different double-side radiographic films 1 to 17.
  • Compound A is a perfluoromethylsulfonylmethide lithium salt having the following formula:
  • compound B is a perfluoromethylsulfonylimide lithium salt having the following formula:
  • compound C is a non-ionic perfluoroalkylenepolyoxyethylene surfactant having the following formula:
  • TritonTM X-200 is the trade name of an anionic surfactant of the alkylphenyloxyethylene sulfonate type having the following formula:
  • TritonTM X-100 is the trade name of a non-ionic surfactant of the alkylphenoxyethylene type having the following formula:
  • ZonylTM FSN is the trade name of a non-ionic surfactant of the perfluoroalkylpolyoxyethylene type, manufactured by DuPont and having the following formula: wherein x is an integer from 10 to 20.
  • the samples 1 to 17 were conditioned for 160 minutes at 70°C and 40% of relative humidity to evaluate the sensitometric properties, and for 15 hours at 50°C and 20% relative humidity to evaluate the physical properties. After conditioning, the samples were exposed and developed. The samples were then evaluated according to the following tests.
  • the static charge dissipation of each of the films was measured.
  • the charge decay time was measured with a Charge Decay Test Unit JCI 155 (manufactured by John Chubb Ltd., London).
  • This apparatus deposits a charge on the surface of the film by a high voltage corona discharge and a fieldmeter allows observation of the decay time of the surface voltage. The lower the time, the better the antistatic properties of the film.
  • this surface was grounded by contacting it with a metallic back surface.
  • This test was performed with a Lhomargy apparatus. It consists of a slide moving on the film at a speed of about 15 cm/min. A force transducer connected to the slide transforms the applied force into an amplified DC voltage which is recorded on a paper recorder. The force applied to start the sliding movement represents the value of static slipperiness. The movement of the slide on the film is not continuous. The discontinuity of the movement can be measured (in terms of slipperiness difference) from the graph of the paper recorder. This value represents the dynamic slipperiness. It was noted that the more the movement was discontinuous (i.e., the higher the value of slipperiness difference), the better was the performance of the film.
  • Samples 9 to 17 of the invention give the best results in terms of decay time and surface resistivity.
  • samples 16 and 17 comprising compound C and compound B give the best results.
  • a tabular grain silver bromide emulsion (having an average dia-meter:thickness ratio of about 7.6:1, prepared in the presence of a deionized gelatin having a viscosity at 60°C in water at 6.67% w/w of 4.6 mPas, a conducibility at 40°C in water at 6.67% w/w of less than 150 ⁇ s/cm and less than 50 ppm of Ca++) was optically sensitized to green light with a cyanine dye and chemically sensitized with sodium p-toluenethiosulfonate, sodium p-toluene-sulfinate and benzothiazoleiodoethylate.
  • non-deionized gelatin having a viscosity at 60°C in water at 6.67% w/w of 5.5 mPas, a conducibility at 40°C in water at 6.67% w/w of 1,100 ⁇ s/cm and 4,500 ppm of Ca++
  • Invention compound 1 is a perfluoromethylsulfonylimide lithium salt having the following formula:
  • SilwetTM L-7605 is the trade name of a polyalkyleneoxide-modified dimethylpolysiloxane surfactant manufactured by Union Carbide and having the following formula: wherein m ranges from 5 to 100, n ranges from 2 to 50, p ranges from 5 to 50, and q ranges from 0 to 50.
  • the samples 1 to 9 were conditioned for 160 minutes at 70°C and 40% of relative humidity to evaluate the sensitometric properties, and for 15 hours at 50°C and 20% relative humidity to evaluate the physical properties. After conditioning the samples were exposed and developed. The samples were then evaluated according to the same tests of Example 1.

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EP95109067A 1994-06-30 1995-06-13 Matériau photographique à l'halogénure d'argent ayant des propriétés antistatiques Withdrawn EP0690338A1 (fr)

Priority Applications (1)

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EP95109067A EP0690338A1 (fr) 1994-06-30 1995-06-13 Matériau photographique à l'halogénure d'argent ayant des propriétés antistatiques

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EP94110158 1994-06-30
EP94110158 1994-06-30
EP95109067A EP0690338A1 (fr) 1994-06-30 1995-06-13 Matériau photographique à l'halogénure d'argent ayant des propriétés antistatiques

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0731147A3 (fr) * 1995-03-06 1997-11-19 Minnesota Mining And Manufacturing Company Colorants cationiques avec un contre-anion alkyle sulfonyle fluoré, solubles dans les solvants organiques
WO2002092719A1 (fr) * 2001-05-10 2002-11-21 3M Innovative Properties Company Sels d'ammonium de polyoxyalkylene et leur utilisation en tant qu'agents antistatiques

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4370254A (en) * 1979-05-25 1983-01-25 Bayer Aktiengesellschaft Use of perfluoroalkane sulphonamide salts as surface active agents
EP0111338A2 (fr) * 1982-12-14 1984-06-20 E.I. Du Pont De Nemours And Company Procédé pour l'étendage avec emploi d'agents tensio-actifs
US4505997A (en) * 1982-06-01 1985-03-19 Agence Nationale De Valorisation De La Recherche (Anvar) Bis perhalogenoacyl -or sulfonyl-imides of alkali metals, their solid solutions with plastic materials and their use to the constitution of conductor elements for electrochemical generators
EP0242853A2 (fr) * 1986-04-21 1987-10-28 Konica Corporation Matériau photographique à l'halogénure d'argent à propriétés antistatiques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4370254A (en) * 1979-05-25 1983-01-25 Bayer Aktiengesellschaft Use of perfluoroalkane sulphonamide salts as surface active agents
US4505997A (en) * 1982-06-01 1985-03-19 Agence Nationale De Valorisation De La Recherche (Anvar) Bis perhalogenoacyl -or sulfonyl-imides of alkali metals, their solid solutions with plastic materials and their use to the constitution of conductor elements for electrochemical generators
EP0111338A2 (fr) * 1982-12-14 1984-06-20 E.I. Du Pont De Nemours And Company Procédé pour l'étendage avec emploi d'agents tensio-actifs
EP0242853A2 (fr) * 1986-04-21 1987-10-28 Konica Corporation Matériau photographique à l'halogénure d'argent à propriétés antistatiques

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0731147A3 (fr) * 1995-03-06 1997-11-19 Minnesota Mining And Manufacturing Company Colorants cationiques avec un contre-anion alkyle sulfonyle fluoré, solubles dans les solvants organiques
WO2002092719A1 (fr) * 2001-05-10 2002-11-21 3M Innovative Properties Company Sels d'ammonium de polyoxyalkylene et leur utilisation en tant qu'agents antistatiques
KR100877638B1 (ko) * 2001-05-10 2009-01-12 쓰리엠 이노베이티브 프로퍼티즈 컴파니 폴리옥시알킬렌 암모늄염 및 그의 정전기 방지제로서의용도
US7678941B2 (en) 2001-05-10 2010-03-16 3M Innovative Properties Company Polyoxyalkylene ammonium salts and their use as antistatic agents
US7893144B2 (en) 2001-05-10 2011-02-22 3M Innovative Properties Company Polyoxyalkylene ammonium salts and their use as antistatic agents

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