EP0844520B1 - Film-Materialien mit farbigen Mattierungsteilchen - Google Patents

Film-Materialien mit farbigen Mattierungsteilchen Download PDF

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Publication number
EP0844520B1
EP0844520B1 EP19970203598 EP97203598A EP0844520B1 EP 0844520 B1 EP0844520 B1 EP 0844520B1 EP 19970203598 EP19970203598 EP 19970203598 EP 97203598 A EP97203598 A EP 97203598A EP 0844520 B1 EP0844520 B1 EP 0844520B1
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EP
European Patent Office
Prior art keywords
silver
blue
silver halide
layer
material according
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EP19970203598
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English (en)
French (fr)
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EP0844520A1 (de
Inventor
Hubert Vandenabeele
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Agfa Gevaert NV
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Agfa Gevaert NV
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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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/32—Matting agents
    • 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
    • G03C1/76—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
    • 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
    • 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

Definitions

  • This invention relates to photosensitive film materials and image-forming systems wherein said materials are forming an image by wet or dry processing after exposure to radiation.
  • Image forming systems wherein photosensitive silver halide film materials are processed after exposure are well-known. Processing of the said materials can be performed wet or dry, depending on the system used.
  • radiology e.g. where classical screen-film systems still remain important
  • phosphors present in an intensifying screen convert X-ray radiation into visible light.
  • the photons of visible light emitted from said phosphors are then absorbed by an adjacent radiographic film material containing light-sensitive silver halide emulsion crystals, whereafter the latent image becomes wet processed in order to give an image ready-for-examination by radiologists.
  • suitable screen-film systems usually contain only one screen.
  • Light-sensitive silver halide photographic layer(s) coated at only one side of a film support are used in this application, wherein the outermost layer of said film should be in close contact with the said screen in favour of sharpness.
  • the screen-film system contains two screens. Between the said screens the film is positioned and comprises on each side of the support at least one light-sensitive silver halide photographic layer.
  • tabular silver halide emulsion crystals are frequently used nowadays.
  • Tabular grains are disclosed e.g. in US-A 4,414,304 for their high covering power (even at high hardening levels of the binder material, thus permitting the coating of lower amounts of silver halide) and developability, and in US-A's 4,425,425 and 4,425,426 for their lower cross-over. All these effects are the result of a higher surface to volume ratio characteristic for said tabular grains.
  • EP-A 0 468 211 and in EP-A 0 655 645 Therein a blue coloured pigment is added to the photographic sensitive layer or another layer of the film in order to reduce residual dye stain but simultaneously to provide a black image tone.
  • the blue pigment used in these EP-A's is characterised by an absorption maximum of from 570 to 630 nm and from 640 to 700 nm respectively.
  • this pigment is added to the light-sensitive emulsion layer containing silver halide emulsion crystals and reduces dye stain after processing by deaggregation of the adsorbed spectral sensitiser, adsorbed at the crystal surface. Distinct images, although not relied with tabular grains and/or image tone, have ever been an object as much earlier, as described in JP-B 47-030205, metalo-phthalocyanine dyes were already incorporated in the film base polymer.
  • a problem arising due to the presence of a blue pigment (besides image tone and dye stain) in a photographic element in operative association with an intensifying screen is the risk of staining of the surface of said screen so that artefacts can occur on the image formed after contact made with such stained screen. This phenomenon especially occurs after cleaning the screen surface with solvents used as screen-cleaners. Further blue pigment escaping from the film material often makes dirty the rollers in the automatic processing machine wherein the exposed film material is processed, thereby disturbing images generated on the following films processed therein.
  • a photosensitive silver halide film material comprising a support and on one or both sides thereof one or more layer(s) comprising a photosensitive silver halide emulsion, particularly a photosensitive silver halide emulsion having tabular silver halide crystals with an average thickness of less than 0.25 •m and an average aspect ratio of 2 or more; characterised in that said photosensitive layer(s) comprise(s) blue coloured polymeric matting particles, wherein said blue coloured polymeric matting particles have a maximum absorption in the visible wavelength region from 570 to 700 nm.
  • said light-sensitive film material which is run in wet processing after exposure is used in an image-forming film-screen system for medical diagnostic imaging wherein said film material is used in operative association with one or two intensifying screens comprising on a support a layer of a visible light emitting luminescent phosphor the said film material comprising a support and on one or both sides thereof a light-sensitive silver halide emulsion layer having spectrally sensitised tabular silver halide and a non-light-sensitive protective layer, characterised in that said light-sensitive silver halide emulsion layer(s) comprise(s) blue coloured polymeric matting particles.
  • blue coloured polymeric matting particles are added in dispersed form to one or more emulsion layer(s) of image-forming materials it remains important that the minimum density is lowered without impairing the desired cold blue-black image tone: addition of lower amounts of blue pigment to the blue coloured support makes base-density decrease and as a function of amounts of blue pigmented polymer matting particles added in dispersed form to one or more emulsion layer(s) of the said material the total minimum density is set at the desired level in order to get a "fresh look" when examining practical images.
  • the support is coloured by means of a blue dye, wherein said blue dye is present in such an amount that the minimum density after processing is not more than 0.25.
  • Preferred blue coloured dyes present in dispersed coloured polymeric matting particles are those having the most suitable absorption spectrum, in the visible range of the wavelength spectrum from 570 to 700 nm, more preferred in the range from 570 to 630 nm. Especially those dyes selected from the group consisting of phthalocyanine dyes and indanthron dyes are preferred. It is further clear that a mixture of blue coloured pigments can be used, the proviso that at least one of these pigments has a maximum absorption in the visible range of the wavelength spectrum from 570 to 700 nm, and more preferred in the range from 570 to 630 nm.
  • the blue pigment(s) present in the support of materials according to this invention have an absorption spectrum that matches the absorption spectrum of the blue dye(s) or pigment(s) present in dispersed blue coloured polymeric matting particles.
  • blue dyes present in the pigmented support and in the emulsion layer(s) coated thereupon as a dispersion of blue coloured polymeric matting particles are the same.
  • said blue pigment(s) or dye(s) present in dispersed polymeric matting particles are coated in one or more light-sensitive emulsion layer(s) in an amount of from 10 mg/m 2 to 1000 mg/m 2 , and more preferably in an amount of from 10 mg/m 2 up to 500 mg/m 2 .
  • Said blue pigments present as blue coloured or blue pigmented polymeric matting particles are preferably present as blue coloured polymethylmethacrylate polymeric matting particles and are preferably prepared starting from colourless polymeric matting particles which are themselves prepared according to the methods described e.g. in US-A's 3,754,924; 4,022,622 and 4,820,615 and in EP-A 0 726 490, wherein polymerisation methods performed by e.g. pearl polymerisation and/or solvent polymerisation have been described.
  • US-A 4,952,484 the preparation of a colored polymer matting agent by incorporating or adsorbing dyes in the inside or on the surface of fine particles of a polymer has been given.
  • said coloured polymer matting agents are coated in the uppermost layer at the emulsion side or at the back side of the support opposite the layer having the silver halide emulsion in order to inhibit the occurrence of black spots in the field of graphic arts materials or more in general in high contrast image-forming systems.
  • Preferred mean particle sizes of the dispersed blue colored polymeric matting particles for use in the materials according to the present invention are preferably from 1 ⁇ m to 10 ⁇ m, more preferably from 1 ⁇ m up to 6 ⁇ m and even more preferably from 1 ⁇ m up to 3 ⁇ m, although smaller particle sizes as e.g. 0.2 ⁇ m are not excluded.
  • light-sensitive spectrally sensitised tabular silver halide grains are used in at least one emulsion layer, wherein said tabular grains have an aspect ratio of from 2 to 20, a thickness from 0.06 to less than 0.25 ⁇ m, more preferably from 0.06 to 0.20 ⁇ m and wherein said grains account for at least 50 %, more preferably for at least 70 % and even more preferably for at least 90 % of the total projective area of all grains.
  • aspect ratios of said tabular grains are from 5 to 20 and still more preferred aspect ratios are from 8 to 20.
  • preferred variation coefficients are less than 0.30, more preferred less than 0.20 and still even more preferred from 0.10 to 0.15.
  • Such low variation coefficient can be attained by application of preparation methods for such tabular grains as has been described e.g. in US-A's 5,147,772; 5,147,773; 5,171,659; 5,210,013 and 5,215,879.
  • Silver halide compositions of said tabular grains are silver bromide, silver bromochloride, silver bromochloroiodide, silver bromoiodide, silver chloride, silver chlorobromide, silver chloroiodide or silver chlorobromoiodide, wherein firstly named halides are present in higher amounts than halides named later.
  • Halide ions may be divided homogeneously or heterogeneously over the grain volume, depending on the preparation method used. Preparation methods for tabular grain emulsions have been described e.g.
  • Coated amounts of silver in the silver halide emulsion layer(s) of the film material according to this invention are in the range from 1 to 6 g/m 2 , and more preferably, from 3 to 5 g/m 2 and per side, expressed as an equivalent amount of silver nitrate.
  • said light-sensitive tabular silver halide grains are spectrally sensitised to the blue, to the green, to the red and even to the infrared region of the wavelength spectrum.
  • the screens comprise blue or green light emitting phosphors blue sensitised or green sensitised emulsion crystals are used.
  • recording materials as e.g. laser recording materials or photothermographic materials red sensitisers and even infrared sensitisers may be used in order to spectrally sensitise tabular emulsion crystals.
  • Development acceleration in order to enhance speed in the same processing cycle or in order to maintain speed in a shorter developing time can be accomplished by incorporating in the emulsion layer or adjacent layers various compounds, preferably polyoxyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US-A's 3,038,805; 4,038,075 and 4,292,400 or development accelerators described in EP-A's 0 634 688 and 0 674 215.
  • the protective antistress layer and, if present, an afterlayer, may contain a polymeric compound in an amount of at least 0.2 g per m 2 and more preferably at least 0.4 g/m 2 .
  • Said protective antistress layer may be composed of two different layers, wherein the layer more close to the support may act as an intermediate layer. Said two different layers may have the same composition, except for e.g. the presence of one or more additional blue dye(s) in dispersed form as described in EP-Application No. 96200417, filed February 19, 1996.
  • the said polymeric compound can be a compound selected from the group consisting of gelatin, a synthetic, semi-synthetic or natural substitute for gelatin, and latex (co)polymers.
  • the presence of (additional) amounts of (natural or synthetic) clay and/or colloidal silica is further highly appreciated in favour of physical surface characteristics as such as glare, slidability, etc.
  • Gelatin is well-known as an essential polymeric compound of hydrophilic colloid layers in photographic materials.
  • 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 polymerisable monomers on gelatin, and cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates.
  • Gelatin can be lime-treated or acid-treated gelatin.
  • the preparation of such gelatin types has been described in e.g. "The Science and Technology of Gelatin", edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 and next pages.
  • the gelatin can also be an enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan, N° 16, page 30 (1966).
  • latex (co)polymers used in the film material according to this invention have been described in e.g. Research Disclosure 19551, July 1980, and further in EP-A's 0 452 568; 0 534 006; 0 558 196 and 0 643 326; in US-A's 3,443,946; 3,589,908; 3,640,721; 4,476,218 and 4,810,624 and in JP-A 06250315.
  • Especially preferred latex polymers are e.g. latex containing polyacrylic acid as described in JP-A 05134336 and in EP-A 0 644 456.
  • Clays used in layers of photographic material are disclosed e.g. in EP-A 0 644 454, wherein i.a. particular synthetic clays have been described, which are very suitable to reach good surface characteristics when used in outermost layers.
  • colloidal silica as disclosed in e.g. EP-A 0 670 517 is added to the coating solution(s) of the protective antistress layer and/or to an afterlayer, if present.
  • gelatin-grafted polymer particles as disclosed e.g. in US-A's 5,393,650 and 5,426,020 or matte polymeric particles covalently bound to gelatin and colloidal silica as disclosed in US-A 5,300,411 are added to the coating solution(s) of the protective antistress layer and/or to an afterlayer, if present.
  • Said polymeric matting particles may be covered by a layer of colloidal inorganic particles as described in e.g. in US-A's 5,288,598 and 5,378,577.
  • Organic polymer particles as described in e.g. US-A's 4,914,012 and 5,342,733 may also be added as well as matting agents described in e.g. JP-A 04162032.
  • Lubricants may further be added as described e.g. in US-A 4,766,059 and in JP-A 05107687.
  • UV absorbing dyes, optical brighteners and luminescent dyes can be used as described in RD 36544, chapter VI.
  • Antifoggants and stabilisers can be used as described in the same RD, chapter VII.
  • useful absorbing dyes used as antihalation dyes are summarised. Further useful filter dyes have been described e.g. in EP-A's 0 656 401 and 0 724 191 and EP-Application No. 93001438, filed December 22, 1993.
  • Coating physical property modifying addenda like coating aids, plasticisers, lubricants, antistats and matting agents useful in the preparation of the coating solutions of the light-sensitive and non-light sensitive film layers are further described in RD 36544, chapter IX.
  • the gelatin binder of the radiographic film materials used in the system according to the present invention 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 or di-(vinylsulphonyl)-methane, ethylene di-(vinyl-sulphone), vinylsulphonyl-ether compounds and vinylsulphonyl compounds having soluble groups, aldehydes like e.g. formaldehyde, glyoxal, and glutaric aldehyde, N-methylol compounds e.g.
  • appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol or di-(vinylsulphony
  • 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.
  • 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.
  • 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.
  • functional groups are especially amino groups, but also carboxylic groups, hydroxy groups, and active methylene groups.
  • a water absorption per gram of gelatin is not more than 3 g per gram of gelatin and even more preferred a water absorption of not more than 2 g per gram of gelatin.
  • Said amount of water absorption is determined after incubating a sample of said film material at 57 °C and 34% RH for 3 days, weighing said sample, immersing it in distilled water at 21°C for 3 minutes, squeezing it in order to get a surface free from water drops and weighing it again. Calculation of the differences in weight, divided by the surface area of the film strip and by the amount of gelatin coated per square metre gives the required value.
  • Another more suitable way to express the requirement to sufficiently harden the binder in the film material used in the screen-film system of this invention is to express it as atempoual swelling degree: the saidtempoual swelling degree, should not exceed a value of 300 %, and more preferably should not exceed a value of 200 %. Therefore after incubating a sample of a material at 57 °C and 34% RH for 3 days 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 (%).
  • Layers and layer arrangements which can be applied to the film material according to this invention are those described in EP-A's 0 752 617, 0 712 036, 0 712 034, 0 677 773 and 0 678 772, in EP-A's 0 610 608; 0 610 609 and in EP-A 0 569 075, in US-A's 4,092,168 and 4,311,787; in DE 2,453,217 and in GB Patent 7,907,440.
  • Supports and subbing layers coated adjacent thereto, useful for the film materials according to this invention can be those as described in RD 36544, chapter XV, polyethylene naphthalate inclusive.
  • a useful subbing layer is disclosed e.g. in JP-A 01166031.
  • Vinylidene chloride and styrenebutadiene copolymers are the most well-known polymers for practical use as subbing layer ingredient in the film material of the screen-film system of this invention.
  • most of the said supports are already blue-coloured by incorporating blue dyes, preferably by incorporating the same blue dyes as in the emulsion layer(s) of materials used in this invention.
  • Antistatic agents can be provided therein as described e.g. in US-A 5,391,472 and in EP-A's 0 534 006, 0 644 454 and 0 644 456.
  • radiographic materials are present in an image-forming system wherein said material is a film for medical diagnostic imaging used in operative association with one or two intensifying screens comprising on a support thereof a layer of a light emitting luminescent phosphor.
  • Light emitting should be understood herein as ultraviolet, blue or green light emitting.
  • a preferred screen in the screen-film system is an intensifying screen comprising a green light-emitting luminescent phosphor, and more preferred a Gd 2 O 2 S:Tb luminescent phosphor or a M or M' Y(Sr,Li)TaO 4 blue emitting phosphor, whether or not mixed together with barium fluorobromide phosphors, doped with europium.
  • a screen or a combination of screens can be used as has been described e.g. in EP-A's 0 592 724, 0 510 754, 0 647 258 and 0 648 254.
  • symmetrical or asymmetrical film arrangement refers to film materials wherein sensitivity, gradation and/or spectral sensitivity is equal or not at opposite sides of the film support.
  • symmetrical or asymmetrical pair of screens refers to screens wherein speed and/or spectral sensitivity is equal or is differing for both screens.
  • the photographic material containing chemically and spectrally sensitised tabular grains used in the system according to the present invention is image-wise exposed to visible light, preferably green light, generated from converted X-rays emitted by an X-ray source emitting X-rays with an energy adapted to the specific application. Conversion of X-rays proceeds by the preferred green light-emitting phosphors making part of the screens of the image-forming film-screen system according to this invention.
  • single-side coated films having thin tabular grains for laser applications wherein said tabular grains are spectrally sensitised with dyes having a maximum absorption in the wavelength region of the correspondingly used laser exposure source, even exceeding the wavelength region of the visible spectrum as by infrared radiation.
  • Said films are used in graphical and in medical diagnostic image-forming applications.
  • a transparent photothermographic recording material having a support bearing a photo-adressable thermosensitive element comprising photosensitive silver halide grains, a reducing agent for silver ions and a binder, wherein silver halide grains are tabular silver halide grains having silver halide, and more preferably silver chloride, in an amount of 50 mole % or more, more preferably in an amount of 70 mole % or more, and an average grain thickness of 0.20 ⁇ m or less and wherein said tabular grains account for at least 50 % of the total projective surface area of all silver halide grains, an emulsion layer wherein said silver halide grains are present preferably comprise(s) blue coloured polymeric matting particles, according to the present invention.
  • Said photo-addressable thermally developable materials apart from blue coloured polymeric matting particles in favour of image tone after heat-processing, comprise a substantially light-insensitive organic silver salt, photosensitive silver halide in catalytic association therewith and an organic reducing agent in thermal working relationship with the substantially light-insensitive organic silver salt and a binder.
  • the element may comprise a layer system with the silver halide in catalytic association with the substantially light-insensitive organic silver salt ingredients, spectral sensitiser optionally together with a supersensitiser in intimate sensitising association with the silver halide particles and the other ingredients active in the thermal development process or pre- or post-development stabilisation of the element being in the same layer or in other layers with the proviso that the organic reducing agent and the toning agent, if present, are in thermal working relationship with the substantially light-insensitive organic silver salt i.e. during the thermal development process the reducing agent and the toning agent, if present, are able to diffuse to the substantially light-insensitive organic silver salt.
  • spectral sensitiser optionally together with a supersensitiser in intimate sensitising association with the silver halide particles and the other ingredients active in the thermal development process or pre- or post-development stabilisation of the element being in the same layer or in other layers with the proviso that the organic reducing agent and the toning agent,
  • EP-Application No. 96203269 filed November 21, 1996.
  • Spectral sensitisation in order to absorb infrared radiation not always requires a supersensitiser as has been illustrated in the EP-Application No. 96202100, filed July 24, 1996.
  • a production method for a photothermographic recording material and a recording process therefor may be applied as disclosed in unpublished EP-Application No. 96200648, filed March 9, 1996, when blue coloured polymer matting particles are included in the photosensitive layer of the said material according to the present invention.
  • thermography In order to conventionally obtain a neutral black image tone in the higher densities and neutral grey in the lower densities of photo-addressable thermally developable element, preferably in admixture with organic heavy metal salts and reducing agents, a so-called toning agent known from thermography or photothermography is used. Suitable toning agents are succinimide and the phthalimides and phthalazinones within the scope of the general formulae described in US-P 4,082,901. Further reference is made to the toning agents described in US-A's 3,074,809, 3,446,648 and 3,844,797.
  • heterocyclic toner compounds of the benzoxazine dione or naphthoxazine dione type and toners described in GB-P 1,439,478 and US-A 3,951,660 are particularly useful toning agents.
  • a toner compound particularly suited for use in combination with polyhydroxy benzene reducing agents is 3,4-dihydro-2,4-dioxo-1,3,2H-benzoxazine described in US-A 3,951,660.
  • Further addition to the support of blue dyes is in favour of colour correction of image tone in the direc-tion of a cold "blue-black" fresh look.
  • a mean particle size for the blue pigmented polymeric matting particles of 3 ⁇ m was obtained after loading cross-linked polymeric particles in the following way.
  • MACROLEXBLAU RR diol A 1 g was dissolved in 20 ml of ethyl acetate. The solution was dispersed in 5 minutes in 50 ml of demineralised water, stirring at 12000 rpm. 5 ml of a 10 % aqueous solution of the sodium salt of n-dodecyl-benzene sulphonic acid was added as a surface active agent.
  • the dispersion of the dye obtained as described hereinbefore was added to 45 g of a 16.5 wt% aqueous dispersion of polymer matting particles having a polymethylmethacrylate composition and an average particle size of 3 ⁇ m. After stirring for 1 hour ethyl acetate was removed by evaporation under reduced pressure. The homodisperse polymeric methylmethacrylate matting particles were loaded with the blue dye A and were free from conglomerates.
  • the matting particles loaded with the blue dye were dispersed in a gelatinous solution (10 wt %) in order to obtain a dispersion of 10 wt % of blue dye A coloured matting particles.
  • the blue dye content of the matting agent was 8 % by weight.
  • a blue dyed polyethylene terephthalate film support of 175 ⁇ m thickness was used.
  • the X-ray screen (format 24 cm x 30 cm) was made slightly wet with Agfa-Gevaert Curix "screen-cleaner".
  • Screen-cleaner mainly consists of isopropanol.
  • the X-ray screen used in this dye stain test was CURIX ORTHO REGULAR 1FFJ5P (trademarketed screen by Agfa-Gevaert NV).
  • Material No. 1 was obtained by coating support 1 as described above with the coating solution of the protective layer, coated at a wet thickness of 25 ⁇ m and at a gelatin content per m 2 and per side of the support of 1.1 g.
  • Material No. 2 was coated just as Material No. 1, except for the use of support 2 instead of support 1 and dispersion of the blue coloured polymeric matting agent was added to the coating solution of the silver halide emulsion layer in an amount corresponding with 120 mg of matting agent per m 2 and per side after coating.
  • Material No. 3 was coated just as Material No. 2, except for the presence of an amount of blue coloured polymeric matting agent of 73 mg/m 2 and per side.
  • Material No. 4 was coated just as Material No. 1, except for the use of support 2 instead of support 1 and the addition of the dispersion of the blue coloured polymeric matting agent to the solution of the protective layer in an amount corresponding with 73 mg/m 2 and per side of matting agent after coating.
  • Material No. 5 was coated just as Material No. 1, except for the use of support 2 instead of support 1 and addition of the milled dye dispersion of blue coloured dye (thus without the presence of polymeric matting particles) to the coating solution of the silver halide emulsion layer in an amount of 10.5 mg/m 2 and per side of the blue dye after coating.
  • Material No. 6 was coated just as Material No. 5, except for the presence of the dispersion of the blue dye in the coating solution of the protectiver layer.

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

Claims (9)

  1. Ein strahlungsempfindliches Silberhalogenid-Filmmaterial mit einem Träger und an einer oder beiden Trägerseiten einer oder mehreren Schichten, die eine strahlungsempfindliche Silberhalogenidemulsion mit tafelförmigen Silberhalogenidkristallen mit einer mittleren Teilchengröße von weniger als 0,25 µm und einem mittleren Aspektverhältnis von zumindest 2 enthält (enthalten), dadurch gekennzeichnet, daß die strahlungsempfindliche(n) Silberhalogenid-Emulsionsschicht(en) blaugefärbte polymere Mattierteilchen enthält (enthalten), wobei die blaugefärbten polymeren Mattierteilchen eine Höchstabsorption im Wellenlängenbereich von sichtbarem Licht zwischen 570 und 700 nm aufweisen.
  2. Material nach Anspruch 1, dadurch gekennzeichnet, daß die tafelförmigen Silberhalogenidkristalle ein Aspektverhältnis von 2 bis 20 und eine Stärke zwischen 0,06 µm und weniger als 0,25 µm aufweisen und zumindest 50% der totalen projizierten Oberfläche aller Körner Tafelkörner sind.
  3. Material nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die blaugefärbten polymeren Mattierteilchen blaugefärbte polymere Methylmethacrylatteilchen sind.
  4. Material nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die blaugefärbten polymeren Mattierteilchen ein Pigment oder einen Farbstoff aus der Gruppe bestehend aus Phthalocyaninfarbstoffen und Indanthronfarbstoffen enthalten.
  5. Material nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die blaugefärbten polymeren Mattierteilchen eine Höchstabsorption im Spektralbereich des sichtbaren Lichts zwischen 570 und 630 nm aufweisen.
  6. Material nach irgendeinem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die blaugefärbten polymeren Mattierteilchen in einer Menge, die einer Menge Blaufarbstoff zwischen 10 mg/m2 und 1.000 mg/m2 entspricht, in der (den) Emulsionsschicht(en) enthalten sind.
  7. Material nach irgendeinem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die blaugefärbten polymeren Mattierteilchen eine mittlere Teilchengröße zwischen 1 µm und 10 µm aufweisen.
  8. Material nach irgendeinem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das Silberhalogenid Silberchlorid, Silberchloridbromid, Silberchloridiodid, Silberchloridbromidiodid, Silberbromid, Silberbromidchlorid, Silberbromidchloridiodid oder Silberbromidiodid ist.
  9. Bilderzeugendes System, in dem das nach irgendeinem der Ansprüche 1 bis 8 definierte Material in wirksamer Beziehung zu einem oder mehreren Verstärkerschirmen, der (die) auf einem Träger eine Schicht aus einem lichtemittierenden selbstleuchtenden Leuchtstoff enthält (enthalten), für die Erzeugung von medizinischen Diagnostikbildern benutzt wird.
EP19970203598 1996-11-21 1997-11-18 Film-Materialien mit farbigen Mattierungsteilchen Expired - Lifetime EP0844520B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19970203598 EP0844520B1 (de) 1996-11-21 1997-11-18 Film-Materialien mit farbigen Mattierungsteilchen

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP96203262 1996-11-21
EP96203262 1996-11-21
EP19970203598 EP0844520B1 (de) 1996-11-21 1997-11-18 Film-Materialien mit farbigen Mattierungsteilchen

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EP0844520A1 EP0844520A1 (de) 1998-05-27
EP0844520B1 true EP0844520B1 (de) 2001-10-04

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7129031B2 (en) 2003-06-19 2006-10-31 Agfa-Gevaert Radiographic silver halide photographic material having a good developing speed, an excellent image tone and low residual color after processing

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01210946A (ja) * 1988-02-18 1989-08-24 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
IT1246185B (it) * 1990-07-20 1994-11-16 Minnesota Mining & Mfg Materiale fotografico agli alogenuri d'argento con ridotta colorazioneresidua da colorante sensibilizzatore.
US5244994A (en) * 1992-03-20 1993-09-14 Eastman Kodak Company Bleachable polymeric filter dyes
US5441865A (en) * 1993-01-07 1995-08-15 Eastman Kodak Company Gelatin-grafted-polymer particles as peptizer for silver halide emulsions
DE69327875D1 (de) * 1993-11-29 2000-03-23 Imation Corp Photographisches Silberhalogenidmaterial mit vermindertem Schleier und verringerter Fleckenbildung

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