EP0890874B1 - Vor Gelbschleierbildung geschützte photographische Silberhalogenidzusammensetzungen - Google Patents

Vor Gelbschleierbildung geschützte photographische Silberhalogenidzusammensetzungen Download PDF

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Publication number
EP0890874B1
EP0890874B1 EP98202001A EP98202001A EP0890874B1 EP 0890874 B1 EP0890874 B1 EP 0890874B1 EP 98202001 A EP98202001 A EP 98202001A EP 98202001 A EP98202001 A EP 98202001A EP 0890874 B1 EP0890874 B1 EP 0890874B1
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Prior art keywords
layer
compound
silver halide
material according
light
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EP98202001A
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English (en)
French (fr)
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EP0890874A1 (de
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Walter Pattyn
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Agfa Gevaert NV
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Agfa Gevaert NV
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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
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • G03C1/93—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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
    • 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
    • G03C1/76—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
    • 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
    • G03C1/0051—Tabular grain emulsions
    • G03C2001/0055—Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • G03C2001/7635—Protective layer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00—Details
    • G03C2200/34—Hydroquinone
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00—Details
    • G03C2200/40—Mercapto compound

Definitions

  • the present invention relates to silver halide photographic compositions and more particularly to radiographic materials comprising additives improving stability against yellow fog formation.
  • Yellow fog formation in light-sensitive silver halide photographic materials is known in the art as a problem which is in most general cases related with the presence of fine silver nuclei. These nuclei generated by reduction before, during or after processing of silver salts present in the emulsion layer and/or more outermost layers of the said materials occur therein as particles.
  • silver halide light-sensitive photographic materials are susceptible to yellowing after storage, the cause thereof has nearly always been sought in the occurrence of adsorption phenomena of finely divided silver particles formed by reduction in more or less exhausted developers at the surface of the processed material where the physical development of silver ions takes place.
  • the yellowing phenomenon is most likely due to the deposition of finely divided silver in a non-light-sensitive colloid layer coated in water-permeable relationship with the light-sensitive emulsion layer.
  • Photographic light-sensitive silver halide materials for radiography are often coated with high amounts of silver per sq.m. in order to reach the required speed.
  • an interleaving paper is used between consecutive films piled up in a package in order to avoid sticking and surface damaging of the said films in contact with each other in the severe preservation conditions described hereinbefore and/or if said films are hardened to a lower extent in order to avoid loss in speed, the problem of "yellowing” or "yellow stain” appears to become even more stringent. Said undesirable stain then often appears in form of depicting fibrous structures of the interleaving paper or spacing paper on the radiographic film material, thereby disturbing a suitable unambiguous medical diagnosis.
  • a first object of the present invention is to provide silver halide light-sensitive photographic materials free from yellowing or yellow staining after processing.
  • a light-sensitive silver halide photographic material comprising a support, one or more water-permeable light-sensitive silver halide layer(s) on one or both sides of the said support, a outermost protective antistress layer, and optionally an after layer on top of the outermost protect layer wherein each layer of said material comprises a non-ionic polyoxyalkylene compound in an amount of from 0 to less than 5 mg/m 2 , wherein said protective antistress layer and/or said light-sensitive layer(s) comprise(s) an ionic polyoxyalkylene compound and wherein said material has a lateral surface resistance, determined as prescribed in DIN 53482, of less than 1 x 10 10 Ohm/square.
  • the said layer is preferably free from any polyoxyalkylene compound.
  • each hydrophilic layer of the said material comprises a non-ionic polyoxyalkylene compound in an amount of from 0 to less than 5 mg/m 2 and more preferred from 0 to less than 3 mg/m 2 .
  • non-ionic polyoxyalkylenes which should be present in minor amounts and the presence of which should even be avoided in each of the hydrophilic water-permeable layers of the single- or double-side coated radiographic material of the present invention are e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, silicone-polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides.
  • polyethylene glycol polyethylene glycol/polypropylene glycol condensation products
  • polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers polyethylene glycol esters
  • polyethylene glycol sorbitan esters polyalkylene glycol alkyl
  • n and m are integers having a value of at least 4 and, more preferably, between 8 and 30, R represents a long chain (substituted or unsubstituted) alkyl or alkylaryl group having at least 10 C-atoms as e
  • non-ionic polyoxyalkylene compounds having fluorinated alkyl chains like e.g. the N-polyoxyethylene ethyl perfluoro caprylic acid amide compound having caprylic acid amide as a terminal group, corresponding to the formula (II), which should particularly be avoided: C 7 F 15 CONH-(C 2 H 4 )-(OC 2 H 4 ) 17 -OH
  • coating solutions may contain non-ionic polyoxyalkylene compounds as preferred surfactants or may contain said compounds as impurities present in minor amounts.
  • ionic polyoxyalkylene compounds instead of the non-ionic polyoxyalkylene compounds discussed hereinbefore it is preferred to use ionic polyoxyalkylene compounds in one or more layers of the photographic material of the present invention in order to reach the objects of the present invention as set forth hereinbefore.
  • An especially preferred ionic polyoxyalkylene compound is C 8 H 17 -Phen-(O-C 2 H 4 ) 8 -CH 2 -COONa
  • any of the generally known polyoxyalkylene compounds having an ionizable group like e.g. a carboxylic acid or sulphonic acid group, may be used in the protective antistress layer.
  • the compound given in formula (III), wherein Phen represents "phenyl” is e.g. very representative therefore and may be further substituted or unsubstituted. References related therewith have also been given in the survey of Research Disclosures 36544, September 1994 and 38957, September 1996, Chapter IX.
  • one or more ionic polyoxyalkylene compound(s) is(are) present in the protective antistress layer and/or in one or more light-sensitive silver halide emulsion layer(s), wherein maximum amounts of less than 30 mg/m 2 , more preferably from 10 to 25 mg/m 2 and even more preferably from 10 to 20 mg/m 2 are present.
  • hydrophilic colloid binder present in the hydrophilic layers of the photographic material according to the present invention proteinaceous colloids, e.g. gelatin, polysaccharides, e.g. (potatoe) starch, and synthetic substitutes as e.g. polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyvinyl imidazole, polyvinyl pyrazole, polyacrylamide, polyacrylic acid, and derivatives thereof can be used. Another preferred alternative is colloidal silica sol. Furthermore the use of mixtures of said hydrophilic colloids is not excluded. Among these binders the most preferred is gelatin. Conventional lime-treated or acid treated gelatin can be used.
  • gelatin The preparation of such gelatin types has been described in e.g. "The Science and Technology of Gelatin", edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 and next pages.
  • the gelatin can also be an enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan, N° 16, page 30 (1966).
  • gelatin can however be replaced in part or integrally by synthetic polymers as cited hereinbefore or by natural or semi-synthetic polymers.
  • Natural substitutes for gelatin are e.g. other proteins such as zein, albumin and casein, cellulose, saccharides, starch, and alginates.
  • Semi-synthetic substitutes for gelatin are modified natural products as e.g.
  • gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents or by grafting of polymerizable monomers on gelatin, and cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates.
  • the silver halide photographic material of the present invention should preferably be completely free from any hydrophobic or hydrophilic polyoxyalkylene compound.
  • Ionic cross-linked copolymers known from e.g. US-A's 4,301,240 and 5,561,032 may be present in the protective antistress coating of the material according to the present invention.
  • a preferred latex used therein is a latex of a cross-linked polymer, being a copolymer of an acrylic and/or methacrylic acid ester including 90-99 mole % of acrylate and/or methacrylate units and 1 to 10 mole % of tetraallyloxyethane units as polyfunctional cross-linking monomer, wherein in said copolymer at least 75 % of the ester groups have been transformed into alkali metal carboxylate groups, thus exhibiting ionic characteristics.
  • An especially preferred latex of a cross-linked ionic polymer is poly([c.l.]tetra-allyloxy-ethane-co-methyl acrylate/acrylic acid) with a 3/18/79 molar ratio.
  • polymers or copolymeric combinations of monomers have been found to be very useful as ionic or nonionic polymers, whether or not in combination with cross-linked copolymers cited hereinbefore: polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, polyamethylacrylate, polyethylacrylate, polymethylmethacrylate, polyethylmethacrylate as well as styrene-male ⁇ c acid or a styrenemale ⁇ c acid anhydrid type copolymer.
  • Cross-linked copolymers are applied in an amount of at least 10% by weight versus the amount of hydrophilic colloid present in the antistress layer.
  • said latex-type copolymers may be present in an outermost gelatin free afterlayer coating (if any) applied over the said antistress layer.
  • the protective antistress layer and the afterlayer may further comprise spacing agents and coating aids such as wetting agents as e.g. perfluorinated surfactants.
  • Spacing agents which may also be present in the protective antistress layer generally have an average particle size which is comprised between 0.2 and 10 ⁇ m. Spacing agents can be soluble or insoluble in alkali. Alkaliinsolu-ble spacing agents usually remain permanently in the photographic element, whereas alkali-soluble spacing agents usually are removed therefrom in an alkaline processing bath. Suitable spacing agents can be made i.a. of polymethyl methacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropylmethyl cellulose hexahydrophthalate. Other suitable spacing agents have been described in US-A 4,614,708.
  • a preferred protective antistress layer is made from gelatin hardened up to a degree corresponding with a water absorption of less than 2.5 grams of water per m 2 at 38°C.
  • the gelatin coverage in the protective layer is preferably not higher than about 1.20 g per m 2 and is more preferably in the range of 1.20 to 0.60 g per m 2 .
  • gelatin in the antistress layer is partially replaced by colloidal silica as it gives rise to a further improvement of physical properties.
  • colloidal silica having an average particle size not larger than 10 nm and with a surface area of at least 300 m 2 per gram is used, the colloidal silica being present at a coverage of at least 50 mg per m 2 .
  • the coverage of said colloidal silica in the antistress layer is preferably in the range of 50 mg to 500 mg per m 2 .
  • Particularly good results which are fully in accordance with the present invention are obtained by using an antistatic layer consisting for at least 50 % by weight of colloidal silica versus the preferred ionic polymer latex described hereinbefore.
  • Especially preferred colloidal silica particles have a surface area of 500 m 2 per gram and an average grain size smaller than 7 nm.
  • Such type of silica is sold under the name KIESELSOL 500 (KIESELSOL is a registered trade name of Bayer AG, Leverkusen, Germany).
  • the antistress layer may further contain friction-lowering substance(s) such as dispersed wax particles (carnaubawax or montanwax) or polyethylene particles, fluorinated polymer particles, silicon polymer particles, in order to further reduce the sticking tendency of the layer especially in an atmosphere of high relative humidity.
  • friction-lowering substance(s) such as dispersed wax particles (carnaubawax or montanwax) or polyethylene particles, fluorinated polymer particles, silicon polymer particles, in order to further reduce the sticking tendency of the layer especially in an atmosphere of high relative humidity.
  • the gelatin binder can be forehardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinyl-sulphonyl-2-propanol, chromium salts e.g. chromium acetate and chromium alum, aldehydes e.g. formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin, dioxan derivatives e.g.
  • appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinyl-sulphonyl-2-propanol, chromium salts e.g. chromium acetate and
  • 2,3-dihydroxy-dioxan active vinyl compounds e.g. 1,3,5-triacryloyl-hexahydro-s-triazine, active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid.
  • These hardeners can be used alone or in combination.
  • the binder can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts as disclosed in US-A 4,063,952 and onium compounds as disclosed in EP-A 0 408 143.
  • the presence in the protective layer of the light-sensitive silver halide photograpic material according to the present invention of a mercapto compound and/or a polyhydroxybenzene compound is highly preferred in order to exclude any risk for yellowing.
  • Those products, if present, are added to the coating composition of the protective antistress layer in an amount of from 0.01 to 10 mg/m 2 , more preferably from 0.04 to 4 mg/m 2 , and/or in an amount of from 2.5 to 250 mg/m 2 and more preferably from 1 to 100 mg/m 2 respectively.
  • Preferred mercapto-compounds are unsubstituted or substituted mercaptotetrazole compounds as e.g. 1-phenyl-5-mercaptotetrazole, wherein, if substituted, a substituent making the said compound(s) soluble in alkaline medium, like e.g. a carboxylic or a sulphonic group, however not being limited thereto, is highly preferred.
  • Preferred polyhydroxybenzene compounds are unsubstituted or substituted dihydroxybenzene compounds, wherein dihydroxybenzene disulphonate is a particularly preferred compound.
  • a common support of a photographic silver halide emulsion material is a hydrophobic resin support or hydrophobic resin coated paper support.
  • Hydrophobic resin supports are well known to those skilled in the art and are made e.g. of polyester, polystyrene, polyvinyl chloride, polycarbonate, preference being given to polyethylene terephthalate or polyethylene naphthalate.
  • the hydrophobic resin support is commonly provided with one or .more.hydrophobic.subbing.layers known to those skilled in the art for adhering thereto a hydrophilic colloid layer.
  • Suitable subbing layers for polyethylene terephthalate supports are known e.g. from US-A's 3,397,988, 3,649,336, 4,123,278 and 4,478,907.
  • the light-sensitive silver halide photographic materials according to the present invention have a lateral surface resistance of less than 1 x 10 10 Ohm/square, and more preferably of not more than 1 x 10 9 Ohm/square, when measured by the method as prescribed in DIN 53482 in order to fully reach the objects of the present invention.
  • the presence of a subbing layer in contact with the said support and a hydrophilic colloidal layer coated thereupon is highly preferred, wherein in a preferred embodiment said hydrophobic subbing layer comprises vinylidene chloride and wherein in a further preferred embodiment of the present invention the said subbing layer comprises a 5 polythiophene compound as a particularly suitable antistatic agent having electronic conductive properties. More particularly for materials according to the present invention a polyethylene dioxythiophene compound should be present in the subbing layer coated onto the support as disclosed e.g. in US-A's 5,312,681 and 5,391,472.
  • the material thus preferably has a subbing layer on one or both sides and adhered to the support, wherein said subbing layer further comprises vinylidene chloride and a polyethylene dioxythiophene compound.
  • a hydrophilic colloidal layer coated upon the subbing layer of the material according to the present invention is a gelatinous layer having gelatin in a preferred amount of from 0.1 to 0.3 g/m 2 , which corresponds with a rather thin intermediate layer between subbing layer and light-sensitive silver halide emulsion layer.
  • Said-intermediate layer may comprise one or more antihalation dyes.
  • Antihalation dyes are non-spectrally sensitising dyes which are widely used in photographic elements in order to absorb reflected and scattered light. Examples of the said dyes have been described e.g. in US-A's 3,560,214; 4,857,446; 5,344,749; 5,478,708; 5,502,205.
  • the filter dye(s) can be coated in layers of photographic elements in the form as has been described in EP-A's 0 401 709; 0 384 633; 0 323 729; 0 274 723; 0 276 566; 0 351 593; in US-A's 4,900,653; 4,904,565; 4,949,654; 4,940,654; 4,948,717; 4,988,611 and 4,803,150; and in Research Disclosure 19551 (July 1980), wherein these examples are not limitative.
  • Light-sensitive silver halide photograpic materials according to the present invention are coated with at least one light-sensitive silver halide emulsion layer.
  • Silver halide emulsions present in said emulsion layer may comprise silver halide emulsion crystals having whatever a crystal habit (e.g. cubic, octahedral, tabular or irregular, in the presence or in the absence of rounded edges, further eventually provided with protrusions, whether or not in form of epitaxial deposits) and a silver halide composition (e.g. silver bromide, silver bromoiodide, silver bromochloride, silver bromochloroiodide, silver chloride, silver chlorobromide, silver chlorobromoiodide, silver chloroiodide).
  • a crystal habit e.g. cubic, octahedral, tabular or irregular, in the presence or in the absence of rounded edges, further eventually provided with protrusions, whether or not in form of epitaxial deposits
  • a silver halide composition e.g. silver bromide, silver bromoiodide, silver bromochloride, silver bromoch
  • emulsions comprising crystals having a tabular crystal habit with ⁇ 100 ⁇ or ⁇ 111 ⁇ major faces are preferred, wherein said crystals have an average crystal thickness of less than 0.3 ⁇ m and an average aspect ratio of more than 2, more preferably a thickness of less than 0.2 ⁇ m and an average aspect ratio of more than 5, and even more preferably more than 8, and wherein tabular crystals account for at least 50 % of the total projective surface of the said crystals. More preferably silver bromoiodide crystals having an iodide concentration of 1 mole % or less are present wherein said crystals have a variation coefficient of less than 25% and more preferably from 10 to 20%.
  • Mixtures of emulsions may be present in one or more emulsion layers as well as crystals differing in crystal habit and/or composition as has been described e.g. in EP-A 0 770 909.
  • Preferred total amounts of silver halide expressed as equivalent amounts of silver nitrate per square meter and per side are in the range from 3 to 5 g and more preferably from 3.5 to 4.5 g.
  • Coating of a gelatin free afterlayer, if present, as well as coating of the protective antistress layer and light-sensitive emulsion layer or layers may proceed by any coating technique known in the art, e.g. by doctor blade coating, air knife coating, curtain coating, slide hopper coating or meniscus coating, which are coating techniques known from the production of photographic silver emulsion layer materials.
  • Curtain coating and slide hopper coating techniques have e.g. been applied in EP-A 0 752 617.
  • Spray coating technique known from US-A 4,218,533, may be applied, e.g. when an afterlayer is coated.
  • any thickening agent may be used in order to regulate the viscosity of the solution used for any of the said coating techniques provided that they do not particularly effect the photographic characteristics of the silver halide light-sensitive photographic material.
  • Preferred thickening agents include aqueous polymers such as polystyrene sulphonic acid, sulphuric acid esters, polysaccharides, polymers having a sulphonic acid group, a carboxylic acid group or a phosphoric acid group, polyacrylamide, polymethacrylic acid or its salt, copolymers from acrylamide and methacrylic acid and salts derived thereof, copolymers from 2-acrylamido-2-methyl-propansulphonic acid, polyvinyl alcohol, alginate, xanthane, carraghenan.
  • Polymeric thickeners well-known from the literature resulting in thickening of the coating solution may be used independently or in combination.
  • Patents concerning thickening agents are US-A 3,167,410, Belgian Patent No. 558.143, JP-A Nos. 53-18687 and 58-36768 and DE 3,836,945.
  • As a particularly interesting thickening agent use can be made of synthetic clay as has been described e.g. in EP-A 0 813 105.
  • said light-sensitive silver halide photograpic material is a radiographic material, either single-side coated or double-side coated.
  • materials according to the present invention also offer advantages in contact of a silver halide emulsion layer side with the rear side of the recording material, friction with substances such as rubber and hydrophobic polymeric binder, e.g. the binder constituent of phosphor screens used as X-ray intensifying screens. Building up of static charges and subsequent dust attraction and/or sparking, e.g. during loading of films in cassettes, e.g. X-ray cassettes, or in cameras, or during the taking or projection of a sequence of pictures as occurs in automatic cameras or film projectors is thus prevented.
  • a blue tinted, longitudinally stretched polyethylene terephthalate film support having a thickness of approximately 0.61 ⁇ m was subbed on both sides (for the comparative subbing layer called "SUBCOMP") with a coating solution at a coverage of 130 m 2 per liter.
  • the composition was as follows per m 2 and per side:
  • the final thickness of the film was 175 ⁇ m.
  • the film was then heat-set while being kept under tension at a temperature of 220°C for about 10 seconds.
  • subbing procedure for the inventive material was analogous and resulted in the following layer composition per m 2 and per side:
  • composition of the gelatinous layer (expressed in amounts per sq. meter) covering the subbing layer was as follows:
  • ULTAVON W is mixture of sulphonic acid sodium salt substituted benzimidazole compounds wherein the 2-position between the two N-atoms is substituted by a C 17 H 35 -group and wherein the said product is partly substituted at one N-atom with a benzyl-group, which is further partially substituted with a sulphonic acid sodium salt group;
  • ARKOPAL N060 is a polyethyleneglycol, having as one terminal group a phenyl-group having a C 9 H 19 -substituent.
  • This emulsion was chemically sensitized in the presence of anhydro-5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyloxacarbocyanine hydroxide, chloro auric acid, sodium thiosulphate and potassium thio-cyanate in order to get an optimized fog-sensitivity relationship.
  • composition of the protective antistress layer (compounds, expressed in grams per square meter per side):
  • gelatin 1.10 polymethylmethacrylate (average particle diameter : 6 ⁇ m) 0.023 1-p-carboxyphenyl-4,4'-dimethyl-3-pyrazolidine-1-one 0.054 C 7 H 15 -CO-NH-(CH 2 -CH 2 -O-) 17 -H 0.0188 C 8 H 17 -Phen-(O-C 2 H 4 ) 8 -CH 2 -COONa 0.004 formaldehyde 0.1
  • the X-ray photographic material was provided with an afterlayer as a gelatin free outermost layer on top of the protective antistress layer covering the silver halide emulsion layer, described hereinbefore.
  • a non-ionic ammoniumperfluoro compound the compound represented by the formula F 15 C 7 COONH 4 was present therein in an amount of 3 mg/m 2 .
  • the Materials Nos. 7-12 were differing from the Materials Nos. 1-6 in that as a polyoxyethylene compound, the compound A was present in the protective antistress layer, whereas for Materials Nos. 1-6 the compound B, N-polyoxyethylene ethyl perfluoro caprilic acid amide corresponding to the formula C 7 F 15 CONH-(C 2 H 4 )-(OC 2 H 4 ) 17 -OH was used.
  • the lateral surface resistance in Ohm/square was measured before processing, as prescribed in DIN 53482, at a relative humidity RH of 30 %.
  • the objects of the present invention i.e. to provide a material, piled up between paper interleaves in an atmosphere of high temperature and high relative humidity,-having sufficient antistatic properties (lateral surface resistance of less than 1 x 10 10 Ohm/square), showing no spark exposure nor yellow fog formation after processing in an exhausted developer (due e.g. to the absence of replenishment) is only realized if in the protective antistress layer and/or the emulsion layer a non-ionic polyoxyalkylene compound is reduced to a minimum amount (from 0 to less than 5 mg/m 2 ) and if a lateral surface resistance of less than 1 x 10 10 Ohm/square is measured before processing, as prescribed in DIN 53482.
  • compound B as a polyoxyalkylene compound having caprylic acid amide as a terminal group an acceptable sensitivity for the formation of sparks is observed, but the risk to get sparks is still present and is only taken away completely (as well as yellow fog formation) if the said compound B is present in an amount within the range as claimed and if a lateral surface resistance as claimed is measured as prescribed in DIN 53482.
  • an ionic polyoxyalkylene compound is present as becomes clear from the composition of the coating solutions of the emulsion layer (1.2.3) and of the antistress layer composition (1.3.1) hereinbefore the risk of getting sparks and yellow fog formation is further reduced to a minimum.

Claims (10)

  1. Ein fotografisches lichtempfindliches Silberhalogenidmaterial, das einen Träger, eine oder mehrere wasserdurchlässige lichtempfindliche Silberhalogenid-Emulsionsschichten auf einer oder beiden Seiten des Trägers, eine äußerste Schutzschicht und wahlweise eine auf die äußerste Schutzschicht aufgetragene Nachschicht enthält, dadurch gekennzeichnet, daß jede Schicht des Materials in einer Menge von 0 bis weniger als 5 mg/m2 eine nicht-ionische Polyoxyalkylenverbindung enthält, wobei die Schutzschicht und/oder die lichtempfindliche(n) Schicht(en) eine ionische Polyoxyalkylenverbindung enthält (enthalten) und das Material einen nach DIN 53482 ermittelten seitlichen Oberflächenwiderstand von weniger als 1 x 1010 Ohm/Quadrat aufweist.
  2. Material nach Anspruch 1, dadurch gekennzeichnet, daß die ionische Polyoxyalkylenverbindung in einer Menge von 10 bis 25 mg/m2 enthalten ist.
  3. Material nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Schutzschicht weiterhin eine Mercaptoverbindung und/oder eine Polyhydroxybenzolverbindung enthält.
  4. Material nach Anspruch 3, dadurch gekennzeichnet, daß die Mercaptoverbindung eine Mercaptotetrazolverbindung ist.
  5. Material nach Anspruch 3, dadurch gekennzeichnet, daß die Polyhydroxybenzolverbindung eine Dihydroxybenzoldisulfonatverbindung ist.
  6. Material nach irgendeinem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Material einseitig oder doppelseitig mit einer Haftschicht überzogen ist und an einem Träger haftet, wobei die Haftschicht Vinylidenchlorid und eine Polyethylendioxythiophenverbindung enthält.
  7. Material nach Anspruch 6, dadurch gekennzeichnet, daß das Material weiterhin zwischen der Haftschicht und einer dem Träger nahe aufgetragenen lichtempfindlichen Schicht eine hydrophile Kolloidschicht enthält.
  8. Material nach Anspruch 7, dadurch gekennzeichnet, daß die hydrophile Kolloidschicht eine Gelatineschicht mit einem Gelatinegehalt zwischen 0,1 und 0,3 g/m2 ist.
  9. Material nach irgendeinem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß zumindest eine lichtempfindliche Silberhalogenidschicht eine Emulsion mit Silberhalogenid-Tafelkornkristallen mit einer mittleren Kristallstärke von 0,3 µm und einem mittleren Aspektverhältnis von mehr als 2 enthält und zumindest 50% der totalen projizierten Oberfläche der Kristalle tafelkörnige Kristalle sind.
  10. Material nach irgendeinem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß zumindest eine lichtempfindliche Silberhalogenidschicht eine Emulsion mit Silberhalogenid-Tafelkornkristallen mit einer mittleren Kristallstärke von 0,2 µm und einem mittleren Aspektverhältnis von mehr als 5 enthält und zumindest 50% der totalen projizierten Oberfläche der Kristalle tafelkörnige Kristalle sind.
EP98202001A 1997-07-10 1998-06-12 Vor Gelbschleierbildung geschützte photographische Silberhalogenidzusammensetzungen Expired - Lifetime EP0890874B1 (de)

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EP98202001A EP0890874B1 (de) 1997-07-10 1998-06-12 Vor Gelbschleierbildung geschützte photographische Silberhalogenidzusammensetzungen

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EP97202115 1997-07-10
EP97202115 1997-07-10
EP98202001A EP0890874B1 (de) 1997-07-10 1998-06-12 Vor Gelbschleierbildung geschützte photographische Silberhalogenidzusammensetzungen

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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6316175B1 (en) 1999-02-22 2001-11-13 Agfa-Gevaert Light-sensitive silver halide radiographic film material having satisfactory antistatic properties during handling
EP1031875A1 (de) * 1999-02-22 2000-08-30 Agfa-Gevaert N.V. Radiographisches lichtempfindliches Silberhalogenidmaterial mit zufriedenstellenden antistatischen Eigenschaften während der Handhabung
EP1103849A1 (de) * 1999-11-26 2001-05-30 Agfa-Gevaert Radiographisches Element mit verbesserter Deckkraft und blauschwarzem Bildton
US6348293B1 (en) 1999-11-26 2002-02-19 Agfa-Gevaert Radiographic film material exhibiting increased covering power and “colder” blue-black image tone

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0644456B1 (de) * 1993-09-17 1997-12-29 Agfa-Gevaert N.V. Photographisches lichtempfindliches Material mit konservierten antistatischen Eigenschaften
GB9319790D0 (en) * 1993-09-24 1993-11-10 Kodak Ltd Antistatic composition
GB2299680B (en) * 1995-04-05 1998-10-28 Kodak Ltd Photographic material

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