EP0757285A1 - Lichtempfindliches photographisches Silberhalogenidmaterial zur Verwendung in schnellen Verarbeitungsverfahren - Google Patents

Lichtempfindliches photographisches Silberhalogenidmaterial zur Verwendung in schnellen Verarbeitungsverfahren Download PDF

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Publication number
EP0757285A1
EP0757285A1 EP95202096A EP95202096A EP0757285A1 EP 0757285 A1 EP0757285 A1 EP 0757285A1 EP 95202096 A EP95202096 A EP 95202096A EP 95202096 A EP95202096 A EP 95202096A EP 0757285 A1 EP0757285 A1 EP 0757285A1
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EP
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Prior art keywords
silver halide
layer
compounds
emulsion
halide emulsion
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EP95202096A
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French (fr)
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Hendrik c/o Agfa-Gevaert N.V. IIE 3800 Lambrecht
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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/164—Infrared processes
    • 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

  • the invention is related to a light-sensitive silver halide photographic material comprising spectrally sensitised emulsions, said material being suitable for rapid processing applications.
  • Rapid processing conditions that can alternatively be applied are development processing at higher pH and higher temperatures of, e.g., 30 to 40°C, to accelerate the said processing.
  • a solution therefor was found by providing a light-sensitive photographic silver halide material comprising a support and on one or both sides thereof at least one silver halide emulsion layer, characterised in that said silver halide emulsion layer(s) comprise(s) at least one synthetic clay, as in EP-A 0 644 455.
  • Silver halide emulsion crystals have an intrinsic sensitivity for near ultra-violet and blue radiation waves.
  • the absorption spectrum may be different, depending on the silver halide composition of the emulsion crystals.
  • the presence of spectral sensitisers may pose a problem: due to the short development, fixing and rinsing times an unacceptable residual colour may be inevitable after processing as the said spectral sensitiser may not have left the material within such a short processing cycle.
  • an unacceptable desensibilisation has been observed.
  • a light-sensitive silver halide photographic material comprising spectrally sensitised gelatino silver halide emulsions, wherein the presence of a synthetic clay in the said emulsions for their benificial effect on avoiding pressure marks does not cause speed desensitisation, the said material further allowing a rapid processing cycle in an automatic processor without the presence of dye stain after processing.
  • a solution therefor has been found by providing a light-sensitive silver halide photographic material comprising a support and on one or both sides thereof one or more gelatino silver halide emulsion layers, spectrally sensitised in the wavelength region between 490 and 850 nm, characterised in that at least one of said spectrally sensitized silver halide emulsion layers comprises a synthetic clay having a fluorosilicate composition.
  • Natural clays are essentially hydrous aluminum silicates, wherein alkali metals or alkaline-earth metals are present as principal constituents. Also in some clay minerals magnesium or iron or both replace the aluminum wholly or in part. The ultimate chemical constituents of the clay minerals vary not only in amounts, but also in the way in which they are combined or are present in various clay minerals.
  • smectite clays are well-known. For the said smectite clays some substitutions in both octahedral and tetrahedral layers of the crystal lattice occur, resulting in a small number of interlayer cations. Smectite clays form a group of "swelling" clays which take up water and organic liquids between the composite layers and which have marked cation exchange capacities.
  • Synthetic chemically pure clays have been produced having an analogous structure as smectite clays and are now available. So a preferred synthetic smectite clay additive for the purposes of this invention is LAPONITE JS, trade mark product of LAPORTE INDUSTRIES Limited, London. Organophilic clays and process for the production thereof have been described in EP-Patent 161 411 B1.
  • LAPONITE JS has been described as a synthetic layered hydrous sodium lithium magnesium fluoro-silicate incorporating an inorganic polyphoshate peptiser.
  • the said fluoro-silicate appears as free flowing white powder and hydrates well in water to give virtually clear and colourless colloidal dispersions of low viscosity, also called "sols".
  • On addition of small quantities of electrolyte highly thixotropic gels are formed rapidly.
  • the said thixotropic gels can impart structure to aqueous systems without significantly changing viscosity. An improvement of gel strength, emulsion stability and suspending power can be observed by making use of it in the said aqueous systems.
  • LAPONITE RD has been described as a synthetic layered hydrous sodium lithium magnesium silicate with analogous properties as LAPONITE JS.
  • Laponite clay as a synthetic inorganic gelling agent for aqueous solutions of polar organic compounds has been presented at the Symposium on “Gums and Thickeners", organised by the Society of Cosmetic Chemists of Great Britain, held at Oxford, October 14, 1969.
  • Laporte Inorganics Laponite Technical Bulletin L104/90/A a complete review about the structure, the chemistry and the relationship to natural clays is presented. Further in “Laporte Inorganics Laponite Technical Bulletin L106/90/c” properties. preparation of dispersions, applications and the product range are disclosed.
  • a detailed description of "Laponite synthetic swelling clay, its chemistry, properties and application” is given by B.J.R. Mayes from Laporte Industries Limited.
  • the primary particles are platelets having a diameter of about 0.025 ⁇ m and a thickness of about 0.001 ⁇ m.
  • the light-sensitive silver halide material of the present invention comprises a support having on at least one side thereof at least one light-sensitive hydrophilic colloid silver halide emulsion layer wherein the synthetic swelling clays according to this invention are present as an extra binder or filler between the silver halide grains in addition to the hydrophilic colloid.
  • gelatin As the main hydrophilic binder in the hydrophilic layers of the photographic material conventional lime-treated or acid treated gelatin can be used.
  • 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).
  • the silver halide crystals can alternatively be prepared in silica sol medium as has been described in EP-B 0 392 092. Additional gelatin can be added in a later stage of the emulsion preparation, e.g., during the flocculation procedure, after washing or by redispersing the flocculate, to establish optimal coating conditions and/or to establish the required thickness of the coated emulsion layer.
  • a ratio by weight of gelatin to silver halide, expressed as the equivalent amount of silver nitrate, ranging from 0.2 to 1.0 is then obtained.
  • Gelatin can, however, be replaced in part or integrally by synthetic, semi-synthetic, or natural polymers.
  • Synthetic substitutes for gelatin are, e.g., polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyvinyl imidazole, polyvinyl pyrazole, polyacrylamide. polyacrylic acid, and derivatives thereof, in particular copolymers thereof.
  • Natural substitutes for gelatin are, e.g., other proteins such as zein, albumin and casein, cellulose, saccharides, starch, and alginates.
  • the semi-synthetic substitutes for gelatin are modified natural products, 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.
  • modified natural products e.g., gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents or by grafting of polymerizable monomers on gelatin
  • cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates.
  • the gelatin binder of the photographic elements can be forehardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulphone type e.g. 1,3-vinylsulphonyl-2-propanol, chromium salts e,g. chromium acetate and chromium alum, aldehydes, e.g.
  • N-methylol compounds e.g., dimethylolurea and methyloldimethylhydantoin
  • dioxan derivatives e.g., 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
  • mucohalogenic acids e.g., mucochloric acid and mucophenoxychloric acid.
  • the binder can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts as disclosed in US Patent 4,063,952 and with the onium compounds as disclosed in EP-A 0 408 143.
  • the halide composition of the silver halide emulsions used in the silver halide photographic material according to the present invention is not specifically limited and may be any composition selected from, e.g., silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, and silver chlorobromoiodide.
  • the content of silver iodide is equal to or less than 20 mol%, preferably equal to or less than 5 mol%, even more preferably equal to or less than 3 mole %.
  • the photographic silver halide emulsions used in the photographic material according to the present invention can be prepared by mixing the halide and silver solutions in partially or fully controlled conditions of temperature, concentrations, sequence of addition, and rates of addition.
  • the silver halide can be precipitated according to the single-jet method, the double-jet method, or the conversion method.
  • the silver halide particles of the photographic emulsions used in the material according to the present invention may have a regular crystalline form such as a cubic or octahedral form or they may have a transition form. They may also have an irregular crystalline form such as a spherical form or a tabular form, or may otherwise have a composite crystal form comprising a mixture of said regular and irregular crystalline forms.
  • the silver halide grains may have a multilayered grain structure. According to a simple embodiment the grains may comprise a core and a shell, which may have different halide compositions and/or may have undergone different modifications such as the addition of dopes. Besides having a differently composed core and shell the silver halide grains may also comprise different phases inbetween.
  • Two or more types of silver halide emulsions that have been prepared differently can be mixed for forming a photographic emulsion for use in accordance with the present invention.
  • the average size of the silver halide grains may range from 0.1 to 2.0 ⁇ m, preferably from 0.1 to 1.0 ⁇ m and still more preferably from 0.2 to 0.6 ⁇ m.
  • the size distribution of the silver halide particles of the photographic emulsions to be used according to the present invention can be homodisperse or heterodisperse.
  • a homodisperse size distribution is obtained when 95% of the grains have a size that does not deviate more than 30% from the average grain size.
  • the silver halide crystals can be doped with Rh 3+ , Ir 4+ , Ru 2+ , Cd 2+ , Zn 2+ , Pb 2+ .
  • the photographic emulsions can be prepared from soluble silver salts and soluble halides according to different methods as described, e.g., by P. Glafkides in "Chimie et Physique Photographique", Paul Montel, Paris (1967), by G.F. Duffin in “Photographic Emulsion Chemistry”. The Focal Press, London (1966), and by V.L. Zelikman et al in “Making and Coating Photographic Emulsion", The Focal Press, London (1966).
  • the emulsion can be desalted in the usual ways. e.g., by dialysis, by flocculation and redispersing, or by ultrafiltration.
  • the light-sensitive silver halide emulsion can be a so-called primitive emulsion, in other words an emulsion that has not been chemically sensitized.
  • the light-sensitive silver halide emulsion can be chemically sensitized as described i.a. in the above-mentioned "Chimie et Physique Photographique” by P. Glafkides, in the above-mentioned “Photographic Emulsion Chemistry" by G.F. Duffin, in the above-mentioned “Making and Coating Photographic Emulsion” by V.L. Zelikman et al, and in "Die Grundlagen der Photographischen mit Silberhalogeniden” edited by H.
  • chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur, e.g., thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodamines, but also the analogous selenium and tellurium compounds.
  • sulphur e.g., thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodamines
  • the emulsions can be sensitized also by means of gold-sulphur ripeners, gold-selenium or gold-tellurium compounds or by means of reductors, e.g.
  • tin compounds as described in GB-A 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • Chemical sensitization can also be performed with small amounts of Ir, Rh, Ru, Pb, Cd, Hg, Tl, Pd, Pt, or Au.
  • One of these chemical sensitization methods or a combination thereof can be used.
  • the silver halide emulsions coated in the layers of the photographic material are sensitised to the green, to the red, to the near-infrared or to the infrared region of the wavelength spectrum.
  • Preferred absorption maxima are situated around the wavelengths of 550 nm, 633 nm, 670 nm, 780 nm and 820 nm.
  • methine dyes such as those described by F.M, Hamer in "The Cyanine Dyes and Related Compounds", 1964. John Wiley & Sons, Further included are cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes, complex merocyanine dyes.
  • spectrally sensitised silver halide photographic emulsions are present wherein the silver halide emulsions are spectrally sensitised with at least one spectrally sensitising dye, the general structure of which is given hereinafter.
  • a dye corresponding to the general structure according to the formula (I) is wherein
  • Preferred spectral sensitisers suitable for use together with the emulsion crystals according to this invention are those of the type where R''' is -C 2 H 5 , Z is an oxygen atom, at least one of R and R' represents -a sulphoalkyl group, preferably corresponding to the one of the formulae
  • EP-A 0 638 841 is incorporated herein by reference.
  • Another class of preferred spectral sensitisers suitable for use together with the emulsion crystals according to this invention are those of the type where R''' is hydrogen, Z is an nitrogen atom, substituted with R'', being a substituted or unsubstituted alkyl; wherein T represents 5-phenyl, 5-Cl, 5-OCH 3 or 5-CH 3 and wherein T' represents 5,6-(Cl) 2 ; 5-CN-6-Cl; 5-CF 3 -6-Cl; 5-Cl: 5-CN, 5-CF 3 , 5-CHF 2 , 5-SO 2 CH 3 , 5-SO 2 R''''' or 5-COOR'''''''(R'''' and R'''''' each representing a fluoro-subsituted or non-fluoro-substituted alkylgroup); and 5-SO 2 -N(R x )(R y ) or 5-CO-N(R x )(R y ), wherein R x and
  • Especially preferred structures of the type wherein Z represents oxygen are those wherein T and T' each represent Cl or T represents 5-Cl and T' represents 5-Phenyl or vice versa and wherein R and R' each independantly represent one of the combinations of the formulae
  • An example of a useful spectral sensitizer according to the general formula given above is anhydro-5,5'-dichloro-3,3'-bis(n-sulphobutyl)-9-ethyloxacarbo-cyanine hydroxide or anhydro-5,5'-dichloro-3,3'-bis(n-sulphopropyl)-9-ethyloxacarbo-cyanine hydroxide.
  • a suitable mixture of spectral sensitizers that can be applied is anhydro-5,5'-dichloro-3,3'-bis(n-sulphobutyl)-9-ethyl oxacarbocyanine hydroxide or anhydro-5,5'-dichloro-3,3'-bis(n-sulphopro pyl)-9-ethyloxacarbo-cyanine hydroxide and anhydro-5,5'-dicyano-1,1'-diethyl-3,3'-di(2-acetoxyethyl)ethyl-imidacarbocyanine bromide.
  • trimethinecyanines corresponding to the general formula (II) trimethinecyanines corresponding to the general formula (II)
  • pentamethines corresponding to the general formula (III) absorbing more bathochromically
  • the general formula (IV) absorbing in the infrared regio
  • the structure can be symmetrical or asymmetrical if Z 1 and Z 2 each represent sulphur.
  • R 1 and R 2 further have the same meaning as in formula (II), which can give rise to a symmetrical or an asymmetrical structure.
  • the presence of an oxygen atom instead of sulphur for Z 2 only appears rarely.
  • red absorbing spectral sensitisers are heptamethines, corresponding to the formulae (V) and (VI) and rhodacyanines, corresponding to the formulae (VII), (VIII) and (IX).
  • T 1 and T 2 each represent hydrogen, 5-Cl, 5-CH 3 , 5-OCH 3 , 6-CH 3 , 6-OCH 3 , 5,6-(CH 3 ) 2 , 5,6-(OCH 3 ) 2 , if the structure is symmetrical; and T 2 preferably represents 4,5 benzo if the structure is asymmetrical, whereas T 1 has the same structure as has been given hereinbefore.
  • the closed ring B can be represented by the following structures:
  • the rhodacyanines represented in the formulae (VII), (VIII) and (IX) have the same benzthiazole substitution as given hereinbefore.
  • R is preferably alkyl;
  • R can be hydrogen, but preferably represents phenyl, -S-CH 3 or
  • R 1 R 2 represents (CH 2 ) 4 SO 3 - or (CH 2 )-CO-N - -SO 2 CH 3 ; or
  • T further preferably represents hydrogen, whereas T 1 represents the common substituents for benzthiazol nuclei given hereinbefore or T and T 1 may be the same.
  • Dimethine merocyanines corresponding to the general formulae (X) and (XI) are also useful as red light absorbing spectral sensitisers, as well as tetramethine merocyanines corresponding to the formula (XII).
  • Q also represents S or NR 3 .
  • R and R 1 preferably represent sulpho-, carboxyalkyl or - CH 2 CH 2 OH with the proviso that at least one alkali soluble group is present and R'' represents hydrogen, methyl, ethyl, isopropyl, phenyl or -SCH 3 ;
  • Q also represents O or S.
  • T has the same meaning as given hereinbefore, R'' represents methyl or ethyl (present on positions differing from each other) and R and R 1 represent carboxy or sulphoalkyl with the proviso that at least one of them has a water soluble goup.
  • Q represents S and NR and has the same meaning as just given hereinbefore.
  • R At least two alkali soluble groups are present in R, R'' and R''.
  • R'' and/or R''' preferably represent by CH 2 CH 2 COOH.
  • R''' can however also represent CH 2 CH 2 SO 3 H.
  • R preferably represents methyl, ethyl, CH 2 CONHSO 2 CH 3 , (CH 2 ) n SO 3 H (wherein n preferably equals 3).
  • T corresponds with Z and has the meaning as given hereinbefore.
  • Q represents sulphur. If each of Z and Q represent sulphur n equals 0; in all other cases n equals 1.
  • n 1 or 4.
  • R preferably represents methyl or ethyl
  • R' preferably represents ethyl or allyl
  • R'' preferably represents phenyl, isopropyl or S(CH 3 ).
  • R and R' have the same meaning as in formula (XIV), whereas R''' has the same meaning as R''.
  • R'' represents hydrogen, methyl or ethyl; n equals 1 or 2 and A equals COOH.base or SO 3 H.base.
  • Suitable supersensitizers are i.a. heterocyclic mercapto compounds containing at least one electronegative substituent as described, e.g., in US-P 3,457,078, nitrogen-containing heterocyclic ring-substituted aminostilbene compounds as described, e.g., in US-P 2,933,390 and in US-P 3,635,721, aromatic organic acid/formaldehyde condensation products as described e.g. in US-P 3,743,510, cadmium salts, and azaindene compounds.
  • the silver halide emulsion for use in accordance with the present invention may comprise compounds preventing the formation of fog or stabilizing the photographic characteristics during the production or storage of photographic elements or during the photographic treatment thereof.
  • Many known compounds can be added as fog-inhibiting agent or stabilizer to the silver halide emulsion. Suitable examples are, e.g., the heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles.
  • nitrobenzimidazoles chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles (preferably 5-methyl-benzotriazole), nitrobenzotriazoles, mercaptotetrazoles, in particular 1-phenyl-5-mercapto-tetrazole, mercaptopyrimidines, mercaptotriazines, benzothiazoline-2-thione, oxazoline-thione, triazaindenes, tetrazaindenes and pentazaindenes, especially those described by Birr in Z.
  • fog-inhibiting compounds are metal salts such as, e.g., mercury or cadmium salts and the compounds described in Research Disclosure N° 17643 (1978), Chaptre VI.
  • Fog-inhibiting agents or stabilizers can be added to the silver halide emulsion prior to, during, or after the ripening thereof and mixtures of two or more of these compounds can be used.
  • the photographic element of the present invention may further comprise various kinds of surface-active agents in the photographic emulsion layer or in at least one other hydrophilic colloid layer.
  • Suitable surface-active agents include non-ionic agents such as saponins, alkylene oxides, 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; anionic agents comprising an acid group such as a carboxy, sulpho, phospho, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic acids, aminoalkyl sulphates or phosphates, alkyl betaines, and amine-N-oxides; and cationic agents such as alkylamine salts, aliphatic, aromatic, or heterocyclic quaternary ammonium salts, aliphatic or heterocyclic ring
  • Such surface-active agents can be used for various purposes, e.g., as coating aids, as compounds preventing electric charges, as compounds improving slidability, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving the photographic characteristics, e.g., higher contrast, sensitization, and development acceleration.
  • Development acceleration can be accomplished with the aid of various compounds, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in, e.g., US-P's 3,038,805 - 4,038,075 - 4,292,400.
  • the photographic element of the present invention may further comprise various other additives such as, e.g., compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents, hardeners, and plasticizers.
  • additives such as, e.g., compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents, hardeners, and plasticizers.
  • Suitable additives for improving the dimensional stability of the photographic element are i.a. dispersions of a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl (meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters, acrylonitriles, olefins , and styrenes, or copolymers of the above with acrylic acids, methacrylic acids, Alpha-Beta-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulphoalkyl (meth)acrylates, and styrene sulphonic acids.
  • a water-soluble or soluble synthetic polymer e.g. polymers of alkyl (meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters,
  • Suitable UV-absorbers are, e.g., aryl-substituted benzotriazole compounds as described in US-P 3,533,794, 4-thiazolidone compounds as described in US-P 3,314,794 and 3,352,681, benzophenone compounds as described in JP-A 2784/71, cinnamic ester compounds as described in US-P 3,705,805 and 3,707,375, butadiene compounds as described in US-P 4,045,229, and benzoxazole compounds as described in US-P 3,700,455 and suitable compounds summarised in Research Disclosure 36544, dated September 1994.
  • the average particle size of spacing agents is comprised between 0.2 and 10 ⁇ m.
  • Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble 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 desribed in US-P 4,614,708.
  • the said hydrophilic layer is an intermediate layer, adjacent to at least one gelatino silver halide emulsion layer or an outermost afterlayer of the material according to this invention.
  • the said hydrophilic layer is an intermediate layer between two emulsion layers, an undercoat layer between the subbing layer and the emulsion layer situated the more close to the support, a protective antistress layer coated on the emulsion layer farthest from the support or even an afterlayer coated on top thereof.
  • an amount of synthetic clay present in the said silver halide emulsion layer or layers is from 0.05 to 0.75 g/m 2 , and more preferably from 0.1 to 0.5 g/m 2 .
  • the synthetic clay when the synthetic clay is present in a hydrophilic layer coated on top of the emulsion layer situated farthest from the support, called "protective antistress layer” or "afterlayer", the said clay is present therein in an amount of from 0.05 to 0.25 g/m 2 .
  • the said hydrophilic layer(s) coated on top of the silver halide layer(s) are containing gelatin in an amount of from 0.5 to 1.2 g/m 2 . More preferably, if an afterlayer is coated on top of the protective antistress layer or layers, the said afterlayer is free from gelatin.
  • a preferred protective layer is further made from gelatin hardened up to a degree corresponding with a water absorption of less than 2.5 grams of water per m 2 .
  • the protective layer may contain friction-lowering substance(s) such as dispersed wax particles (carnaubawax or montanwax) or polyethylene particles, fluorinated polymer particles, silicon polymer particles etc.
  • friction-lowering substance(s) such as dispersed wax particles (carnaubawax or montanwax) or polyethylene particles, fluorinated polymer particles, silicon polymer particles etc.
  • the said friction lowering substance(s) are present in an antistatic layer on top of the antistress layer serving as outermost layer.
  • colloidal silica is added to the antistress layer composition on top of the silver halide emulsion layer(s).
  • the said colloidal silica has an average particle size not larger than 0.010 ⁇ m, a surface area of at least 300 m 2 per gram. A coverage in the range of 50 mg to 500 mg per m 2 is used. Particularly good results can be obtained if in the protective antistress coating at least 50 % by weight of colloidal silica versus the binder is present.
  • Especially preferred colloidal silica particles have a surface area of 500 m2 per gram and an average grain size smaller than 0.007 ⁇ m.
  • KIESELSOL 500 KIESELSOL is a registered trade name of Bayer AG, Leverkusen, West-Germany.
  • the presence of at least one ionic or non-ionic polymer or copolymer latex or at least one synthetic clay as described hereinbefore contributes to the preservation of the antistatic characteristics of the material before processing as has been described in EP-A 0 644 454.
  • the said layer composition provides excellent surface characteristics as sufficient surface glare and the absence of water spot defects after processing, in addition to the improvement of pressure marks from the rollers in automatic processing machines as has also been mentioned in EP-A 0 644 455.
  • 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 and polyethylene naphthalate.
  • a preferred resin coated paper support is a poly-Alpha-olefin coated paper support such as a polyethylene coated paper support.
  • the hydrophobic resin support may be provided with one or more subbing layers known to those skilled in the art for adhering thereto a hydrophilic colloid layer.
  • subbing layers for polyethylene terephthalate supports are described, e.g., in US-P's 3,397,988, 3,649,336, 4,123,278 and 4,478,907.
  • Photographic silver halide emulsion materials containing a silver halide emulsion layer according to the present invention may be of any type known to those skilled in the art.
  • the hydrophilic silver halide emulsion layer(s) is (are) useful in continuous tone or halftone photography, micrography and radiography, in black-and-white as well as colour photographic materials.
  • the photographic material containing emulsions spectrally sensitised to the wavelength region between 490 and 850 nm is a medical X-ray material or a laser material.
  • the said medical X-ray material may be single-side coated or double side coated, whereas the laser material is usually single-side coated.
  • a photographic recording material comprising (a) silver halide emulsion layer(s) with a composition wherein silver halide photographic materials have been spectrally sensitised in order to make them sensitive to green, red or near-infrared radiation and comprising synthetic clay having a fluorosilicate structure according to the present invention, even in rapid processing cycles in automatic processing machines an enhanced minimum density due to the presence of dye stain can be avoided. Moreover there is no problem of desensitisation anymore and even for thin coated layers there are no disturbing roller marks.
  • a photographic silver iodobromide emulsion containing 2.0 mole % of silver iodide was prepared by a conventional single jet method in a vessel containing 42 g of phthaloyl gelatin.
  • the ammoniacal silver nitrate solution was held at 40°C as well as the emulsion vessel, containing the halide salts.
  • the precipitation time was ended after 10 minutes and followed by a physical ripening time of 30 minutes. After that time an additional amount of 20 g of gelatin was added.
  • the obtained emulsion was of an average grain size of 0.62 ⁇ m and contained an amount of silver halide corresponding to approximately 90 g of silver nitrate per kg of the dispersion after addition of 3 moles of silver nitrate.
  • the emulsion 150 g of gelatin were added so that the weight ratio of gelatin to silver halide expressed as silver nitrate was 0.40, the emulsion containing an amount of silver bromoiodide equivalent with 190 g of silver nitrate per kg.
  • the emulsion was chemically ripened with sulphur and gold compounds at 47°C for 4 hours to get an optimized relation between fog and sensitivity and was spectrally sensitised by successiveively adding the spectral sensitisers according to the formulae SS-1 and SS-2.
  • Stabilisation was performed with 4-hydroxy-6-methyl-1,3,3a-tetrazaindene before coating the prepared layers on both sides of a polyester support of 175 ⁇ m thickness.
  • a protective layer was coated thereover with a coating amount of 1.1 g of gelatin per m 2 .
  • Amounts of spectral sensitiser added to the emulsion were about 0.67 mmoles per mole of silver halide.
  • the type of spectral sensitiser and the type of synthetic clay added has been given in Table 1.
  • Per side coating amounts of silver halide crystals expressed as the equivalent amount of silver nitrate and of gelatin in the emulsion layer were: 4.41 g/m 2 and 1.05 g/m 2 respectively.
  • the film was exposed to light through a step wedge before processing to make the evaluation more realistic.
  • the exposed radio-graphic materials were processed in the processing machine CURIX HT530 (Agfa-Gevaert trademarked name) with the following time (in seconds) and temperature (in °C) characteristics: loading 0.2 sec. developing 9.3 sec. 35°C in developer I described below cross-over 1.4 sec. rinsing 0.9 sec. cross-over 1.5 sec. fixing 6.6 sec. 35°C in fixer I described below cross-over 2.0 sec. rinsing 4.4 sec. 20°C cross-over 4.6 sec. drying 6.7 sec. total 37.6 sec. ⁇
  • composition of the fixer is Composition of the fixer:
  • ammonium thiosulfate (78% solution) 661 grams sodium sulphite 54 grams boric acid 25 grams sodium acetate-trihydrate 70 grams acetic acid 40 grams water to make 1 liter pH adjusted with acetic acid to 5.30 at 25°C
  • ammonium thiosulfate 78% solution
  • boric acid 25 grams sodium acetate-trihydrate
  • acetic acid 40 grams water to make 1 liter pH adjusted with acetic acid to 5.30 at 25°C
  • a pH of 5.25 was measured at 25°C.

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  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP95202096A 1995-08-01 1995-08-01 Lichtempfindliches photographisches Silberhalogenidmaterial zur Verwendung in schnellen Verarbeitungsverfahren Withdrawn EP0757285A1 (de)

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EP95202096A EP0757285A1 (de) 1995-08-01 1995-08-01 Lichtempfindliches photographisches Silberhalogenidmaterial zur Verwendung in schnellen Verarbeitungsverfahren

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EP95202096A EP0757285A1 (de) 1995-08-01 1995-08-01 Lichtempfindliches photographisches Silberhalogenidmaterial zur Verwendung in schnellen Verarbeitungsverfahren

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6974663B2 (en) 2001-12-21 2005-12-13 Eastman Kodak Company Silver halide imaging element containing intercalated photographically useful compounds
CN101654575B (zh) * 2009-07-27 2011-12-28 深圳市佳宇源油漆颜料有限公司 激光标记用颜料组合物和含有该颜料组合物的树脂组合物及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0444326A1 (de) * 1990-03-01 1991-09-04 Agfa-Gevaert N.V. Blatt- oder bahnförmiges Material mit antistatischen Eigenschaften
EP0644454A1 (de) * 1993-09-17 1995-03-22 Agfa-Gevaert N.V. Photographisches lichtempfindliches Material mit konservierten antistatischen Eigenschaften
EP0644455A1 (de) * 1993-09-17 1995-03-22 Agfa-Gevaert N.V. Photographisches lichtempfindliches Material zur Verwendung für schnelle Verarbeitung
EP0655646A1 (de) * 1993-11-29 1995-05-31 Minnesota Mining And Manufacturing Company Radiographisches Material mit verbesserten antistatischen Eigenschaften

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0444326A1 (de) * 1990-03-01 1991-09-04 Agfa-Gevaert N.V. Blatt- oder bahnförmiges Material mit antistatischen Eigenschaften
EP0644454A1 (de) * 1993-09-17 1995-03-22 Agfa-Gevaert N.V. Photographisches lichtempfindliches Material mit konservierten antistatischen Eigenschaften
EP0644455A1 (de) * 1993-09-17 1995-03-22 Agfa-Gevaert N.V. Photographisches lichtempfindliches Material zur Verwendung für schnelle Verarbeitung
EP0655646A1 (de) * 1993-11-29 1995-05-31 Minnesota Mining And Manufacturing Company Radiographisches Material mit verbesserten antistatischen Eigenschaften

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6974663B2 (en) 2001-12-21 2005-12-13 Eastman Kodak Company Silver halide imaging element containing intercalated photographically useful compounds
CN101654575B (zh) * 2009-07-27 2011-12-28 深圳市佳宇源油漆颜料有限公司 激光标记用颜料组合物和含有该颜料组合物的树脂组合物及其制备方法

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