EP0752617B1 - Erzeugungsverfahren für photographisches Silberhalogenidmaterial geeignet für schnelle Verarbeitungsanwendungen - Google Patents

Erzeugungsverfahren für photographisches Silberhalogenidmaterial geeignet für schnelle Verarbeitungsanwendungen Download PDF

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Publication number
EP0752617B1
EP0752617B1 EP19960201684 EP96201684A EP0752617B1 EP 0752617 B1 EP0752617 B1 EP 0752617B1 EP 19960201684 EP19960201684 EP 19960201684 EP 96201684 A EP96201684 A EP 96201684A EP 0752617 B1 EP0752617 B1 EP 0752617B1
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EP
European Patent Office
Prior art keywords
layer
dye
gelatin
silver halide
layers
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EP19960201684
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English (en)
French (fr)
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EP0752617A1 (de
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Marc c/o Agfa-Gevaert N.V. Van den Zegel
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—Hardeners
    • G03C1/301—Aldehydes or derivatives thereof, e.g. bisulfite addition products
    • 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
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • 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
    • G03C1/74—Applying photosensitive compositions to the base; Drying processes 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes

Definitions

  • This invention relates to a method of manufacturing a silver halide photographic material suitable for rapid processing applications.
  • a radiographic element which exhibits a high covering power, a reduced crossover without emulsion desensitisation, a reduced wet pressure sensitivity and rapid processing applicablity in a total processing time of less than 90 seconds.
  • the radiographic element is comprised of tabular grain emulsion layers on opposite sites of a transparent film support and a hydrophilic colloid layer comprising dye particles is interposed between the emulsion layer and the support to reduce cross-over. In the processing the said dye particles are completely decolourised. Amounts of hydrophilic colloid coated on both sides of the support are in the range from 3.5 to 6.5 g/m 2 ; and in the interposed layer at least 1 g/m 2 is coated. This coated amount of 1 g/m 2 is necessary to avoid coating uneveness.
  • the amount of gelatin coated per m 2 it is preferred to reduce the amount of gelatin coated per m 2 .
  • the amount of gelatin should be reduced to a minimum, without decreasing the amount of dye(s) as the said amount is reducing the crossover percentage of the radiographic material.
  • a silver halide photographic material comprising a dye containing hydrophilic antihalation layer wherein the coating weight of the hydrophilic colloid is not more than 0.5 g/m 2 and the swelling ratio not higher then 180%. It is stated therein that when this antihalation layer is coated on a subbing layer containing a hydrophobic polymer and dried after coating, then the material built up further adjacent to the said antihalation layer with an emulsion layer and a protective antistress layer, shows the presence of a disturbing residual colour, also called "dye stain", after processing.
  • a primary object of this invention to provide a method of manufacturing a forehardened radiographic material, comprising a support provided with a subbing layer comprising vinylidene chloride and a dye containing layer in contact with said subbing layer in order to enhance sharpness, the said material being suitable for rapid processing applications without leaving residual stain, without drying problems and without posing adhesion problems.
  • a method is described to provide a radiographic silver halide material by coating on at least one side of a support, covered with a hydrophobic subbing layer, comprising as a latex copolymer vinylidene chloride, methylacrylate and itaconic acid, in consecutive order following hydrophilic layers: at least one gelatinous dye containing layer comprising one or more dyes, at least one silver halide emulsion layer, at least one protective antistress layer, and optionally an afterlayer, characterised in that said hydrophilic layers have a swelling ratio of not more than 200 % and in that said hydrophilic layers are coated simultaneously by the slide-hopper coating or by the slide-hopper curtain coating technique.
  • the method according to our invention shows many advantages over the method applied in the manufacturing of the material, described in US-P 5,077,184.
  • a solution can be found by coating a layer arrangement comprising at one or both sides of a support, covered with a hydrophobic subbing layer, a hydrophilic layer arrangement consisting of a gelatinous dye containing layer comprising at least one dye, at least one silver halide emulsion layer, at least one protective antistress layer, and, optionally, comprising an afterlayer.
  • the necessary condition to get excellent adhesion properties after processing for a photographic material having the layer arrangement as described hereinbefore is that the so-called hydrophilic layers are coated simultaneously by the well-known techniques as the slide-hopper technique and the slide-hopper curtain coating technique, which have been described e.g. in EP's 0 051 238; 0 107 818; 0 300 098; DE 3 238 904; JP-A 04 001 635; WO 94/029769 and US-P's 4,191,213; 4,313,980; 4,384,015; 4,569,863; 4,877,639; 4,942,068 and 5,264,339, without however being limited thereto.
  • the slide-hopper technique and the slide-hopper curtain coating technique which have been described e.g. in EP's 0 051 238; 0 107 818; 0 300 098; DE 3 238 904; JP-A 04 001 635; WO 94/029769 and US-P'
  • Subbing layers have been described in e.g. DE 2 747 231; in GB 2,033,598; and in WO's 84/000621 and 87/006723.
  • the subbing layer applied in the method of this invention consists of the latex copolymer vinylidene chloride (88 wt%), methylacrylate (10 wt%) and itaconic acid (2 wt%); the latex copolymer of methylmethacrylate (47.5 wt%), 1,3-butadiene (47.5 wt%) and itaconic acid (2 wt%); polymethylmethacry-late-particles as a matting agent, and coating aids therefor.
  • the layer adjacent to the subbing layer is a dye containing layer comprising a dispersion of at least one dye.
  • Said dye(s) is(are) selected in such a way as to reach the preferred objects of this invention set forth hereinbefore.
  • double side coated X-ray film materials are exposed with light emitting phosphors, wherein the dye containing layers present at both sides of the support and in close contact therewith, reduce the amount of light passing through the said support to the opposite layer and, correspondingly, the so-called cross-over exposure related thereto.
  • Reduction of scattering of incident exposure light not only depends on the absorption spectrum which should match the emission spectrum of the phosphor particles in the screen(s), brought in close contact with the radiographic film material.
  • the absorption spectrum of the dye(s) depends on the nature of the dye(s), which is further determining the wavelength region in which exposure light absorption occurs, but also on the way in which the dye is dispersed in the binder medium of the antihalation layer, which is decisive for the amount of dye that has to be added to the antihalation coating solution.
  • fine solid particle dispersions of dyes are preferred and in another embodiment fine particle dispersions prepared in silica sol, so-called “silica solid particle dispersions", the dispersion of which has been described in e.g. EP-A 0 569 074, are preferred.
  • the size of the dispersed dye particles and the dispersing aids are further determining the amount of dye(s) required in the dye containing layer, in order to get sufficient absorption of incident exposure rays and reduction of the scattering effect.
  • Lower amounts of dye(s) coated are further in favour of rapid processing applications as the dye(s) can be removed more quickly in the processing.
  • Well-known phosphor screens are those emitting blue and ultraviolet light or green light.
  • the dyes should be selected in order to absorb light of the corresponding wavelengths.
  • Especially dyes absorbing green light are preferred as problems relating to sharpness are connected to a larger extend with emitted light of longer wavelenghts than those in the ultraviolet and/or blue wavelength region.
  • Preferred antihalation dyes for use in the materials prepared by the method of this invention are described e.g. in EP-A 0 586 748, EP-A 0 656 401, in EP-Application No. 94203766 (filed December 27, 1994) and in US-P's 5,380,634 and 5,344,749 which are incorporated herein by reference.
  • microprecipitated dispersion refers to the method used to prepare a dispersion of the dye which should be soluble in alkaline medium, due to the presence of alkaline soluble groups. Microprecipitation occurs by controlling acidifying of the said alkaline medium, resulting in precipitation of the dye in "microprecipitated form”.
  • the presence of the dyes in the said microprecipitated form is recommended in favour of lowering the required concentration of dyes in the dye containing layer(s).
  • the amount of dye incorporated in the dye containing layer is optimised in order to get a cross-over lower than 15 % and more preferably lower than 10 % for double side coated materials.
  • the total concentration of dyes is not higher than 300 mg/m 2 and, more preferably, not more than 150 mg/m 2 in order to avoid adhesion problems between the subbing layer and the adjacent dye containing layer.
  • a total amount of hydrophilic binder in the dye containing layer(s) is preferably not more than 750 mg/m 2 , as the ratio between the ratio by weight of dye to hydrophilic binder should preferably exceed a value of 0.4, but remain lower than 1.3 for adhesion reasons as disclosed hereinbefore.
  • the said dye containing layer is split up into a first layer, containing e.g. at least one dye, and, adjacent thereto, a second layer, containing e.g. at least one other or the same dye or dye mixture.
  • the amount of dye, present in the first dye containing layer in contact with the subbing layer is not more than 100 mg/m 2 , and more preferably not more than 50 mg/m 2 , which means that for a ratio by weight of dye to hydrophilic binder of more than 0.4, the said binder amount should not exceed 0.125 g/m 2 in the hydrophilic layer in contact with the subbing layer in a split up dye containing layer arrangement.
  • the dye or mixtures of dyes may be the same or different in both layers.
  • tabular shaped silver halide crystals are present in the emulsion layer(s).
  • the main photographic advantages of tabular crystals compared to normal globular grains are a high covering power at high forehardening levels, a high developability and higher sharpness, especially in double side coated spectrally sensitised materials. The thinner the tabular grains the greater these advantages.
  • tabular crystals have two important disadvantages: the susceptibility to mechanical stress and the unacceptable reddish-brown colour compaired with the cold-black colour shown by more globular grains of the developed silver.
  • a more convenient way to reach this goal has been described in EP-A's 0 569 075, 0 634 688 and 0 674 215; which are incorporated herein by reference and wherein the favourable developability, known from thin tabular grains is reached.
  • a thickness of the silver bromide or silver bromoiodide emulsion crystals between 0.15 and 0.30 ⁇ m is highly preferred therein for crystals having an aspect ratio of at least 2, wherein at least 70 % of the total projected area of all the grains are provided by tabular grains.
  • Silver halide compositions are not restricted to silver bromide and/or silver bromoiodide as has e.g. been shown in EP-Application No. 95200651 (filed March 17, 1995), which is incorporated herein by reference, and wherein it has been shown that with the said tabular silver halide crystals rich in chloride, known for a very good developability and a suitable black image tone, a sufficiently high speed is obtained, even for a thickness of the crystals used therein from 0.08 to 0.20 ⁇ m.
  • the tabular silver halide emulsions which can be used in the silver halide emulsion layer(s) from the materials manufactured by the method of this invention can be chemically sensitised as described e.g. in "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 Sawe mit Silberhalogeniden” edited by H. Frieser and published by Akademische Verlagsgesellschaft (1968).
  • chemical sensitisation 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.
  • the emulsions may be sensitised also by means of gold-sulphur ripeners or by means of reductors e.g. tin compounds as described in GB Patent 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, dialdehyde bisulphite adducts and aromatic sulphinic acid as described in US-P 4,175,970 and silane compounds.
  • More preferred sensitising agents in addition to or replacing sulphur compounds, are selenium and/or tellurium compounds as has been described e.g. in JP-A's 04 016 838; 04 324 855; 04 328 740; 04 330 433; 05 045 769; 06 266 034; in EP-A 0 590 593; 0 619 515; 0 622 665; 0 638 840; in WO 93/012460; and in US-P's 4,861,703; 5,246,826; 5,273,872; 5,273,874; 5,306,613; 5,342,750 and 5,364,754.
  • the tabular silver halide emulsions may be spectrally sensitised with methine dyes such as those described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons.
  • Dyes that can be used for the purpose of spectral sensitisation include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.
  • Especially preferred green sensitiser in connection with the present invention are anhydro-5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyloxacarbocyanine hydroxide and anhydro-5,5'-dichloro-3,3'-bis(n.sulfopropyl)-9-ethyloxacarbo-cyanine hydroxide.
  • spectral sensitisation traditionally follows the completion of chemical sensitisation. However, in connection with tabular grains, it is specifically considered that spectral sensitisation may occur simultaneously with or may even precede completely the chemical sensitisation step: the chemical sensitisation after spectral sensitisation is believed to occur at one or more ordered discrete sites of tabular grains.
  • emulsions of the present invention may also be done with the emulsions of the present invention, wherein the chemical sensitisation proceeds in the presence of one or more phenidone and derivatives, a dihydroxy benzene as hydroquinone, resorcinol, catechol and/or a derivative(s) therefrom, one or more stabiliser(s) or antifoggant(s), one or more spectal sensitiser(s) or combinations of said ingredients.
  • the silver halide emulsion layer(s) in accordance with the present invention or the non-light-sensitive layers adjacent thereto may comprise compounds preventing the formation of fog or stabilising the photographic characteristics during the production or storage of the photographic elements or during the photographic treatment thereof.
  • Many known compounds can be added as fog-inhibiting agent or stabiliser to the silver halide emulsion layer or to other coating layers in water-permeable relationship therewith such as an undercoat or a protective layer. Suitable examples are e.g.
  • 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.
  • benzothiazolium salts such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlor
  • gelatin in the hydrophilic layers of the material prepared according to the method of this invention conventional lime-treated or acid treated gelatin can be used as a hydrophilic colloid.
  • 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).
  • a gelatin concentration of from about 0.05 % to 5.0 % by weight in the dispersion medium. Additional gelatin is added in a later stage of the emulsion preparation e.g. after washing, to establish optimal coating conditions and/or to establish the required thickness of the coated emulsion layer.
  • a gelatin/silver halide ratio ranging from 0.3 to 1.0, and more preferably from 0.3 to 0.5 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. Also synthetic clays are very useful as has been shown in EP-A 0 644 455.
  • a very useful binder is colloidal silica as is known from EP-B 0 392 092; EP-A's 0 517 961; 0 528 476; 0 649 051; 0 682 287; 0 704 749 and EP-Application No. 95200645 (filed March 17, 1995).
  • the photographic material can contain several non-light sensitive layers. Besides a hydrophilic protective antistress layer, coated simultaneously with at least one emulsion and at least one antihalation layer, according to the method of this invention, one or more intermediate layers, optionally containing filter or antihalation dyes, are coated.
  • Suitable light-absorbing dyes used in these intermediate layers are described in e.g. US-Patents 4,092,168 and 4,311,787, in DE 2,453,217, and in GB Patent 7,907,440. Coated in such an intermediate layer between the emulsion layer(s) and the support there will be a small negligable loss in sensitivity only but in rapid processing conditions discolouration of the filter dye layers may form a problem. Therefor it should be recommended to decrease the thickness of the whole layer arrangement coated, resulting in shorter drying times after washing in the processing cycle. In a preferred embodiment a total amount of gelatin over the whole layer arrangement should not exceed 3.5 g/m 2 , and more preferably not more than 3.2 g/m 2 .
  • one or more backing layers can be provided at the non-light sensitive side of the support of the said material.
  • These layers which may 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.
  • Antistatic agents may be present in the afterlayer and/or in the protective antistress layer(s); in the subbing layer and/or in the backing layer(s).
  • Preferred antistatic agents are e.g. polythiophenes, which have been described e.g. in US-P's 5,108,885; 5,312,681 and 5,391,472.
  • the simultaneously coated hydrophilic layers being the dye containing layer(s), the emulsion layer(s) and the protective antistress layer(s) have a swelling degree in the processing of not more than 200 %, this is indicative for a high degree of hardening.
  • Said swelling degree is determined by means of the following procedure: a sample of each coated material is incubated at 57 °C and 34% RH for 3 days, whereafter the thickness (a) of the layer assemblage is measured. Thereafter the sample is immersed in distilled water at 21°C for 3 minutes and the thickness (b) of the swollen layer is measured. The swelling ratio is then calculated as: (b-a)/a x 100 (%).
  • the hydrophilic 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, chromium salts as e.g. chromium acetate and chromium alum, aldehydes as e.g. formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds as e.g. dimethylolurea and methyloldimethylhydantoin, dioxan derivatives as e.g. 2,3-dihydroxy-dioxan, active vinyl compounds as e.g.
  • appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, chromium salts as e.g. chromium acetate and chromium alum, aldehydes as e.g. formaldehyde, glyoxal,
  • 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-P 4,063,952 and with the onium compounds as disclosed in EP-A 0 408 143.
  • a preferred hardening agent in the method of this invention is formaldehyd.
  • the hydrophobic subbing layer comprises a latex copolymer of vinylidene chloride, methylacrylate and itaconic acid formaldehyd hardening is in favour of good adhesion properties.
  • the hardener is added to the protective antistress layer, just before coating or added to an afterlayer.
  • the said afterlayer may further contain antistatic agents as described e.g. in EP-B 0 300 259 and in EP-A 0 644 456, which is incorporated herein by reference, and may be coated alternatively by means of the spray-coating technique as has e.g. been described in GB 1,334,429 and in WO 92/14188.
  • the addition of the hardening agent to the protective antistress layer or to the afterlayer can also be performed by means of a dose feeder.
  • Amounts of hardener are chosen in such a way as to obtain a swelling degree of the hydrophilic layers of not more than 200 % as described hereinbefore.
  • Materials prepared according to this invention are both single-side coated and double-side coated materials.
  • dye containing layers are recommended in favour of sharpness: scattering of the exposure light reflecting on the support has to be avoided for single-side coated materials and double-side coated materials and moreover cross-over has to be reduced to a minimum for double-side coated, also called “duplitized” materials.
  • the materials manufactured by the method of this invention are duplitized materials.
  • a material with a single or a duplitized emulsion layer coated on one or both sides of the support may contain one single emulsion layer, as it is the case for many applications, or it can be built up by two or even more emulsion layers.
  • 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.
  • the method used in connection with the present invention can further also be applied to the manufacturing of various other types of photographic elements as e.g. colour sensitive materials, as those described e.g. in EP-A 0 582 000; EP-A No. 95201015 (filed April 21, 1995) and US-P 4,770,984.
  • colour sensitive materials e.g. in EP-A 0 582 000; EP-A No. 95201015 (filed April 21, 1995) and US-P 4,770,984.
  • each of the blue, green and red sensitive layers can be single coated, but generally the said layers consist of double or even triple layers.
  • the photographic material and the several light-insensitive layers as e.g. the protective antistress layer, one or more backing layers (in the case of single-side coated materials), one or more subbing layers, one or more dye containing layers, one or more filter layers can be present on top of the emulsion layer(s).
  • the said filter layer(s) comprising one or more filter dye(s) can be used for safety-light purposes. Even for the more complicated layer arrangement, it is required, according to the method of this invention, to coat these layers simultaneously by means of the slide-hopper or slide-hopper curtain coating technique.
  • the support of the photographic material may be opaque or transparent e.g. a paper support or resin support.
  • a paper support preference is given to one coated at one or both sides with an Alpha-olefin polymer, e.g. a polyethylene layer.
  • an organic resin support e.g. cellulose nitrate film, cellulose acetate film, poly(vinyl acetal) film, polystyrene film, poly(ethylene terephthalate) film, poly(ethylene naphthalate) 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.
  • the photographic material prepared by the method according to the present invention can be image-wise exposed by any convenient radiation source in accordance with its specific application.
  • processing conditions and composition of processing solutions are dependent from the specific type of photographic material prepared according to the present invention.
  • materials for X-ray diagnostic purposes may be adapted to rapid processing conditions.
  • 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 from 30 seconds up to 90 seconds, known as common praxis, are possible. From an ecological point of view it is even recommended to use sodium thiosulphate instead of ammonium thiosulphate.
  • a blue tinted, longitudinally stretched polyethylene terephtalate film support having a thickness of approximately 0.61 mm was subbed on both sides with a coating solution at a coverage of 130 m 2 per liter.
  • the layer was dried in a hot air stream whereafter the coated support was stretched transversally to 3.5 times its original width, at a temperature of about 110°C.
  • 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. After heat setting the film was cooled. This subbing procedure resulted in the following layer composition per m 2 and per side:
  • Support 2 was coated on both sides with a second subbing layer at a coverage of 30 m 2 per liter coating solution.
  • the coating solution was applied at 40 °C.
  • the layer was dried in a hot air stream at 130 °C during 2 minutes, resulting in the following layer composition per m 2 and per side:
  • Support 3 was coated similar as support 2 except for the fact that part of the gelatin was replaced by a gelatinous dispersion of dye I. Per m 2 and per side 0.19 g of gelatin and 0.05 g of dye I were coated.
  • 100 g of dye I was dispersed at 40 °C and at a pH value of 5.5 in 900 g of an aqueous gelatin solution, containing 50 g of gelatin, by using a rotating pearl mill containing as a milling material zirconium oxide pearls sizing 1.0 to 1.6 mm. At a dye particle size of 1 ⁇ m the milling process was stopped, the dispersion was separated from the milling material and chilled.
  • Support 4 is similar to support 3, except for a doubling of the quantity of dye dispersion. Per m 2 and per side 0.19 g of gelatin and 0.1 g of dye I were coated.
  • Support 5 is similar to support 4, except for a further doubling of the quantity of the dye dispersion. Per m 2 and per side 0.19 g of gelatin and 0.2 g of dye I were coated.
  • Support 6 is similar to support 4, except for an increase of the amount of gelatin. Per m 2 and per side 0.5 g of gelatin and 0.1 g of dye I were coated.
  • This emulsion was chemically sensitised in the presence of anhydro-5,5'-dichloro-3,3'-bis(n.sulfobutyl)-9-ethyloxacarbocyanine hydroxide, chloro auric acid, sodium thiosulphate and potassium thiocyanate in order to get an optimised fog-sensitivity relationship.
  • demineralised water To 800ml of demineralised water the following ingredients were added: 44 g of gelatin; 0.92 g of polymethylmethacrylate (average particle diameter : 3.5 ⁇ m); 0.3 g of ammoniumperfluorocaprylate; 0.752 g of C 17 H 15 -CO-NH-(CH 2 -CH 2 -O-) 17 -H and 4 g of formaldehyde.
  • Demineralised water was added to get the desired wet coating thickness and gelatine per m 2 .
  • Materials 1 to 5 were obtained by coating simultaneously the emulsion layer and the protective layer at both sides of the supports 2 to 6 making use of the coating solutions for the emulsion and protective layer, held at 38°C, the composition of which has been described hereinbefore, and dried under controlled humidity and temperature conditions, never exceeding a temperature of 30 °C.
  • the emulsion and protective layer were coated simultaneously by means of the slide hopper technique with the protective layer on top. Before drying the thicknesses of the emulsion layer and protective layer were 44 and 25 ⁇ m respectively.
  • Per m 2 and per side the emulsion layer was containing 3.75 g of silver, expressed as the equivalent amount of silver nitrate and 1.87 g of gelatin.
  • the protective antistress layer was containing 1.1 g of gelatin.
  • the antihalation layer was containing 0.19 g of gelatin and 0.100 g of dye I
  • the emulsion layer was containing 3.75 g of silver, expressed as the equivalent amount of silver nitrate and 1.87 g of gelatin and the protective topcoat layer was containing 1.1 g of gelatin.
  • the layers were dried under controlled conditions of humidity and temperature (never exceeding 30 °C).
  • Material 7 is similar to material 6 except for the solution containing dye I which was prepared with 200 g of the dispersion of dye I and 9.0 g of gelatin. After drying the said layer was containing per m 2 and per side: 0.19 g gelatin and 0.20 g dye I.
  • a CURIX HT530 (Agfa-Gevaert trademarked name) processor was used with the following processing time (in seconds) and processing temperature (in °C) characteristics: function time temperature condition loading 0.2 developing 11.5 35 o C developer described below cross-over 1.7 rinsing 1.1 cross-over 1.8 fixing 8.2 35 o C fixer described below cross-over 2.5 rinsing 5.4 20 o C cross-over 5.8 drying 8.3 total 46.5
  • composition of the concentrated part :
  • composition of the fixer is Composition of the fixer:
  • composition of the concentrated part is composition of the concentrated part:
  • ammonium thiosulfate 78% solution: 661 g; sodium sulphite: 54 g; boric acid: 25 g; sodium acetate-trihydrate: 70 g; acetic acid: 40 g and water to make 1 liter. The pH was adjusted with acetic acid to 5.30 at 25°C.
  • the thickness (a) of the layer assemblage was measured. Thereafter the sample was immersed in distilled water at 21°C for 3 minutes and the thickness (b) of the swollen layer was measured. The swelling ratio is then calculated as: (b-a)/a x 100 (%).
  • the thickness of the layers was measured using a stamper moving up and down with respect to the surface of the sample.
  • the surface of the stamper contacting the surface of the sample was curved with a curvature radius of 17 mm.
  • the weight that the stamper exerted on the sample is 6 g.
  • the stamper thereby moved through a spool causing an induction current which was proportional to the thickness of the sample.
  • the stamper was first callibrated using a sample of known thickness.
  • the swelling ratio of the materials were all between 170 and 190%.
  • Samples of the materials were dipped for 4 minutes into water of 25 °C, whereupon the layer arrangement was scratched cross-wise with a pen tip reaching the film base.
  • the adhesion in wet stage was checked by rubbing the wetted layer arrangement with finger tip for 10 seconds.
  • the quality of the wet adhesion was evaluated by giving the result of the rubbing a rating from 0 to 4, wherein 0 stands for non-removal and 4 for complete removal by said rubbing.
  • the dye layer which was dried at 130°C separately from the emulsion layer and from the protective layer is called “DLA”, referring to the comparative materials.
  • DLA the dye layer which was dried simultaneously with the emulsion layer and the protective layer
  • DLB the dye containing layer which was coated simultaneously with the emulsion layer and the protective layer
  • the amounts of gelatin and of dye, expressed in g per m 2 and per side, are given in Table I.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (9)

  1. Verfahren zur Bereitstellung eines Röntgenmaterials aus Silberhalogenid mit dem Schritt : Auftragen der nachstehenden hydrophilen Schichten in der Reihenfolge auf wenigstens eine Seite eines Trägers, der mit einer hydrophoben Haftschicht, die Vinylidenchlorid, Methylacrylat und Itakonsäure als Copolymerisatlatex enthält, überzogen wurde :
    wenigstens eine farbstoffhaltige gelatineartige Schicht, die einen oder mehrere Farbstoffe enthält,
    wenigstens eine Silberhalogenid-Emulsionsschicht,
    wenigstens eine Schutzschicht,
    dadurch gekennzeichnet, dass
    die hydrophilen Schichten einen maximalen Schwellkoeffizient von 200% aufweisen
    und dadurch, dass
    die hydrophilen Schichten unter Verwendung des Kaskadenbeschichtungs- oder Kaskadenvorhangsbeschichtungsverfahrens gleichzeitig aufgetragen werden.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass eine Nachschicht als eine hydrophile Außenschicht vorliegt.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Farbstoff bzw. die Farbstoffe aus der Reihe: ein Oxonolfarbstoff und/oder ein Merostyrylfarbstoff, der während der Verarbeitung bei einem minimalen pH-Wert von 8,0 löslich ist und bei einem pH-Wert kleiner als 6,0 unlöslich ist, ausgewählt wird bzw. werden.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Farbstoff bzw. die Farbstoffe in Form einer mikrogefällten Dispersion enthalten ist bzw. sind.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Farbstoff bzw. die Farbstoffe in einer maximalen Gesamtmenge von 300 mg/m2 in einer derartigen Menge an hydrophilem Bindemittel enthalten ist bzw. sind, dass Gewichtsverhältnis des Farbstoffes zu der Gelatine 0,4 bis 1,3 beträgt.
  6. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass zwei farbstoffhaltige Schichten vorliegen: eine erste Schicht, die wenigstens einen Farbstoff enthält, und in Nachbarstellung dazu eine zweite Schicht, die wenigstens den gleichen Farbstoff oder einen anderen Farbstoff enthält.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass der Farbstoff bzw. die Farbstoffe in der ersten Schicht in einer Höchstmenge von 100 mg/m2 enthalten ist bzw. sind.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Silberhalogenid-Emulsionsschicht bzw. die Silberhalogenid-Emulsionsschichten wenigstens eine Emulsion aus tafelförmigem Silberhalogenid enthält bzw. enthalten.
  9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die hydrophilen Schichten mit Formaldehyd gehärtet werden.
EP19960201684 1995-07-04 1996-06-17 Erzeugungsverfahren für photographisches Silberhalogenidmaterial geeignet für schnelle Verarbeitungsanwendungen Expired - Lifetime EP0752617B1 (de)

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Publication number Priority date Publication date Assignee Title
EP0790526B1 (de) 1996-02-19 2002-07-24 Agfa-Gevaert System von Film und Schirm zur Herstellung radiographischen Bildes
US6071681A (en) * 1997-05-20 2000-06-06 Konica Corporation Method for producing silver halide photographic light-sensitive material
EP0911694A1 (de) * 1997-10-20 1999-04-28 Agfa-Gevaert N.V. Photoempfindliches Silberhalogenidmaterial, das eine Anordnung von Schichten enthält

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US4175970A (en) * 1978-07-24 1979-11-27 E. I. Du Pont De Nemours And Company Process for sensitizing photographic silver halide emulsions
DE3774704D1 (de) * 1987-07-21 1992-01-02 Agfa Gevaert Nv Beschichtungsverfahren.
EP0554834B1 (de) * 1992-02-03 1998-06-03 Fuji Photo Film Co., Ltd. Verfahren zur Dispergierung eines Farbstoffs und ein Farbstoff enthaltendes photographisches Silberhalogenidmaterial
JPH07168299A (ja) * 1993-12-16 1995-07-04 Konica Corp ハロゲン化銀写真乳剤、ハロゲン化銀写真感光材料及びその処理方法

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