EP0712034B1 - Verfahren zur spektralen Sensibilisierung von tafelförmigen Silberhalogenidkörnern - Google Patents

Verfahren zur spektralen Sensibilisierung von tafelförmigen Silberhalogenidkörnern Download PDF

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Publication number
EP0712034B1
EP0712034B1 EP19950203024 EP95203024A EP0712034B1 EP 0712034 B1 EP0712034 B1 EP 0712034B1 EP 19950203024 EP19950203024 EP 19950203024 EP 95203024 A EP95203024 A EP 95203024A EP 0712034 B1 EP0712034 B1 EP 0712034B1
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EP
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Prior art keywords
emulsion
silver halide
grains
equals
tabular
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French (fr)
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EP0712034A1 (de
Inventor
Hubert C/O Agfa-Gevaert N.V. Vandenabeele
Hendrik c/o Agfa-Gevaert N.V. Lambrecht
Ann C/O Agfa-Gevaert N.V. Verbeeck
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/22—Methine and polymethine dyes with an even number of CH groups
    • 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
    • G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images

Definitions

  • the present invention relates to spectrally sensitized silver halide emulsions comprising tabular crystals, to the preparation method thereof and to light-sensitive photographic materials containing said emulsions.
  • Tabular grain emulsions having a high aspect ratio are known to provide several advantages over more conventional spherical grains as, e.g., a high covering power, a high (spectral) sensitivity and a lower coating weight, which saves costs in manufacturing. Said lower coating weight is especially preferred if rapid processing applications are required, which is nowadays an ever more returning demand.
  • Spectrally sensitizing dyes are well known in the art of photography for green and red sensitization of flat tabular grains, but for blue and/or ultraviolet sensitization the number of examples is rather limited. Recently arylidene sensitizing dyes for tabular grains have been disclosed in WO 93/11458. Spectral supersensitization of tabular silver halide grains with J-aggregate forming benzothiazolorhodanine zeromethine-merocyanines in combination with a tetraazaindene derivative has been described in EP-A 00 487 010.
  • One particular sensitizer which is frequently mentioned in the patent literature is 3-ethyl-5-[1-(4-sulfobutyl)-4-(1H)-pyridylidene] rhodanine, as, e.g., in EP-A 0 300 382; in EP-A 0 404 142; in EP-A 0 438 135 and in EP-A 0 509 519.
  • radiographic screen-film combinations comprising at least one X-ray intensifying screen in operative association with a photographic element comprising tabular grains spectrally sensitized to the blue and ultra-violet spectral region.
  • photographic elements which for being subjected after exposure to rapid processing, show high sensitivity, high image quality and good physical properties, especially no dye stain and brilliant surface characteristics.
  • a method for manufacturing a tabular silver halide emulsion wherein the tabular silver halide grains have an aspect ratio of at least 2:1, an average crystal diameter between 0.3 ⁇ m and 3.0 ⁇ m and an average thickness of less than 0.50 mm, and more preferably less than 0.3 ⁇ m, accounting for at least 50 % of the total projective surface area of said grains, and wherein said method comprises the steps of precipitating said grains, spectrally sensitizing and chemically ripening, characterized by adding to the emulsion before during chemically ripening at least one spectrally sensitizing dye corresponding to the general formula (I) wherein
  • a light-sensitive silver halide emulsion comprising tabular grains spectrally sensitized by the method disclosed hereinbefore, as well as a photographic material comprising a support and on at least one side of said support at least one hydrophilic colloid layer and at least one photosensitive layer comprising at least one photographic silver halide emulsion with tabular grains spectrally sensitized as defined and wherein the total amount of silver coated on one side of said support, expressed as the equivalent amount of silver nitrate, is less than 10 g/m 2 , more preferably less than 7 g/m 2 , and still more preferably less than 5.5 g/m 2 and wherein the time to dissolve the coated layers of said material, determined by the method disclosed herein, is not less than 45 minutes.
  • a radiographic element comprising at least one ultra-violet and blue light emitting X-ray intensifying screen in operative association with said photographic material is also provided.
  • Silver halide tabular grains used in the method of this invention are crystals possessing two parallel faces with a ratio between the diameter of a circle having the same area as these faces, and the thickness, being the distance between the two major faces, equal to at least 2:1.
  • the main photographic advantages of tabular grains compared to normal globular grains are a high covering power at high forehardening levels, a high developability and a higher sharpness especially in double side coated spectrally sensitized materials.
  • the light-sensitive silver halide emulsions comprising tabular grains used in the method according to this invention are characterized by an average grain thickness of not more than 0.5 ⁇ m, and more preferably not more than 0.3 ⁇ m, with an average aspect ratio of at least 2:1, and more preferably at least 5:1. For practical use, an aspect ratio between 5:1 and 8:1 is recommended.
  • more preferred grains used according to this invention have an average grain thickness of not more than 0.2 ⁇ m and not less than 0.05 ⁇ m. From electron microscopic photographs taken from the silver halide tabular crystals, it is possible to calculate the average grain thickness and the average crystal diameter of a circle, having a surface equivalent with the crystal surface.
  • the light-sensitive tabular silver halide grains used in the method according to this invention account for a total projective area of at least 70% and a total projective area of at least 90% is even more preferred.
  • Emulsions comprising tabular silver halide grains in accordance with this invention preferably have silver halide compositions as, e.g., silver chloride, silver chlorobromide, silver chlorobromoiodide, silver chloroiodide, silver bromide or silver bromoiodide.
  • Iodide ions can be provided in the preparation step by anorganic iodide salts and/or organic compounds releasing iodide ions as has e.g. been described in EP-A's 0 561 415, 0 563 701 and 0 563 708, and in EP-A's 0 649 052 and 0 651 284.
  • Iodide ion concentrations up to 10 mole % may be present but concentrations up to 3 mole % are particularly preferred.
  • Silica sols can be used as a protective colloid instead of gelatin for the preparation of tabular silver bromide and silver bromoiodide emulsions that are spectrally sensitized according to this invention as has been described in EP-A 0 678 772 and in EP-A 0 677 773 wherein the preparation of tabular grains rich in chloride has been described.
  • the photographic emulsions according to this invention comprising silver halide tabular crystals may have a homogeneous or a heterogeneous halide distribution within the crystal volume.
  • a heterogeneous halide distribution may be obtained by application of growth steps having a different halide composition or by conversion steps, e.g., by addition of halide ions that provide less soluble silver salts, onto existing tabular cores.
  • a heterogenous distribution of halide ions a multilayered grain structure is obtained.
  • the tabular form has to be maintained in this case, in order to get tabular emulsion crystals in accordance with this invention.
  • the crystals may further be doped with whatever a dope, as e.g. with Rh 3+ , Ir 4+ , Cd 2+ , Zn 2+ , Pb 2+ .
  • grain growth restrainers or accelerators may be added to obtain crystals with a preferred average crystal size between 0.05 and 5 ⁇ m.
  • grain growth accelerators are compounds carrying, e.g., a thioether function as methionine or 1,8-dihydroxy-3,6,-dithiooctane.
  • Silver halide nuclei can also be formed in a separate vessel and added to the reaction vessel wherein the growth step is performed.
  • the light-sensitive emulsion comprising silver halide tabular crystals, prepared in accordance with the present invention is; after redispersion, a so called primitive emulsion.
  • said emulsion can be chemically sensitized as described i.a. "Chimie et Physique Photographique” by P. Glafkides, in “Photographic Emulsion Chemistry” by G.F. Duffin, in "Making and Coating Photographic Emulsion” by V.L. Zelikman et al, and in "Die Grundlagen der Photographischen mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968).
  • chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur, selenium and/or tellurium, e.g., thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodanines or the corresponding selenium or tellurium compounds thereof.
  • compounds containing sulphur, selenium and/or tellurium e.g., thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodanines or the corresponding selenium or tellurium compounds thereof.
  • the emulsions can be sensitized also by means of gold-sulphur, gold-selenium or gold-tellurium ripeners 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.
  • reductors e.g., tin compounds as described in GB-A 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • Combinations of sulphur, selenium and gold ion providing compounds in the-chemical ripening step of blue sensitized tabular grain emulsions prepared according to the method of this invention are particularly preferred as an improved sensitivity is obtained for an equal or even lower fog level than the one obtained with the classical sulphur and gold providing ripening agents and as preservation characteristics of the material in which said emulsions are used are remarkably improved.
  • tabular grain emulsions according to this invention are less sensitive to darkroom light.
  • 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.
  • a mixture can also be made of two or more separately precipitated emulsions being chemically sensitized before mixing them.
  • spectral sensitization is performed before and/or during chemical ripening, with at least one blue and/or ultra violet light absorbing spectral sensitiser according to the formula (I), given above.
  • spectral sensitization traditionally follows the completion of chemical sensitization.
  • spectral sensitization occurs simultaneously with or even precedes completely the chemical sensitization step; the chemical sensitization after spectral sensitization is believed to occur at one or more ordered discrete sites of tabular grains.
  • the chemical sensitization may further proceed in the presence of one or more 1-phenyl-3-pyrazolidine-1-one compound and derivatives, dihydroxy benzene, e.g., hydroquinone, resorcinol, catechol and/or derivative(s) thereof, one or more stabilizer(s) or antifoggant(s), one or more spectral sensitizer(s) or combinations of said ingredients.
  • dihydroxy benzene e.g., hydroquinone, resorcinol, catechol and/or derivative(s) thereof, one or more stabilizer(s) or antifoggant(s), one or more spectral sensitizer(s) or combinations of said ingredients.
  • tabular silver halide emulsion crystals are spectrally sensitized with at least one dye having a structure corresponding to the formula (II) or (III) given below. wherein all symbols have the same meaning as in formula (I) given hereinbefore.
  • More preferred structures of the blue sensitizing dyes are pyridyl rhodanines, given in formula (IV).
  • 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 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 ratio of gelatin to silver halide is determined at the stage of precipitation and/or by further addition of gelatin at the redispersion stage or later. If added, it is preferred, to make the emulsion(s) comprising silver halide tabular grains ready for coating by addition to the emulsion(s) of an amount of hydrogen-bridge forming polymer in such an amount that the ratio of hydrogen bridge-forming polymer to silver halide expressed as silver nitrate is comprised between 0.05 and 0.40 and, more preferably, between 0.15 and 0.30.
  • a preferred ratio of silica to silver halide expressed as silver nitrate is comprised between 0.03 and 0.3 and, more preferably, between 0.05 and 0.15 as has been disclosed in EP-A 0 528 476.
  • the binder added in addition before coating of hydrophilic colloidal layers on a suitable support is determining the physical properties of the resulting coated film material. Properties as, e.g., dimensional stability, scratchability, curl, pressure sensitivity and sludge formation after processing are highly dependant on the choice of the protective colloid. Gelatin is the most universal protective colloid used in photography, but alternatives, like e.g. colloidal silica and/or synthetic clays are not excluded.
  • Emulsion layers in accordance with the present invention, and more particularly thin emulsion layers, are showing remarkable improvements concerning both resistance to stress and rapid processability compared to conventional emulsions prepared in gelatinous medium.
  • emulsion(s) comprising silver halide tabular grains prepared in accordance with the present invention may be added compounds preventing the formation of fog or stabilizing the photographic characteristics prior to, during, or after the chemical ripening thereof or during the production or storage of photographic elements or during the photographic treatment thereof. Mixtures of two or more of these compounds can be used.
  • Suitable examples are i.a. 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.
  • heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles,
  • the silver halide emulsions prepared in accordance with the present invention can be used to form one or more silver halide emulsion layers coated on a support to form a photographic silver halide element according to well known techniques.
  • Two or more types of emulsions comprising silver halide tabular grains that have been prepared similarly or differently according to the method of this invention can be mixed in at least one emulsion layer for forming a photographic emulsion for use in accordance with the present invention.
  • the photographic element of the present invention may 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 and 4,292,400 and in EP-A's 0 634 849 and in EP-A 0 674 215.
  • 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 as described below.
  • a light-sensitive photographic material having a support and, on at least one side thereof, at least one hydrophylic colloid layer including at least one light-sensitive silver halide emulsion layer characterised in that said light-sensitive layer comprises at least one of said emulsions having spectrally sensitized tabular grains as defined.
  • the layers of the photographic element can be hardened 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-vinylsulphonyl-2-propanol, bis-(vinyl sulphonyl)-methane, 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., 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.
  • aldehydes e.g., formaldehyde, glyoxal, and glutaraldehyde
  • N-methylol compounds e.g., dimethylolurea and
  • the hardeners can be used alone or in combination.
  • the binders can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts as disclosed in US-P 4,063,952 and with the onium compounds as disclosed in EP-A 0 408 143.
  • the emulsion may be coated on any suitable substrate such as, preferably, a thermoplastic resin, e.g., polyethyleneterephtalate or a polyethylene coated paper support.
  • the support of the photographic material may be opaque or transparent, e.g., a paper support or resin support.
  • an Alpha-olefin polymer e.g., a polyethylene layer which optionally contains an anti-halation dye or pigment.
  • an organic resin support e.g., cellulose nitrate film, cellulose acetate film, poly(vinyl acetal) film, polystyrene film, poly(ethylene terephthalate) film,.
  • polycarbonate film polyvinylchloride film or poly-Alpha-olefin films such as polyethylene or polypropylene film.
  • the thickness of such organic resin film is preferably comprised between 0.07 and 0.35 mm.
  • These organic resin supports are preferably coated with a subbing layer which can contain water insoluble particles such as silica or titanium dioxide.
  • Suitable additives for improving the dimensional stability of the photographic element may be added, i.a., dispersions of a watersoluble 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, ⁇ - ⁇ -unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulphoalkyl (meth)acrylates, and styrene sulphonic acids.
  • a watersoluble or soluble synthetic polymer e.g., polymers of alkyl (meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl est
  • Plasticizers suitable for incorporation in the emulsions according to the present invention are, e.g., glycol, glycerine, or the latexes of neutral film forming polymers including polyvinylacetate, acrylates and methacrylates of lower alkanols, e.g., polyethylacrylate and polybutylmethacrylate.
  • Suitable UV-absorbers are, i.a., aryl-substituted benzotriazole compounds as described in US-P 3,533,794, 4-thiazolidone compounds as described in US-P's 3,314,794 and 3,352,681, benzophenone compounds as described in JP-A 2784/71, cinnamic ester compounds as described in US-A 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.
  • the average particle size of spacing agents is comprised between 0.2 ⁇ m 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 described in US-A 4,614,708.
  • the photographic material can contain several non-light sensitive layers, e.g., a protective antistress topcoat layer, one or more backing layers, and one or more intermediate layers eventually containing filter- or antihalation dyes that absorb scattering light and thus promote the image sharpness, although for the blue to ultra-violet sensitized material the problem will be less than for green- and/or red-sensitised materials.
  • Suitable light-absorbing dyes used in these intermediate layers are yellow dyes described in, e.g., US-P's 4,092,168 and 4,311,787 and in DE 2,453,217.
  • the photographic tabular silver halide emulsions can be used in various types of photographic elements such as, i.a., in photographic elements for so-called amateur and professional photography, for graphic arts, diffusion transfer reversal photographic elements, low-speed and high-speed photographic elements, X-ray materials, micrografic materials, etc..
  • the photographic silver halide emulsions are used in X-ray materials.
  • a material with a single or a duplitized emulsion layer coated on one or both sides of the support may contain tabular silver halide emulsions spectrally sensitised according to the invention.
  • duplitized emulsions differing in photographic speed by at least 0.15 log E a gain in cross-over exposure in double side coated materials can be obtained.
  • a light-sensitive silver halide emulsion comprising tabular grains spectrally sensitized by the method disclosed hereinbefore, as well as a photographic material comprising a support and on at least one side of said support at least one hydrophilic colloid layer and at least one photosensitive layer comprising at least one photographic silver halide emulsion with tabular grains spectrally sensitized as defined and wherein the total amount of silver coated on one side of said support, expressed as the equivalent amount of silver nitrate, is less than 10 g/m 2 , more preferably less than 7 g/m 2 and still more preferably less than 5.5 g/m 2 .
  • the time to dissolve the coated layers of said material determined by the method disclosed hereinafter, is not less than 45 minutes and, more preferably, not less than 60 minutes.
  • the said "time” means "the period of time from the moment when a silver halide photographic light-sensitive material cut into a sample having a size of 1 cm x 2 cm is dipped into an aqueous solution of 1.5 % by weight of NaOH at 50°C, until the moment when at least one of the silver halide emulsion layers constituting the said material starts to dissolve".
  • the material contains blue, green and red sensitive layers each of which can be single coated, but generally consist of double or even triple layers.
  • the photographic material may contain several light-insensitive layers, e.g., a protective antistress layer, one or more backing layers, one or more subbing layers, one or more intermediate layers, e.g., filter layers and even an afterlayer containing e.g. the hardening agent(s), the antistatic agent(s), filter dyes for safety-light purposes, etc.
  • One or more backing layers can be provided at the non-light sensitive side of the support of materials coated with at least one emulsion layer at only one side of the support.
  • These layers which can serve as anti-curl layer can contain, e.g., matting agents like silica particles, lubricants, antistatic agents, light absorbing dyes, opacifying agents, e.g., titanium oxide and the usual ingredients like hardeners and wetting agents.
  • the photographic material containing blue-sensitized tabular grains according to the present invention can be image-wise exposed by any convenient radiation source in accordance with its specific application.
  • a radiographic screen-film combination comprising at least one X-ray intensifying screen emitting blue and/or ultraviolet light, more specifically in the 400 to 500 nm range, in operative association with the material according to this invention is preferred.
  • Particularly useful X-ray intensifying screens emitting blue and/or ultraviolet radiation have been described in WO93/11457 and 93/11458.
  • processing conditions and composition of processing solutions are dependent from the specific type of photographic material in which the tabular grains prepared according to the present invention are applied.
  • said materials may be adapted to rapid processing conditions, including the steps of developing, fixing, rinsing and drying.
  • an automatically operating processing apparatus is used provided with a system for automatic regeneration of the processing solutions.
  • the forehardened material may be processed using one-part package chemistry or three-part package chemistry, depending on the processing application determining the degree of hardening required in said processing cycle.
  • applications within total processing times of up to 30 s are possible, whereas applications up to 90 seconds are known as common praxis. From an ecological point of view it is even possible to use sodium thiosulphate instead of ammonium thiosulphate and to reduce the regeneration amounts of developer and fixer.
  • Emulsion No. 1 (comparative):
  • a photographic silver iodobromide emulsion containing 2.0 mole % of silver iodide was prepared by a conventional single jet method in a vessel containing 40 g of phthaloyl gelatin.
  • the ammoniacal silver nitrate solution was held at 42°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 40 minutes. After that time an additional amount of 20 g of gelatin was added.
  • the obtained emulsion was of an average grain diameter of 0.62 ⁇ m and contained 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 nitrate was 0.42, the emulsion containing an amount of silver bromoiodide equivalent with 190 g of silver nitrate pro kg.
  • the emulsion crystals were chemically ripened with sulphur and gold at 47°C for 4 hours to get an optimized relation between fog and sensitivity.
  • Emulsion No. 2 (invention):
  • the preparation steps were a nucleation and a first neutralization step, followed by a first growth step, a second neutralization step and a second growth step.
  • reaction vessel 41.3 ml of solutions 1 and 2 were introduced into a reaction vessel in 28 seconds using the double jet technique.
  • Said reaction vessel initially contained 2.16 liter of distilled water at 45°C, 12.6 grams of potassium bromide and 12.5 grams of gelatin. After one minute the reaction temperature of this mixture was raised to 70°C in 20 minutes and 47.5 grams of phthalated gelatin in 475 ml destilled water were added. After 10 minutes the neutralization step was started.
  • a double jet precipitation was started using solutions 1 and 2 which continued for 40 minutes 51 seconds. During this precipitation, the pBr value was kept constant at 1.63. The flowing rate of solution 1 was 7.5 ml per minute at the start, linearly increasing to 26.7 ml per minute at the end of the precipitation. Thereafter the second neutralisation phase was started.
  • Second growth step (during which 47.0 % of the total amount of AgNO 3 was used):
  • the tabular grain emulsion obtained had the following characteristics, measured with electron microscopic techniques:
  • the emulsion was optimally sulphur and gold sensitized in the presence of sodium thiocyanate, toluene thiosulphinic acid, sulphite ions and stabilizing compound phenylmercaptotetrazol in the presence of the blue spectral sensitizer, according to the formula (V) in an amount of 2.1 mmole per mole of silver bromoiodide.
  • Emulsion No. 5 same emulsion as emulsion No. 4 but another blue sensitising dye, according to the formula (VI) was added after the chemical ripening step and before addition of further coating solutions (see further).
  • Emulsion No. 9 same emulsion as emulsion No. 2 but another blue sensitising dye, according to the formula (VII), without solubilizing group, was added in the same amount before chemically ripening the emulsion grains.
  • a protective coating composition was prepared containing per liter the following ingredients in demineralized water:
  • Samples of these coatings were exposed to visible light coming from projection lamps (130V; 250W) of an exposure voltage of 90V during 0.1 s at a distance of 1.8 m from the film, through a continuously varying carbon-coated wedge(wedge constant 0.15), a densitometric filter with a density of 0.30 and a "Corning filter 5850" as a blue filter with a density 2.64 (measured with a Macbeth TR 924 densitometer).
  • the exposed samples were processed during the 90 seconds cycle described below.
  • the density as a function of the light dose was measured and therefrom were determined the following parameters:
  • a spectrally sensitizing dye differing from the preferred type according to this invention is used (see Em. No. 9), or if spectral sensitization is not applied during the chemical sensitisation step or before, a remarkable loss in speed occurs.
  • Composition of Developer - concentrated part : water 200 ml potassium bromide 12 grams potassium sulphite (65% solution) ethylenediaminetetraacetic acid, 249 grams sodium salt,trihydrate 9.6 grams hydroquinone 106 grams 5-methylbenzotriazole 0.076 grams 1-phenyl-5-mercaptotetrazole 0.040 grams sodiumtetraborate (decahydrate) 70 grams potassium carbonate 38 grams potassium hydroxide 49 grams diethylene glycol 111 grams potassium iodide 0.022 grams 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone 3 grams Water to make 1 liter pH adjusted to 11.15 at 25°C with potassium hydroxide.
  • Emulsion No. 2 (invention) from Example 1 was taken and experiments were performed during chemical sensitization in the presence of triphenylphosphorselenide as a selenium ion providing compound.
  • Table 3 the most relevant sensitometric results are given, said results being given as a function of variations in amounts of sulphur and gold, added in combination with the said triphenylphosphorselenide compound.
  • Amounts of sulphur (S), selenium (Se) and gold (Au) (expressed in ⁇ mole per mole of silver) are also summarized in Table 3.
  • Coatings (emulsion, protective layer) were performed just as described in Example 1.

Claims (12)

  1. Ein Verfahren zur Herstellung einer Tafelkorn-Silberhalogenidemulsion, wobei die tafelförmigen Silberhalogenidkörner ein Aspektverhältnis von zumindest 2:1, einen mittleren Kristalldurchmesser zwischen 0,3 µm und 3,0 µm und eine mittlere Stärke von weniger als 0,50 µm aufweisen und zumindest 50% der totalen projizierten Oberfläche aller Körner verkörpern, und wobei das Verfahren als Stufen die Fällung der Körner, die spektrale Sensibilisierung und die chemische Reifung umfaßt, gekennzeichnet durch Zugabe in der Emulsion, vor oder während der chemischen Reifung, von zumindest einem spektral sensibilisierenden Farbstoff der allgemeinen Formel (I) :
    Figure 00310001
    in der bedeuten :
    X die zur Bildung eines heterocyclischen 5- oder 6-gliedrigen Ringes benötigten Atome,
    Q S, NR3, O oder -(C=O)-N(R4)-,
    M+ ein Kation,
    n 0, 1 oder 2,
    p 0 oder 1,
    R1, R2, R3 und R4 unabhängig voneinander jeweils eine substituierte oder nicht-substituierte C1-C5-Alkylkette,
    mit der Maßgabe, daß zumindest eines von R2, R3 und R4 eine wäßrig-alkalische solubilisierende Gruppe oder eine latente wäßrig-alkalische solubilisierende Gruppe enthält.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die mittlere Stärke der tafelförmigen Silberhalogenidkörner weniger als 0,30 µm beträgt.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die zumindest eine solubilisierende Gruppe enthaltende Alkylkette im Farbstoff der allgemeinen Formel (I) einer der folgenden Formeln entspricht :
    (CH2)mSO3 - oder (CH2)mN(R)SO3 -, in denen m 1, 2, 3 oder 4 bedeutet und R dieselbe Bedeutung wie R1 bis R4 hat,
    (CH2)2CH(Y)SO3 -, in der Y CH3-, -Cl oder -OH bedeutet,
    (CH2)qOSO3 -, in der q 2 oder 3 bedeutet,
    (CH2)rCO2 -(H+), in der r 1, 2 oder 3 bedeutet,
    (CH2)sSO2 -(CH2)tH, in der s 2 oder 3 und t 1 oder 2 bedeutet,
    (CH2)x-Phen-W, in der W -COO- oder SO3 -, Phen eine substituierte oder nicht-substituierte Phenylgruppe und x 1, 2, 3 oder 4 bedeutet.
  4. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die zumindest eine latente wäßrig-alkalische solubilisierende Gruppe enthaltende Alkylkette im Farbstoff der allgemeinen Formel (I) der Formel (CH2)m'-(C=O)-O-CH2-(C=O)-CH3 entspricht, in der m' eine ganze Zahl zwischen 1 und 5 bedeutet.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Farbstoff der Formel (II) oder (III) entspricht :
    Figure 00320001
    Figure 00330001
    in denen Q, M+, n, R1 und R2 die diesen Symbolen in Anspruch 1 zugeordnete Bedeutung haben.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Farbstoff der Formel (IV) entspricht :
    Figure 00330002
    in der R1, R2, n und M+ die diesen Symbolen in Anspruch 1 zugeordnete Bedeutung haben.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Farbstoff der Formel (V)
    Figure 00330003
    entspricht.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Körner ein mittleres Aspektverhältnis von zumindest 5:1 aufweisen.
  9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die chemische Reifung der blausensibilisierten Tafelkörner in Gegenwart von Kombinationen von Schwefel-, Selen- und Goldionen liefernden Verbindungen erfolgt.
  10. Eine lichtempfindliche Silberhalogenidemulsion, die nach dem Verfahren nach einem der Ansprüche 1 bis 9 hergestellte Tafelkörner enthält.
  11. Ein lichtempfindliches fotografisches Silberhalogenid-Röntgenmaterial, das einen Träger und auf zumindest einer Seite des Trägers zumindest eine hydrophile Kolloidschicht und zumindest eine strahlungsempfindliche Schicht mit zumindest einer fotografischen Silberhalogenidemulsion nach Anspruch 10 enthält, wobei die als die äquivalente Menge Silbernitrat ausgedrückte Gesamtmenge des auf eine Seite des Trägers aufgetragenen Silbers weniger als 10 g/m2 beträgt und die nach dem in der vorliegenden Erfindung offenbarten Verfahren ermittelte Zeit zum Lösen der aufgetragenen Schichten des Materials zumindest 45 Minuten beträgt.
  12. Eine radiografische Film-Folien-Kombination, die zumindest eine Blaulicht und Ultraviolettlicht emittierende Verstärkerfolie in wirksamer Beziehung zu einem Material nach Anspruch 11 enthält.
EP19950203024 1994-11-11 1995-11-08 Verfahren zur spektralen Sensibilisierung von tafelförmigen Silberhalogenidkörnern Expired - Lifetime EP0712034B1 (de)

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EP1045282B1 (de) * 1999-04-16 2002-10-16 Agfa-Gevaert UV/Blauempfindlicher Röntgenfilm und Kombination eines Verstärkungsschirms mit einem Film
US6403276B1 (en) 1999-04-16 2002-06-11 Agfa-Gevaert Radiographic UV/blue film material and intensifying screen-film combination
US6686118B1 (en) 2003-03-26 2004-02-03 Eastman Kodak Company Blue-sensitive film for radiography and imaging assembly and method
US6686117B1 (en) 2003-03-26 2004-02-03 Eastman Kodak Company Blue-sensitive film for radiography with reduced dye stain
US6686116B1 (en) 2003-03-26 2004-02-03 Eastman Kodak Company Blue spectrally sensitized film for radiography, imaging assembly and method
US6682868B1 (en) 2003-03-26 2004-01-27 Eastman Kodak Company Radiographic imaging assembly with blue-sensitive film
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